CN115324671A - High-temperature carbon capture and in-situ conversion utilization system and method for fuel gas-steam combined cycle power generation coupled with electrolyzed water - Google Patents
High-temperature carbon capture and in-situ conversion utilization system and method for fuel gas-steam combined cycle power generation coupled with electrolyzed water Download PDFInfo
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- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 106
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 100
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- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims 1
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
- F01K—STEAM ENGINE PLANTS; STEAM ACCUMULATORS; ENGINE PLANTS NOT OTHERWISE PROVIDED FOR; ENGINES USING SPECIAL WORKING FLUIDS OR CYCLES
- F01K11/00—Plants characterised by the engines being structurally combined with boilers or condensers
- F01K11/02—Plants characterised by the engines being structurally combined with boilers or condensers the engines being turbines
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
- F01D—NON-POSITIVE DISPLACEMENT MACHINES OR ENGINES, e.g. STEAM TURBINES
- F01D15/00—Adaptations of machines or engines for special use; Combinations of engines with devices driven thereby
- F01D15/10—Adaptations for driving, or combinations with, electric generators
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
- F01K—STEAM ENGINE PLANTS; STEAM ACCUMULATORS; ENGINE PLANTS NOT OTHERWISE PROVIDED FOR; ENGINES USING SPECIAL WORKING FLUIDS OR CYCLES
- F01K23/00—Plants characterised by more than one engine delivering power external to the plant, the engines being driven by different fluids
- F01K23/12—Plants characterised by more than one engine delivering power external to the plant, the engines being driven by different fluids the engines being mechanically coupled
- F01K23/14—Plants characterised by more than one engine delivering power external to the plant, the engines being driven by different fluids the engines being mechanically coupled including at least one combustion engine
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
- F01K—STEAM ENGINE PLANTS; STEAM ACCUMULATORS; ENGINE PLANTS NOT OTHERWISE PROVIDED FOR; ENGINES USING SPECIAL WORKING FLUIDS OR CYCLES
- F01K25/00—Plants or engines characterised by use of special working fluids, not otherwise provided for; Plants operating in closed cycles and not otherwise provided for
- F01K25/08—Plants or engines characterised by use of special working fluids, not otherwise provided for; Plants operating in closed cycles and not otherwise provided for using special vapours
- F01K25/14—Plants or engines characterised by use of special working fluids, not otherwise provided for; Plants operating in closed cycles and not otherwise provided for using special vapours using industrial or other waste gases
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F02—COMBUSTION ENGINES; HOT-GAS OR COMBUSTION-PRODUCT ENGINE PLANTS
- F02C—GAS-TURBINE PLANTS; AIR INTAKES FOR JET-PROPULSION PLANTS; CONTROLLING FUEL SUPPLY IN AIR-BREATHING JET-PROPULSION PLANTS
- F02C3/00—Gas-turbine plants characterised by the use of combustion products as the working fluid
- F02C3/20—Gas-turbine plants characterised by the use of combustion products as the working fluid using a special fuel, oxidant, or dilution fluid to generate the combustion products
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F02—COMBUSTION ENGINES; HOT-GAS OR COMBUSTION-PRODUCT ENGINE PLANTS
- F02C—GAS-TURBINE PLANTS; AIR INTAKES FOR JET-PROPULSION PLANTS; CONTROLLING FUEL SUPPLY IN AIR-BREATHING JET-PROPULSION PLANTS
- F02C6/00—Plural gas-turbine plants; Combinations of gas-turbine plants with other apparatus; Adaptations of gas-turbine plants for special use
- F02C6/18—Plural gas-turbine plants; Combinations of gas-turbine plants with other apparatus; Adaptations of gas-turbine plants for special use using the waste heat of gas-turbine plants outside the plants themselves, e.g. gas-turbine power heat plants
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/10—Process efficiency
- Y02P20/129—Energy recovery, e.g. by cogeneration, H2recovery or pressure recovery turbines
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- Engineering & Computer Science (AREA)
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Abstract
The invention provides a high-temperature carbon capture and in-situ conversion utilization system and method for coupling fuel gas-steam combined cycle power generation with electrolyzed water. The carbon capture and in-situ conversion subsystem carries out carbon capture on high-temperature carbon-containing flue gas exhausted by a gas turbine generator set of the combined cycle generator set subsystem and carries out in-situ conversion to obtain a target chemical product, and the high-temperature decarbonized flue gas and the product gas respectively return to a waste heat boiler to push a steam turbine generator set to generate electricity; hydrogen required by the carbon conversion process is provided by an electrolytic water system; the electric energy of the water electrolysis subsystem is carried out by utilizing valley electricity or green electricity of a power plant, and oxygen generated by water electrolysis provides oxygen-enriched combustion atmosphere for the gas turbine generator set. The invention couples the high-temperature carbon capture and in-situ conversion system of the electrolyzed water with the gas-steam combined cycle generator set to carry out process coupling and energy integration, and realizes the subversive carbon-negative technology on the premise of hopefully maintaining the existing power generation energy efficiency of a power plant through full-process energy coupling and optimization.
Description
Technical Field
The invention belongs to the technical field of carbon dioxide capture and conversion utilization, relates to high-temperature carbon dioxide capture and in-situ conversion utilization, and particularly relates to a system and a method for capturing and in-situ conversion utilization of fuel gas-steam combined cycle power generation coupling electrolyzed water.
Background
Electric power is the largest carbon emission source in the energy industry, and accounts for nearly 40% of the carbon emission related to global energy. In view of the structural characteristics of energy in China, fossil fuel thermal power generation is still the main body in the power industry. Therefore, the carbon capture, utilization and sequestration (CCUS) technology will become one of the important means for promoting low-carbon utilization of fossil energy in the power industry. The gas-steam combined cycle technology in thermal power generation greatly improves energy utilization and power generation efficiency through gradient utilization of energy, and is considered to be a clean and efficient comprehensive utilization technology of fossil fuels in the future. The technology takes a gas turbine, a waste heat boiler and a steam turbine as main equipment, the gas turbine is ignited and heated to push the gas turbine to rotate, high-temperature flue gas (550-610 ℃) enters the waste heat boiler through a gas turbine diffusion section, high-temperature high-pressure steam is generated after water is fed to the boiler by heating to push the steam turbine, the heat efficiency is further improved, and the flue gas (about 90 ℃) of the waste heat boiler after heat exchange is discharged into the atmosphere. The process is due to large flue gas treatment capacity and carbon dioxide (CO) 2 ) Partial pressure is low<5 vol%), so that the energy consumption and the trapping cost of the separation process are greatly increased.
Existing large-scale CO for thermal power generation 2 The trapping technology mainly adopts a solvent absorption method, and the high-temperature flue gas needs to be cooled to low temperature<50 ℃) can be absorbed, and has larger heat loss, and high cost and high regeneration energy consumption of the solvent, so that the fire coal is burntThe additional energy consumption of the power plant is increased (the power supply efficiency is reduced by 10-15%). Second captured CO 2 And CO associated therewith 2 The problems of high cost caused by compression, transportation and the like also restrict the large-scale adoption of CCUS (carbon neutralization) in a thermal power plant to realize carbon neutralization.
CO is introduced into 2 High-value utilization is a mode for realizing artificial carbon circulation, and meanwhile, part of trapping cost can be offset, so that certain economic benefit is generated. But due to CO 2 Is extremely stable in thermodynamics, needs to provide a large amount of hydrogen source and input extra energy (high-temperature condition) to be converted into high value-added chemicals (such as methane, synthesis gas and the like), so that large-scale CO can be obtained 2 Resource utilization also faces the problems of high cost and large energy consumption. Because the temperatures of the traditional low-temperature carbon capture and high-temperature carbon conversion processes are often not matched, how to couple the carbon capture process and the carbon conversion process into a key problem of the CCUS.
Based on the heat energy of high-temperature flue gas discharged by a gas turbine of the combined cycle generator set, the valley electricity of a power plant and the large-scale electrolyzed water of renewable power to provide high-purity green hydrogen, the research on a low-cost and low-energy-consumption high-temperature carbon capture and in-situ conversion technology for coupling the electrolyzed water and the integration technology of the gas-steam combined cycle generator set is of great significance. The research and development of the technology can eliminate CO from the source 2 The artificial carbon circulation is realized by utilizing the heat energy of the flue gas, the high energy consumption required by CCUS is reduced, and CO is introduced 2 The product is converted into a product with an additional value, and the bottleneck problem of low-carbon development of the power industry is solved.
Disclosure of Invention
The invention aims at a gas-steam combined cycle power generation system, high-temperature flue gas (550-650 ℃) discharged by a gas turbine is introduced into a waste heat boiler to drive the steam turbine to generate power, and finally CO in carbon-containing flue gas (90-110 ℃) is discharged 2 The problem of low concentration and difficult treatment is solved, and a system and a method for high-temperature carbon capture and in-situ conversion utilization of coupled electrolyzed water are provided, so that a new mode of low-carbon power generation of a power plant is established from a production source.
Carrying out carbon capture on high-temperature flue gas discharged by a gas turbine, and simultaneously carrying out in-situ conversion on captured carbon as a resource to obtain a target chemical product so as to form an artificial chemical carbon cycle; or providing raw materials for the chemical industry to perform inter-industry synergistic carbon neutralization. The hydrogen required by the carbon conversion process is provided by an electrolytic water system, the valley electricity or green electricity of the power plant is used as a power supply in the electrolytic process, the peak regulation capacity of the power plant is improved, and oxygen generated by the electrolytic water can provide oxygen-enriched combustion atmosphere for the gas turbine. Therefore, the high-temperature carbon capture and in-situ conversion system coupled with the electrolyzed water and the gas-steam combined cycle generator set are subjected to process coupling and energy integration, and the subversive carbon-negative technology is hopefully realized on the premise of keeping the existing power generation energy efficiency of the power plant through full-process energy coupling and optimization.
The invention provides a high-temperature carbon capture and in-situ conversion utilization system for fuel gas-steam combined cycle power generation coupled electrolyzed water, which has the following technical characteristics: the system comprises a combined cycle generator set subsystem, a carbon capture and in-situ conversion subsystem and an electrolytic water subsystem.
The combined cycle generator set subsystem comprises a gas turbine generator set and a steam turbine generator set: the gas turbine power generation set comprises a compressor, a combustion chamber, a gas turbine generator and a heat exchanger; the steam turbine power generation unit comprises a waste heat boiler, a steam turbine generator, a condenser, a gas conveying unit and a circulating pump.
In the gas turbine power generation set, a compressor, a combustion chamber and a gas turbine are sequentially connected to form a Brayton cycle unit, so as to drive a gas turbine generator to generate power; the waste heat boiler, the steam turbine, the condenser and the circulating pump are sequentially connected in a circulating mode to form a Rankine cycle unit, and the Rankine cycle unit drives the turbine generator to generate power.
The carbon capture and in-situ conversion subsystem is embedded between the Brayton cycle unit and the Rankine cycle unit, namely between the gas turbine outlet of the gas turbine power generation unit and the waste heat boiler inlet of the steam turbine power generation unit, and comprises an air inlet control unit, an adsorption and conversion reaction tower, a detection control system, a water-vapor separator and a gas conveying unit.
The air inlet control unit comprises a flue gas, hydrogen and nitrogen inlet program control device; the adsorption and conversion reaction towers are at least two arranged in parallel and comprise a reactor and an internal heat exchange unit, wherein the reactor is a fixed bed, a fluidized bed or a moving bed and is internally provided with a heat exchange unitIs provided with an adsorption/catalysis dual-function material, and realizes CO through switching between high-temperature flue gas and hydrogen 2 The trapping and in-situ conversion are continuously operated; the detection control system comprises various sensors, instruments, controllers and the like, monitors various parameters in real time, and controls the reaction process to be in a normal range; the water-steam separator comprises a condenser, and the water-steam separator condenses steam into water; the gas delivery unit comprises a pipeline and various valves arranged on the pipeline.
The electrolytic water subsystem comprises a water electrolytic cell, an oxygen storage tank and a hydrogen storage tank which are respectively connected with the anode and the cathode of the electrolytic cell; the oxygen storage tank is connected with the compressor through a valve, and the hydrogen storage tank is connected with the adsorption and conversion reaction tower through a valve.
In a second aspect of the present invention, a method for high temperature carbon capture and in-situ conversion and utilization by using the above system is provided, which is characterized by comprising the following steps:
(1) CO in the high-temperature carbon-containing flue gas generated by the gas turbine of the combined cycle generator set subsystem in a carbon capture and in-situ conversion subsystem 2 Adsorbed by the adsorption/catalysis dual-function material, and is converted into a target chemical product by in-situ catalytic hydrogenation under the participation of hydrogen generated by the electrolytic water subsystem;
(2) Respectively carrying out heat exchange on the high-temperature decarbonized flue gas and the high-temperature product gas generated in the step (1) in a waste heat boiler to push a steam turbine generator to generate electricity; directly exhausting the low-temperature decarbonized flue gas after heat exchange, storing a low-temperature target chemical product as a chemical production raw material or as fuel for gas power generation, and providing a water source for an electrolytic water subsystem by using condensed water;
(3) The combined cycle generator set subsystem provides electric energy for the electrolyzed water subsystem, and oxygen generated by electrolysis provides an oxygen-enriched environment for fuel combustion in a combustion chamber of the combined cycle generator set subsystem.
Preferably, the step (1) specifically comprises the following steps:
according to the reaction temperature required in the carbon capture and in-situ conversion process, the high-temperature carbon-containing flue gas is subjected to heat exchange and temperature reduction by a heat exchanger or directly enters an adsorption and conversion reaction tower, and CO 2 Is absorbed and trapped by the absorption/catalysis double-function material,and controlling the reaction temperature in the trapping process; after the current reaction tower is saturated in adsorption, the current reaction tower is switched to other parallel reaction towers for carbon capture, and after nitrogen purging is carried out on the current reaction tower, preheated hydrogen is introduced to adsorb CO 2 Carrying out in-situ catalytic conversion to obtain a target chemical product, and sequentially carrying out adsorption, blowing and in-situ hydrogenation conversion by reaction towers arranged in parallel.
The carbon trapping and in-situ conversion system adopts an adsorption/catalysis bifunctional material, wherein an adsorption active component is an alkali metal oxide, and a catalysis active component is a bimetallic catalyst.
The high temperature carbon capture technology is based primarily on the reaction of cycles of carbonation and decarbonation occurring between alkali metal oxides, alkaline earth metal oxides and their carbonates, as in equations 1-4. The main alkali metals are calcium adsorbent and magnesium adsorbent.
CaO+CO 2 ＝CaCO 3 , ΔH 298K ＝-178kJ/mol (1)
MgO+CO 2 ＝MgCO 3 , ΔH 298K ＝-101kJ/mol (2)
Na 2 O+CO 2 ＝Na 2 CO3 ΔH 298K ＝-322kJ/mol (3)
K 2 O+CO 2 ＝K 2 CO 3 ΔH 298K ＝-348kJ/mol (4)
The manner of controlling the reaction temperature during the trapping process was as follows: for exothermic reaction, heat is required to be led out through a heat exchange unit in the adsorption and conversion reaction tower; for the endothermic reaction, high temperature flue gas at 900-1100 ℃ generated after the fuel gas passes through the combustion heater is introduced into a jacket of the adsorption and conversion reaction tower to supplement heat for the carbon conversion reaction.
In situ CO 2 The catalytic hydrogenation reduction is mainly based on the reactions of reverse water gas Reaction (RWGS), methanation reaction, methanol preparation by hydrogenation, olefin preparation by hydrogenation and the like (as shown in an equation 5-7).
CO 2 +H 2 ＝CO+H 2 O, ΔH 298K ＝+41kJ/mol (5)
CO 2 +4H 2 ＝CH 4 +2H 2 O ΔH 298K ＝-63kJ/mol (6)
CO 2 +H 2 ＝CH 3 OH+H 2 O ΔH 298K ＝-49.5kJ/mol (7)
nCO 2 +(3n+1)H 2 ＝C n H 2n+1 +2nH 2 O ΔH 298K ＝-128kJ/mol (8)
In situ CO 2 The main catalyst for catalytic hydrogenation reduction is a noble metal catalyst such as nickel-series bimetal, iron-series bimetal, copper-series bimetal, platinum, ruthenium, rhodium, zirconium and the like.
In situ CO 2 The target products of catalytic hydroconversion can be, but are not limited to, methane, syngas, lower alcohols, olefins, light fuels, and the like.
Preferably, the step (2) comprises the steps of:
high-temperature decarbonized flue gas and high-temperature product gas generated in the adsorption and conversion reaction tower are respectively introduced into a waste heat boiler for heat exchange to transfer heat to steam, so that a steam turbine power generation unit is pushed to generate power; the low-temperature decarbonized flue gas is directly emptied, and the low-temperature product gas enters a storage tank after being dehydrated by a water-gas separator, wherein the low-temperature product gas can be used as fuel product gas for gas power generation and is introduced into a combustion chamber for combustion utilization, so that artificial carbon cycle is formed, and other products are used for high added value utilization of chemical engineering; and water generated by the steam separator of the water-gas separator is introduced into the electrolytic cell through the circulating pump for electrolysis.
The step (3) comprises the following steps:
inputting the redundant valley electricity or green electricity after peak shaving of the combined cycle power generation subsystem into an electrolytic cell for water electrolysis to generate oxygen and hydrogen which are respectively conveyed into an oxygen storage tank and a hydrogen storage tank through pipelines; oxygen in the oxygen storage tank is mixed with air, compressed by the compressor and then introduced into the combustion chamber together with fuel for oxygen-enriched combustion, so as to drive the gas turbine generator to generate electricity.
The invention has the following beneficial guarantee and effects:
1. the carbon capture and in-situ conversion utilization system of the fuel gas-steam combined cycle power generation coupling electrolyzed water integrates the original independent combined cycle power generation system, the carbon capture process, the carbon conversion utilization system and the electrolyzed water system into an organic whole on the basis of the combined cycle power generation unit, realizes the high-efficiency utilization of energy and the cyclic utilization of raw materials, and realizes the low-energy-consumption high-temperature flue gas CO on the premise of keeping the existing power generation energy efficiency of a power plant 2 Trapping and high-value utilization.
2. Compared with the traditional carbon capture process of a thermal power plant, the method provided by the invention fully utilizes the high-temperature flue gas heat discharged by a gas turbine unit in combined cycle power generation and the reaction heat in the adsorption process, and directly captures the CO 2 In-situ conversion, high-efficiency utilization of energy and avoidance of normal-temperature CO 2 The contradiction that the high-temperature flue gas needs to be cooled and the temperature needs to be raised in the reaction conversion process is collected, so that the energy consumption is greatly reduced, and the energy utilization of the high-temperature flue gas is realized.
3. The method provided by the invention realizes the trapped CO 2 The in-situ hydrogenation conversion of added-value products is realized, the same reactor is used for carbon capture and conversion processes, the processes of gas compression, pipeline transportation and the like are avoided, the flow is relatively simple, the equipment investment is reduced, and meanwhile, the generated chemical products can directly enter a gas turbine unit to serve as fuel or downstream chemical production raw materials, so that a certain economic value is generated, the artificial carbon circulation is realized, and the use of fossil fuel is reduced.
4. The invention provides electric energy for hydrogen production by electrolyzing water by utilizing valley electricity or green electricity generated by combined cycle power generation, thereby enhancing the peak regulation capability of a power plant. Electrolysis of water to CO 2 The in-situ conversion provides a hydrogen source, and the generated oxygen replaces part of air introduced by the gas turbine, so that the oxygen content in the gas turbine set is improved, and the combustion efficiency of the gas turbine is favorably improved. Meanwhile, water generated in the in-situ conversion hydrogenation process can be returned to the electrolytic water subsystem as a raw material, so that the water can be recycled.
Drawings
FIG. 1 is a block diagram of the carbon capture and in-situ conversion technology of the fuel gas-steam combined cycle power generation coupled electrolysis water of the present invention.
FIG. 2 is a schematic diagram of a process flow of a high-temperature carbon capture and in-situ methane conversion system for water electrolysis coupled with gas-steam combined cycle power generation.
Wherein, the combustion chamber F-1; a waste heat boiler F-2; an air compressor C-1; a gas turbine M-1; a steam turbine M-2; an electrolytic cell M-3; heat exchangers E-1 and E-3; condensers E-2, E-4; circulating pumps P-1 and P-2; a methane storage tank S-1; a hydrogen storage tank S-2; an oxygen storage tank S-3; adsorption and conversion reaction towers T-1 and T-2; two-way valves V-1-2 and V-9-12; three-way valves V-3 to V-7; and a four-way valve V-8.
FIG. 3 is a schematic process flow diagram of a system for high-temperature carbon capture and in-situ conversion of synthesis gas by coupling gas-steam combined cycle power generation with electrolysis of water.
Wherein, the combustion chamber F-1; a waste heat boiler F-2; a fired heater F-3; an air compressor C-1; a gas turbine M-1; a steam turbine M-2; an electrolytic cell M-3; heat exchangers E-1 and E-3, condensers E-2 and E-4; circulating pumps P-1 and P-2; a synthesis gas storage tank S-1; a hydrogen storage tank S-2; an oxygen storage tank S-3; adsorption and conversion reaction towers T-1 and T-2; two-way valves V-1, V-3, V-7, V-11 and V-13-15; three-way valves V-2, V-4, V-5-6, V-8-9 and V-12; and a four-way valve V-10.
Detailed Description
The invention will be further illustrated with reference to the following specific examples. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention.
According to fig. 1, a coupled electrolyzed water high temperature carbon capture and in situ conversion system 100 based on a gas-steam combined cycle power generation unit comprises: a combined cycle generator set subsystem 1, a carbon capture and in-situ transformation subsystem 2 and an electrolyzed water subsystem 3.
With reference to fig. 1 and 3, the combined cycle generator set subsystem 1 includes a gas turbine generator set and a turbine generator set: the gas turbine power generation set comprises a compressor, a combustion chamber, a gas turbine generator and a heat exchanger; the steam turbine power generation unit comprises a waste heat boiler, a steam turbine generator, a condenser, a gas conveying unit and a circulating pump.
Fuel and oxygen enter a gas turbine to be compressed and combusted for power generation, generated high-temperature flue gas is output at the gas turbine, after high-temperature adsorption and conversion are carried out through a carbon capture and in-situ conversion system 2, the obtained high-temperature flue gas and product gas respectively enter a waste heat boiler to heat water vapor, a turbonator is pushed to generate power, low-temperature decarbonized flue gas after heat exchange is directly exhausted, light fuel such as methane and the like in the low-temperature product gas is combusted in a combustion chamber in a gas power generation set, and synthetic gas, low-carbon alcohol, olefin and the like enter a gas storage tank for chemical application. After oxygen generated by the electrolyzed water subsystem 3 enters the air compressor, an oxygen-enriched environment is provided to improve the efficiency of the gas turbine.
The carbon capture and in-situ conversion subsystem 2 comprises a gas inlet control unit, an adsorption and conversion reaction tower, a detection control system, a water-vapor separator and a gas conveying unit.
The air inlet control unit comprises a flue gas, hydrogen and nitrogen inlet program control device; the adsorption and conversion reaction towers are at least two arranged in parallel and comprise reactors and internal heat exchange units, the reactors are fixed beds, fluidized beds or moving beds, adsorption/catalysis dual-function materials are arranged in the reactors, and CO is realized by switching high-temperature flue gas and hydrogen 2 The trapping and in-situ conversion are continuously operated; the detection control system comprises various sensors, instruments, controllers and the like, monitors various parameters in real time, and controls the reaction process to be within a normal range; the water-steam separator comprises a condenser, and the water-steam separator condenses steam into water; the gas delivery unit comprises a pipeline and various valves arranged on the pipeline.
High-temperature flue gas output from a gas turbine of the combined cycle generator set subsystem 1, hydrogen output from a hydrogen storage tank of the electrolyzed water subsystem 3 and nitrogen output from a nitrogen storage tank respectively enter an air inlet control unit, are subjected to heat exchange by a preheater and enter an adsorption and conversion reaction tower by a program; and respectively outputting the obtained high-temperature decarbonized flue gas and high-temperature product gas from the adsorption and conversion reaction tower, and entering a waste heat boiler of the combined cycle generator set subsystem 1 for heat exchange.
The electrolytic water subsystem 3 comprises a water electrolysis cell, and an oxygen storage tank and a hydrogen storage tank which are respectively connected with the anode and the cathode of the electrolysis cell; the oxygen storage tank is connected with the compressor through a valve, and the hydrogen storage tank is connected with the adsorption and conversion reaction tower through a valve.
The redundant electric energy after peak regulation of the combined cycle power generation subsystem 1 provides electric energy for the electrolytic cell. Oxygen generated by the anode is output from the oxygen tank to the gas turbine air compressor of the combined cycle power generation unit subsystem 1 to provide an oxygen-enriched environment for fuel combustion. Hydrogen generated by the cathode is output from the hydrogen tank to the carbon capture and in-situ conversion subsystem 2 air inlet system, and captured CO is output 2 And in-situ hydrogenation is carried out to convert the product into a target product. The water generated in the conversion process is condensed by a water-vapor separator and enters an electrolytic cell for electrolyzing water.
In situ CO 2 The catalytic hydrogenation reduction is mainly based on the reaction of reverse water gas Reaction (RWGS), methanation reaction, methanol preparation by hydrogenation, olefin preparation by hydrogenation and the like. The specific process of integrating the high-temperature carbon capture coupled with electrolyzed water and the in-situ converted methane and gas-steam combined cycle power generation will be described in detail below by taking methanation reaction and reverse water gas Reaction (RWGS) reaction as examples. The two reactions also belong to exothermic reactions and endothermic reactions, respectively, and the temperature control mode in the reaction process is also displayed at the same time.
Example 1 integration of high temperature carbon capture and in situ conversion of methane with gas-steam combined cycle power generation based on methanation coupled with electrolysis of water
See fig. 2. In the embodiment, the high-temperature carbon capture and in-situ methane conversion subsystem and the electrolytic water subsystem are coupled and then integrated with the fuel gas-steam combined cycle power generation subsystem. Firstly, redundant electric energy after peak shaving of the combined cycle power generation subsystem is input into an electrolytic cell M-3 for water electrolysis, and oxygen and hydrogen generated are respectively conveyed into an oxygen storage tank S-3 and a hydrogen storage tank S-2 through pipelines. And (3) opening the two-way valve V-12, mixing oxygen in the oxygen storage tank S-3 with air, compressing the mixture by the air compressor C-1, introducing the mixture and fuel (methane) into the combustion chamber F-1 to generate high-temperature and high-pressure flue gas, pushing the gas turbine M-1 to do work, driving the gas turbine generator to generate power, and discharging the high-temperature carbon-containing flue gas at about 600 ℃.
Then the two-way valve V-11 is opened, the high-temperature carbon-containing flue gas exchanges heat through the heat exchanger E-3, the temperature is reduced to 400 ℃, and then the high-temperature carbon-containing flue gas enters carbonA capture and conversion subsystem. The adsorption and conversion reaction towers T-1 and T-2 are filled with a magnesium-based adsorption/nickel-based bimetallic catalysis dual-function material. Opening a three-way valve V-7, entering an adsorption and conversion reaction tower T-1 for carbon capture, wherein the chemical reaction process generated in the adsorption process is as shown in a reaction equation 2, heat is discharged in time in the adsorption process through a heat exchange unit in the reaction tower due to heat release in the adsorption process, the temperature of the adsorption and conversion reaction tower is controlled to be 350-450 ℃, and the temperature of the decarbonized flue gas is increased to 500 ℃. And opening the three-way valve V-7 to introduce the high-temperature flue gas into the adsorption and conversion reaction tower T-2 for carbon capture after the adsorption and conversion reaction tower T-1 is saturated in adsorption. Meanwhile, a two-way valve V-9 is opened, and nitrogen is introduced into the adsorption and conversion reaction tower T-1 by controlling a four-way valve V-8 to purge for 5 minutes. Then the four-way valve V-8 is switched to hydrogen, the hydrogen in the storage tank S-2 is preheated by a heat exchanger E-3 and then is introduced into an adsorption and conversion reaction tower T-1, and the adsorbed CO is removed 2 Catalytic conversion to methane with regeneration of the adsorbent, CO generated in this process 2 The methanation reaction is an exothermic reaction, and needs to lead out heat through a heat exchange unit in the adsorption and conversion reaction tower, and the temperature of the reactor is controlled to be 350-450 ℃, as shown in a reaction equation 6. After the conversion reaction is completed, it is ready to proceed to the next carbon capture stage. The two adsorption and conversion reaction towers T-1 and T-2 run in parallel, the carbon capture and carbon utilization processes are switched by controlling the three-way valve V-7 and the four-way valve V-8, and nitrogen purging is realized during the switching from the carbon capture to the carbon conversion process by controlling the four-way valve V-8. Because the reactions in the adsorption and reaction tower are exothermic reactions, extra heat does not need to be supplemented in the processes of carbon capture and in-situ conversion systems, the high-temperature flue gas heat is used for preheating the hydrogen, and the exothermic reaction heat is fully utilized.
High-temperature decarbonized flue gas (500 ℃) and high-temperature product methane (450 ℃) generated in the two adsorption and conversion reaction towers T-1 and T-2 can pass through a three-way valve V-3-V-6 to be regulated and controlled, heat is transferred to the waste heat boiler F-2 through the heat exchanger E-1, steam generated by the waste heat boiler F-2 enters the steam turbine M-2 to do work to drive the steam turbine generator to generate electricity, so that the combined cycle power generation energy efficiency is improved, and then the steam enters the condenser E-2 to be changed into water and enters the waste heat boiler F-2 again through the circulating pump P-1 to be recycled. After passing through the heat exchanger E-1, low-temperature decarbonized flue gas (at 90 ℃) can be directly evacuated through the two-way valve V-2, low-temperature methane (at 90 ℃) can be purified by separating water through the condenser E-4 and then enters the methane storage tank S-1, and the methane can be used as fuel gas and is introduced into the combustion chamber F-1 through the two-way valve V-1 for combustion utilization, so that an artificial carbon cycle is formed. The water generated by the condenser E-4 is introduced into the electrolytic cell M-3 for electrolysis through the two-way valve V-10 and the circulating pump P-2, so that the self-sufficiency of the raw materials and the energy is realized.
Electrolyzing water by utilizing redundant valley electricity or green electricity of a power plant, and taking hydrogen obtained by a cathode as captured CO 2 Preparing a raw material of a chemical product by in-situ hydrogenation; meanwhile, oxygen generated by the anode can replace air of the original combined cycle power generation system, so that an oxygen-rich environment of fuel is provided, the power generation efficiency of the gas turbine is improved, and the peak regulation capacity of a power plant is enhanced.
Example 2 high temperature carbon capture of coupled electrolyzed water based on reverse water gas Reaction (RWGS) and integration of in situ reformed syngas with gas-steam combined cycle power generation
See fig. 3. In this embodiment, the high-temperature carbon capture and in-situ conversion syngas subsystem is coupled with the electrolytic water subsystem and then integrated with the gas-steam combined cycle power generation subsystem. Firstly, redundant electric energy after peak regulation of a combined cycle power generation subsystem is utilized to provide electrolytic water energy of an electrolytic cell M-3, oxygen and hydrogen are generated and stored in a hydrogen storage tank S-2 and an oxygen storage tank S-3 respectively. And opening the two-way valve V-15, mixing oxygen in the oxygen storage tank S-3 with air, compressing the mixture by the air compressor C-1, introducing the compressed mixture and fuel (methane) into the combustion chamber F-1 to generate high-temperature and high-pressure flue gas, pushing the gas turbine M-1 to do work to drive the gas turbine generator to generate power, and generating high-temperature carbon-containing flue gas at the temperature of about 600 ℃. And then the high-temperature carbon-containing flue gas enters a carbon capture and conversion subsystem through a two-way valve V-7.
The absorption and conversion reaction towers T-1 and T-2 are filled with calcium absorption/iron bimetal catalytic dual-function materials. The high-temperature carbon-containing flue gas enters an adsorption and conversion reaction tower T-1 through a three-way valve V-9 to carry out a carbon capture process, the adsorption process is carried out as a reaction equation 1, and heat is released in the adsorption process, so that adsorption and conversion are carried out in the adsorption processThe heat exchange unit in the chemical reaction tower discharges heat in time, the temperature of the adsorption and conversion reaction tower is controlled to be 600-650 ℃, and the high-temperature flue gas after decarburization is about 700 ℃. When the adsorption and conversion reaction tower T-1 is saturated, the three-way valve V-9 is controlled to introduce the high-temperature flue gas into the adsorption and conversion reaction tower T-2 to carry out a new carbon capture process. Meanwhile, the two-way valve V-11 is opened, and nitrogen is introduced into the adsorption and conversion reaction tower T-1 by controlling the four-way valve V-10 to purge for 5 minutes. Then the four-way valve V-10 is switched to hydrogen, the hydrogen in the storage tank S-2 is preheated by a heat exchanger E-3 and then is introduced into an adsorption and conversion reaction tower T-1, and the adsorbed CO is treated 2 The catalyst is converted into CO, and the CO and excessive hydrogen are added to form synthesis gas, and meanwhile, the calcium adsorbent is regenerated. The chemical reaction generated in the process is shown as a reaction equation 5, because the reaction is an endothermic reaction, a two-way valve V-13 needs to be opened, fuel gas (methane) generates high-temperature flue gas with the temperature of about 900-1100 ℃ after passing through a combustion heater F-3, the high-temperature flue gas is introduced into a jacket of an adsorption and conversion reaction tower T-1 through a three-way valve V-12 to supplement heat for the carbon conversion reaction, the temperature of the reaction tower is controlled to be 600-650 ℃, the temperature of the high-temperature flue gas after heat supplement is maintained at 700 ℃, the high-temperature flue gas after heat supplement passes through a three-way valve V-8, hydrogen is preheated through a heat exchanger E-3, the hydrogen is heated to 600 ℃, and the high-temperature flue gas after heat exchange is merged into high-temperature carbon-containing flue gas generated by a gas turbine through the two-way valve V-3 and enters a carbon trapping and utilizing subsystem. The reaction column after completion of the conversion reaction is ready to enter the next carbon capture stage. The two adsorption and conversion reaction towers T-1 and T-2 run in parallel, carbon capture, purging and conversion process switching are carried out by controlling a three-way valve V-9 and a four-way valve V-10, and the adsorption and conversion reaction tower T-1 or T-2 in the carbon utilization stage is supplemented with heat by using high-temperature flue gas generated by methane gas in a combustion heater F-3 by controlling the three-way valve V-12.
High-temperature decarbonized flue gas (700 ℃) and high-temperature product synthesis gas (600 ℃) generated in two adsorption and conversion reaction towers T-1 and T-2 can be subjected to heat transfer to a waste heat boiler F-2 through regulating three-way valves V-2 and V-4-6 by a heat exchanger E-1, steam generated by the waste heat boiler F-2 enters a steam turbine M-2 to do work to drive a steam turbine generator to generate power, so that the combined cycle power generation energy efficiency is improved, then the steam enters a condenser E-2 to be changed into water, and the water is introduced into the waste heat boiler F-2 again through a circulating pump P-1 to be recycled. After passing through the heat exchanger E-1, low-temperature decarbonized flue gas (90 ℃) can be directly evacuated through the two-way valve V-1, and low-temperature synthesis gas (90 ℃) can be introduced into the condenser E-4 for separation and purification and then enters the synthesis gas storage tank S-1, so that the subsequent chemical high-added-value conversion and utilization are realized. And water generated by the condenser E-4 is introduced into the electrolytic cell M-3 through the two-way valve V-10 and the circulating pump P-2 for electrolytic recycling.
Electrolyzing water by utilizing redundant valley electricity or green electricity of a power plant, and taking hydrogen obtained by a cathode as captured CO 2 Preparing a raw material of a chemical product by in-situ hydrogenation; meanwhile, oxygen generated by the anode can replace air of the original combined cycle power generation system, so that an oxygen-enriched environment of fuel is provided, and the power generation efficiency of the gas turbine is improved. Meanwhile, the peak regulation capacity of the power plant is enhanced.
Those not described in detail in this specification are well within the skill of the art.
The present invention is not limited to the embodiments described above, and those skilled in the art can make various equivalent modifications or substitutions without departing from the spirit of the present invention, and these equivalent modifications or substitutions are included in the scope defined by the claims of the present application.
Claims (9)
1. A high-temperature carbon capture and in-situ conversion utilization system for coupling gas-steam combined cycle power generation with electrolysis water is characterized by comprising: a combined cycle generator set subsystem, a carbon capture and in-situ conversion subsystem and an electrolytic water subsystem,
the carbon capture and in-situ conversion subsystem carries out carbon capture on high-temperature carbon-containing flue gas exhausted by a gas turbine generator set of the combined cycle generator set subsystem and carries out in-situ conversion to obtain a target chemical product, and the high-temperature decarbonized flue gas and the product gas respectively return to a waste heat boiler to push a steam turbine generator set to generate electricity; hydrogen required by the carbon conversion process is provided by an electrolytic water system; the electric energy of the water electrolysis subsystem is provided by valley electricity or green electricity of a power plant, and oxygen generated by water electrolysis provides oxygen-enriched combustion atmosphere for the gas turbine.
2. The system for high-temperature carbon capture and in-situ conversion utilization of coupled electrolyzed water by gas-steam combined cycle power generation as claimed in claim 1, wherein the combined cycle power generation unit subsystem comprises a gas turbine power generation unit and a steam turbine power generation unit,
the gas turbine power generation set comprises a compressor, a combustion chamber, a gas turbine generator and a heat exchanger; the steam turbine power generation unit comprises a waste heat boiler, a steam turbine generator, a condenser, a gas conveying unit and a circulating pump,
in the gas turbine power generation set, a compressor, a combustion chamber and a gas turbine are sequentially connected to form a Brayton cycle unit, and a gas turbine generator is driven to generate electricity; the waste heat boiler, the steam turbine, the condenser and the circulating pump are sequentially connected in a circulating mode to form a Rankine cycle unit, and the Rankine cycle unit drives the turbine generator to generate power.
3. The system for high-temperature carbon capture and in-situ conversion utilization of coupled electrolyzed water generated by gas-steam combined cycle power generation as claimed in claim 2, wherein:
wherein the carbon capture and in-situ conversion subsystem is embedded between the gas turbine outlet of the gas turbine power generation unit and the waste heat boiler inlet of the steam turbine power generation unit and comprises an air inlet control unit, an adsorption and conversion reaction tower, a detection control system, a water-vapor separator and a gas conveying unit,
the electrolytic water subsystem comprises a water electrolysis cell, an oxygen storage tank and a hydrogen storage tank which are respectively connected with the anode and the cathode of the water electrolysis cell; the oxygen storage tank is connected with the compressor through a valve, and the hydrogen storage tank is connected with the adsorption and conversion reaction tower through a valve.
4. The gas-steam combined cycle power generation coupled electrolyzed water high-temperature carbon capture and in-situ conversion utilization system of claim 3, characterized in that:
the air inlet control unit comprises an air inlet program control device for high-temperature carbon-containing flue gas, hydrogen and nitrogen;
the adsorption and conversion reaction towers are at least two arranged in parallel and comprise reactors and internal heat exchange units, and adsorption/catalysis bifunctional materials are arranged in the reactors.
5. The gas-steam combined cycle power generation coupled electrolyzed water high-temperature carbon capture and in-situ conversion utilization system of claim 4, characterized in that:
wherein the reactor is a fixed bed, a fluidized bed or a moving bed.
6. A method for high temperature carbon capture and in situ conversion utilization using the system of any one of claims 1 to 4, comprising the steps of:
(1) In a carbon capture and in-situ conversion subsystem, carbon dioxide is absorbed by an absorption/catalysis dual-function material in high-temperature carbon-containing flue gas generated by a gas turbine of the combined cycle generator set subsystem, and is converted into a target chemical product by in-situ catalytic hydrogenation under the participation of hydrogen generated by an electrolytic water subsystem;
(2) Respectively carrying out heat exchange on the high-temperature decarbonized flue gas and the high-temperature product gas generated in the step (1) in a waste heat boiler to push a steam turbine generator to generate electricity; directly exhausting the low-temperature decarbonized flue gas after heat exchange, storing a low-temperature target chemical product as a chemical production raw material or as fuel for gas power generation, and providing a water source for an electrolytic water subsystem by using condensed water;
(3) The combined cycle generator set subsystem provides electric energy for the electrolyzed water subsystem, and oxygen generated by electrolysis provides an oxygen-enriched environment for fuel combustion in a combustion chamber of the combined cycle generator set subsystem.
7. The method of claim 6, wherein:
wherein, the step (1) comprises the following steps:
according to the reaction temperature required in the carbon capture and in-situ conversion process, the high-temperature carbon-containing flue gas is subjected to heat exchange and temperature reduction or directly enters an adsorption and conversion reaction tower, and the carbon dioxide in the flue gas is subjected to dual functions of adsorption and catalysisAdsorbing and trapping the material, and controlling the reaction temperature in the trapping process; after the current reaction tower is saturated in adsorption, the current reaction tower is switched to other parallel reaction towers for carbon capture, and after nitrogen purging is carried out on the current reaction tower, preheated hydrogen is introduced to adsorb CO 2 Carrying out in-situ catalytic conversion to obtain a target chemical product, and sequentially carrying out adsorption, blowing and in-situ hydrogenation conversion on other reaction towers which are arranged in parallel;
the step (2) comprises the following steps:
high-temperature decarbonized flue gas and high-temperature product gas generated in the adsorption and conversion reaction tower are respectively introduced into a waste heat boiler for heat exchange to transfer heat to steam, so that a steam turbine generator unit is pushed to generate electricity; the low-temperature decarbonized flue gas is directly evacuated, and the low-temperature product gas enters a storage tank after being dehydrated by a water-gas separator, wherein the low-temperature product gas can be used as fuel product gas for gas power generation and is introduced into a combustion chamber for combustion utilization, so that artificial carbon cycle is formed, and other products are used for high added value utilization in chemical engineering; water generated by the water-gas separator is introduced into the electrolytic cell through the circulating pump for electrolysis;
the step (3) comprises the following steps:
inputting the redundant valley electricity or green electricity after peak shaving of the combined cycle power generation subsystem into an electrolytic cell for water electrolysis to generate oxygen and hydrogen which are respectively conveyed into an oxygen storage tank and a hydrogen storage tank through pipelines; oxygen in the oxygen storage tank is mixed with air, compressed by the compressor and then introduced into the combustion chamber of the gas turbine generator set together with fuel for oxygen-enriched combustion, so as to push the gas turbine generator to generate electricity.
8. The method of claim 7, wherein:
in the step (1), in the adsorption/catalysis dual-function material, the adsorption active component is alkali metal oxide or alkaline earth metal oxide, and the catalysis active component is a bimetallic catalyst, including nickel bimetallic, iron bimetallic, copper bimetallic, platinum, ruthenium, rhodium or zirconium noble metal catalyst;
the reaction temperature was controlled during the trapping process in the following manner: for exothermic reaction, heat is required to be led out through a heat exchange unit in the adsorption and conversion reaction tower; for the endothermic reaction, high-temperature flue gas at 900-1100 ℃ generated after fuel gas passes through a combustion heater is introduced into a jacket of an adsorption and conversion reaction tower to supplement heat for the carbon conversion reaction;
in situ CO 2 The catalytic conversion is mainly based on the reactions of reverse water gas reaction, methanation reaction, methanol preparation by hydrogenation or olefin preparation by hydrogenation;
the target chemical product is methane, synthesis gas, low-carbon alcohol, olefin or light fuel.
9. The method of claim 7, wherein:
wherein, in the step (1), when the adsorption active component is calcium oxide, the high-temperature carbon-containing flue gas directly enters the adsorption and conversion reaction tower; when the adsorption active component is magnesium oxide, the high-temperature carbon-containing flue gas enters the adsorption and conversion reaction tower after heat exchange and temperature reduction.
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