CN112939023A - System and method for storing energy and denitrating ammonia produced by thermal power plant - Google Patents
System and method for storing energy and denitrating ammonia produced by thermal power plant Download PDFInfo
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- CN112939023A CN112939023A CN202110354102.3A CN202110354102A CN112939023A CN 112939023 A CN112939023 A CN 112939023A CN 202110354102 A CN202110354102 A CN 202110354102A CN 112939023 A CN112939023 A CN 112939023A
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01C—AMMONIA; CYANOGEN; COMPOUNDS THEREOF
- C01C1/00—Ammonia; Compounds thereof
- C01C1/02—Preparation, purification or separation of ammonia
- C01C1/04—Preparation of ammonia by synthesis in the gas phase
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F23—COMBUSTION APPARATUS; COMBUSTION PROCESSES
- F23J—REMOVAL OR TREATMENT OF COMBUSTION PRODUCTS OR COMBUSTION RESIDUES; FLUES
- F23J15/00—Arrangements of devices for treating smoke or fumes
- F23J15/003—Arrangements of devices for treating smoke or fumes for supplying chemicals to fumes, e.g. using injection devices
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F23—COMBUSTION APPARATUS; COMBUSTION PROCESSES
- F23J—REMOVAL OR TREATMENT OF COMBUSTION PRODUCTS OR COMBUSTION RESIDUES; FLUES
- F23J2215/00—Preventing emissions
- F23J2215/10—Nitrogen; Compounds thereof
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F23—COMBUSTION APPARATUS; COMBUSTION PROCESSES
- F23J—REMOVAL OR TREATMENT OF COMBUSTION PRODUCTS OR COMBUSTION RESIDUES; FLUES
- F23J2215/00—Preventing emissions
- F23J2215/10—Nitrogen; Compounds thereof
- F23J2215/101—Nitrous oxide (N2O)
Abstract
The invention relates to a flue gas denitration technology of a thermal power plant, in particular to a system and a method for storing energy and denitration during ammonia preparation of the thermal power plant. The system comprises an electrochemical ammonia production device connected and arranged on a boiler; the electrochemical ammonia production device comprises a power supply assembly, a reaction tank and an ammonia storage tank; the output end of the power supply assembly is connected with a power supply of the reaction tank; the outlet of the reaction tank is connected with the inlet of the ammonia storage tank through an ammonia pipeline; the outlet of the ammonia storage tank is respectively communicated with the combustion area in the boiler and the flue at the tail part of the boiler through pipelines; the reaction tank is provided with an electrode cathode and an electrode anode, and electrolyte is filled in the reaction tank; and nitrogen is introduced into the cathode of the electrode, and hydrogen is introduced into the anode of the electrode. The invention has reasonable design, simple system and small occupied area, can safely operate under normal pressure, has no influence on the arrangement and the operation safety of the existing equipment of the thermal power plant, and can improve the operation economy of the unit.
Description
Technical Field
The invention relates to a flue gas denitration technology of a thermal power plant, in particular to a system and a method for storing energy and denitration during ammonia preparation of the thermal power plant.
Background
Ammonia (NH)3) Is an important chemical raw material, and about 1.8 hundred million tons of NH are generated every year3Is produced and transported. The industrial synthesis of ammonia is carried out by the conventional Haber-Bosch process, using N2And H2The method is carried out under the action of high temperature, high pressure and catalyst, and has the advantages of complex process flow, low hydrogen equilibrium conversion rate and high energy consumption. In recent years, the electrochemical ammonia preparation method draws wide attention in the research field of synthetic ammonia, and under the promotion of electric energy, the thermodynamics can not spontaneously synthesize ammonia, the reaction is not limited by or less thermal mechanical equilibrium, and the leap of the synthetic ammonia from 'high pressure' to 'normal pressure' is realized. The development of the electrochemical ammonia preparation method is expected to get rid of the dependence of Haber-Bosch synthesis of ammonia on coal or natural gas fossil energy as raw materials, and realize the clean, low-temperature and normal-pressure synthesis of ammonia.
Ammonia is both a reductant and a carbon-free fuel. The energy density of ammonia is 22.5MJ/kg, which is comparable to fossil fuels. Reacting NH3Direct combustion can reduce cracking to H2Energy loss in the process, but NH3Direct combustion with low flame speed and NOxThe challenge of high emissions. Related research reports the application of ammonia fuel in gas turbines, power station boilers, industrial boilers and the like, namely, NH3The emission behavior of the downstream flame injection from the pulverized coal burner into the furnace hardly changed, showing NH3The possibility of fuel co-combustion with coal in a boiler. For convenience of transportation and storage, gaseous ammonia is usually pressurized or cooled to obtain liquid ammonia. Liquid ammonia is widely used in industry, and SCR systems of thermal power plants generally adopt liquid ammonia to prepare denitration reducing agents. Liquid ammonia is corrosive and easy to volatilize, belongs to a great hazard source, and has greater safety risk in transportation and storage. In order to reduce the safety risk of denitration of heat-engine plant by using liquid ammonia, some new ammonia production technologies are applied to the heat-engine plant, such as urea hydrolysis ammonia production technology, urea pyrolysis ammonia production technology, urea direct injection ammonia production technology, ammonia water ammonia production technology and the like, but the methods still depend on input of external raw materials, the transportation and storage risks of dangerous raw materials cannot be thoroughly eliminated, the ammonia production cost is high, and the influence on the transportation and storage risks of dangerous raw materials is causedThe operating economy of the denitration device is improved.
Disclosure of Invention
Aiming at the problems in the prior art, the invention provides a system and a method for storing energy and denitrating ammonia in a thermal power plant, which have the advantages of reasonable design, simple structure, safety, reliability, economy and feasibility.
The invention is realized by the following technical scheme:
a system for storing energy and denitrating ammonia generated in a thermal power plant comprises an electrochemical ammonia generating device connected and arranged on a boiler;
the electrochemical ammonia production device comprises a power supply assembly, a reaction tank and an ammonia storage tank; the output end of the power supply assembly is connected with a power supply of the reaction tank; the outlet of the reaction tank is connected with the inlet of the ammonia storage tank through an ammonia pipeline; the outlet of the ammonia storage tank is respectively communicated with the combustion area in the boiler and the flue at the tail part of the boiler through pipelines;
the reaction tank is provided with an electrode cathode and an electrode anode, and electrolyte is filled in the reaction tank; and nitrogen is introduced into the cathode of the electrode, and hydrogen is introduced into the anode of the electrode.
Furthermore, an ammonia nozzle is arranged on a pipeline which is communicated with the boiler outlet flue of the ammonia storage tank; the ammonia nozzles are uniformly arranged in a flue at the inlet of the SCR reactor, and the injection direction is consistent with the flowing direction of flue gas.
Furthermore, the power supply assembly comprises a reheater/reheater, a steam turbine and a generator which are connected in sequence; the pass/reheater is arranged in the horizontal flue of the boiler, and the outlet of the pass/reheater is connected with the steam turbine through a steam pipeline; the output end of the generator is connected with the power supply of the reaction tank.
Furthermore, the electrolyte in the reaction tank adopts mixed molten salt.
Furthermore, a first control valve and a second control valve are respectively arranged on pipelines communicated with the outlet of the ammonia storage tank, the combustion area in the boiler and the flue at the tail of the boiler.
A method for storing energy and denitrating ammonia produced in a thermal power plant comprises the following steps,
step 1, filling electrolyte into a reaction tank, introducing nitrogen into an electrode cathode, introducing hydrogen into an electrode anode, providing reaction energy by a power supply assembly, carrying out chemical reaction on the nitrogen and the hydrogen at normal pressure to generate ammonia, and sending the ammonia into an ammonia storage tank through an ammonia pipeline for storage;
further, in the step 2, controlling the flow of ammonia gas entering the boiler through a first control valve according to the load of the unit, and opening the first control valve to send the ammonia gas into the boiler to be combusted with the pulverized coal when the boiler is operated in a peak shaving mode; when the boiler operates in a stable load mode, closing the first control valve;
and controlling the flow of the ammonia gas entering the tail flue of the boiler through a second control valve.
Further, in the step 1, water vapor in the boiler is extracted by a pass/reheater in the power supply assembly and is sent to a steam turbine through a water vapor pipeline, so that the steam turbine is pushed to rotate and drives a generator to generate electricity; when the boiler operates with stable load, the heat required for heating the water vapor is provided by burning the pulverized coal.
Furthermore, in the step 1, the power supply assembly provides reaction energy, when the boiler is in peak shaving operation, surplus electricity is sent into a power supply, the ammonia production amount of the electrochemical ammonia production device is increased, and the generated ammonia is stored in the ammonia storage tank and is used as energy storage fuel; during the steady load operation of the boiler, the current density of the power supply is determined by the ammonia production rate required for denitration.
Compared with the prior art, the invention has the following beneficial technical effects:
according to the system, the electrochemical ammonia production device is arranged in the boiler of the thermal power plant, the peak-load-adjusting electric quantity of the thermal power plant is utilized to electrochemically produce ammonia, and the ammonia is used for unit energy storage and SCR reactor denitration, namely reaction energy is provided through the power supply assembly, ammonia gas is prepared in situ in the reaction tank and stored in the ammonia storage tank, one part of the ammonia gas is introduced into a combustion area in the boiler according to the actual working condition requirement, and the other part of the ammonia gas is used as a reducing agent for SCR reactor denitration, so that the risk of the ammonia gas in the transportation and storage process can be reduced, a major hazard source of the thermal power plant is eliminated, and; meanwhile, compared with the traditional Haber process, the electrochemical ammonia production device for producing ammonia gas can be used for reaction at low temperature and low pressure, the energy consumption can be reduced by 20%, the reaction is not limited by thermodynamics, the theoretical one-way hydrogen conversion rate can reach 100%, the electrochemical ammonia production device is simple in system, small in floor area, capable of safely operating at normal pressure and free of influence on the arrangement and operation safety of the existing equipment of a power plant.
Furthermore, the system adopts a plurality of ammonia nozzles to spray ammonia gas into the SCR reactor, so that the ammonia gas can be more uniformly subjected to chemical reaction with the flue gas, nitrogen oxides in the flue gas are converted into clean substances such as nitrogen, water and the like, and the system is environment-friendly and economical.
Furthermore, the system provides reaction energy through the power supply assembly, and an external power supply required by the electrochemical ammonia production device can be directly obtained from a steam turbine of the thermal power plant, so that the system has good synchronism with the operation of the thermal power plant.
Furthermore, the system adopts the first control valve and the second control valve to respectively control the feeding amount of the ammonia gas according to the actual working condition requirements, and is convenient to operate, reasonable and reliable.
The method adopts the method of electrochemical ammonia production, and prepares ammonia gas in situ through an electrochemical ammonia production device in a thermal power plant, and because ammonia has fuel property, the energy density is equivalent to that of fossil fuel; when the coal-fired unit is in load-rising operation, the ammonia and the pulverized coal can be mixed and then fed into a boiler for combustion, so that the load-rising rate is increased, and NO is reducedxDischarging; when the coal-fired unit needs low-load operation, the surplus electric quantity is sent to an electrochemical ammonia production device to prepare ammonia gas and store the ammonia gas in an ammonia storage tank to serve as energy storage fuel. On the one hand, the demand of ammonia for denitration of the coal-fired unit is met, and the ammonia gas is used for storing energy, so that the requirement of deep peak shaving of the thermal power unit is met, and the running economy of the unit is improved.
Drawings
FIG. 1 is a schematic diagram of the connection structure of the system of the present invention.
In the figure: 1. nitrogen, 2, hydrogen, 3, an electrode cathode, 4, an electrode anode, 5, a reaction tank, 6, a power supply, 7, an ammonia gas pipeline, 8, an ammonia storage tank, 9, a first control valve, 10, a boiler, 11, an ammonia nozzle, 12, an SCR reactor, 13, a filter/reheater, 14, a water vapor pipeline, 15, a steam turbine, 16, a generator and 17, a second control valve.
Detailed Description
The present invention will now be described in further detail with reference to specific examples, which are intended to be illustrative, but not limiting, of the invention.
The invention relates to an energy storage and denitration system for ammonia production in a thermal power plant, which comprises an electrochemical ammonia production device connected and arranged on a boiler 10, as shown in figure 1; the electrochemical ammonia production device comprises a power supply assembly, a reaction tank 5 and an ammonia storage tank 8; the power supply assembly is connected with the reaction tank 5, the outlet of the reaction tank 5 is connected with the inlet of the ammonia storage tank 8, and the outlet of the ammonia storage tank 8 is connected with the boiler 10;
the power supply assembly comprises a pass/reheater 13, a steam turbine 15 and a generator 16 which are connected in sequence; the pass/reheater 13 is arranged in the horizontal flue of the boiler 10, and the outlet of the pass/reheater is connected with a steam turbine 15 through a steam pipeline 14 to push the steam turbine 15 to rotate and drive a generator 16 to generate electricity; the output end of the generator 16 is connected with the power supply 6 of the reaction tank 5;
the reaction tank 5 is provided with an electrode cathode 3 and an electrode anode 4, and mixed molten salt electrolyte is filled in the reaction tank; nitrogen 1 is introduced into the electrode cathode 3, and hydrogen 2 is introduced into the electrode anode 4; the outlet of the reaction tank 5 is connected with the inlet of an ammonia storage tank 8 through an ammonia pipeline 7;
the outlet of the ammonia storage tank 8 is respectively communicated with the internal combustion area of the boiler 10 and the tail flue of the boiler 10 through an ammonia pipeline 7; a second control valve 17 and an ammonia nozzle 11 are sequentially arranged on a pipeline communicated with an outlet flue of the boiler 10 and the ammonia storage tank 8; a plurality of ammonia nozzles 11 are uniformly arranged in the flue above the SCR reactor 12, and the injection direction is consistent with the flow direction of flue gas; a first control valve 9 is arranged on a pipeline of the ammonia storage tank 8 communicated with the combustion area in the boiler 10.
In actual practice, the following is particularly true,
1) an electrochemical ammonia production device is arranged in a thermal power plant, and nitrogen 1 and hydrogen 2 are used as raw material gases to be mixedThe fused salt is electrolyte, wherein nitrogen 1 is introduced into an electrode cathode 3 of a reaction tank 5, hydrogen 2 is introduced into an electrode anode 4, a power supply 6 provides energy for reaction, the nitrogen 1 and the hydrogen 2 are subjected to chemical reaction under normal pressure to generate ammonia gas, and the ammonia gas is sent into an ammonia storage tank 8 through an ammonia gas pipeline 7 to be stored. Wherein the chemical reaction at the electrode anode 4 is 3H2→ 6H + +6e-, the chemical reaction on the electrode cathode 3 is 6H + +6e- + N2→2NH3The overall chemical reaction is, 3H2+N2→2NH3。
2) A part of ammonia gas in the ammonia storage tank 8 is sent to the ammonia nozzle 11 through the ammonia gas pipeline 7, and reacts with nitrogen oxides in the flue gas in the SCR reactor 12 to generate nitrogen and water, and the reaction equation is as follows: NOx+NH3→N2+H2O, wherein the flow of ammonia gas is regulated by a second control valve 17, and an ammonia nozzle 11 and an SCR reactor 12 are arranged in the back pass of the boiler 10.
3) When the boiler 10 is in peak-shaving operation, a part of ammonia in the ammonia storage tank 8 is introduced into a combustion area in the boiler 10 through the ammonia pipeline 7 and is combusted together with pulverized coal, and the combustion reaction is as follows: NH (NH)3+O2→NO+H2And O, heating the water vapor, and controlling the flow of the ammonia gas according to the load of the unit. The steam is extracted from the pass/reheater 13 and sent to the turbine 15 through the steam line 14, so as to drive the turbine 15 to rotate and drive the generator 16 to generate electricity. Wherein the pass/reheater 13 is arranged in the horizontal flue of the boiler 10.
When the boiler 10 is in steady load operation, ammonia gas is not introduced into the boiler 10, and the heat required for heating the water vapor is provided by burning pulverized coal.
4) The electric quantity output by the generator 16 is sent to the electrochemical ammonia production device to supply energy to the power supply 6 of the reaction tank 5 besides being connected to the Internet; when the boiler 10 is in steady load operation, the current density of the power supply 6 is determined by the ammonia production rate required for denitration; when the boiler 10 is in peak shaving operation, surplus electricity is sent into the power supply 6, the ammonia production amount of the electrochemical ammonia production device is increased, and the generated ammonia is stored in the ammonia storage tank 8 and serves as energy storage fuel.
Based on the system, the invention also provides a method for storing energy and denitrating ammonia produced by the thermal power plant, which comprises the following steps,
step 1, filling electrolyte into a reaction tank 5, introducing nitrogen 1 into an electrode cathode 3, introducing hydrogen 2 into an electrode anode 4, providing reaction energy by a power supply assembly, carrying out chemical reaction on the nitrogen 1 and the hydrogen 2 at normal pressure to generate ammonia gas, and sending the ammonia gas into an ammonia storage tank 8 through an ammonia gas pipeline 7 for storage;
in the step 2, the flow of ammonia gas entering the boiler 10 is controlled through the first control valve 9 according to the load of the unit, and when the boiler 10 operates in a peak shaving mode, the first control valve 9 is opened to send the ammonia gas into the boiler 10 to be combusted with pulverized coal; when the boiler 10 operates with stable load, the first control valve 9 is closed;
the flow of ammonia into the back pass of the boiler 10 is controlled by a second control valve 17.
In the step 1, the water vapor in the boiler 10 extracted by the pass/reheater 13 in the power supply assembly is sent to the steam turbine 15 through the water vapor pipeline 14, so that the steam turbine 15 is pushed to rotate and the generator 16 is driven to generate power; the heat required to heat the water vapor is provided by pulverized coal combustion during steady load operation of the boiler 10.
In the step 1, the generator 16 provides reaction energy, when the boiler 10 operates in a peak shaving mode, surplus electricity is sent into the power supply 6, the ammonia production amount of the electrochemical ammonia production device is increased, and the produced ammonia 7 is stored in the ammonia storage tank 8 and serves as energy storage fuel; the current density of the power supply 6 during steady load operation of the boiler 10 is determined by the ammonia production rate required for denitration.
Claims (9)
1. A system for storing energy and denitrating ammonia generated in a thermal power plant is characterized by comprising an electrochemical ammonia generating device connected and arranged on a boiler (10);
the electrochemical ammonia production device comprises a power supply assembly, a reaction tank (5) and an ammonia storage tank (8); the output end of the power supply assembly is connected with a power supply (6) of the reaction tank (5); the outlet of the reaction tank (5) is connected with the inlet of an ammonia storage tank (8) through an ammonia pipeline (7); the outlet of the ammonia storage tank (8) is respectively communicated with the internal combustion area of the boiler (10) and the tail flue of the boiler (10) through a pipeline;
the reaction tank (5) is provided with an electrode cathode (3) and an electrode anode (4), and electrolyte is filled in the reaction tank; and nitrogen (1) is introduced into the electrode cathode (3), and hydrogen (2) is introduced into the electrode anode (4).
2. The system for storing energy and denitrating ammonia generated by a thermal power plant as claimed in claim 1, wherein an ammonia nozzle (11) is arranged on a pipeline of the ammonia storage tank (8) communicated with an outlet flue of the boiler (10); the ammonia nozzles (11) are uniformly arranged in a flue at the inlet of the SCR reactor (12), and the injection direction is consistent with the flowing direction of flue gas.
3. The system for storing energy and denitrating ammonia generated by a thermal power plant as claimed in claim 1, wherein the power supply assembly comprises a superheater/reheater (13), a steam pipeline (14), a steam turbine (15) and a generator (16) which are connected in sequence; the pass/reheater (13) is arranged in a horizontal flue of the boiler (10), and the outlet of the pass/reheater is connected with a steam turbine (15) through a steam pipeline (14); the output end of the generator (16) is connected with the power supply (6) of the reaction tank (5).
4. The system for storing energy and denitrating ammonia generated by a thermal power plant as claimed in claim 1, wherein the electrolyte in the reaction tank (5) is mixed molten salt.
5. The system for storing energy and denitrating ammonia generated in the thermal power plant as claimed in claim 1, wherein a first control valve (9) and a second control valve (17) are respectively arranged on a pipeline for communicating an outlet of the ammonia storage tank (8) with an internal combustion area of the boiler (10) and a tail flue of the boiler (10).
6. A method for storing energy and denitrating ammonia generated in a thermal power plant, which is characterized by comprising the following steps based on the system of any one of the claims 1-5,
step 1, filling electrolyte into a reaction tank (5), introducing nitrogen (1) into an electrode cathode (3), introducing hydrogen (2) into an electrode anode (4), providing reaction energy by a power supply assembly, carrying out chemical reaction on the nitrogen (1) and the hydrogen (2) at normal pressure to generate ammonia gas, and conveying the ammonia gas into an ammonia storage tank (8) through an ammonia gas pipeline (7) for storage;
step 2, feeding a part of ammonia gas in the ammonia storage tank (8) into a flue at the tail of the boiler (10) to react with nitrogen oxides in the flue gas; according to the actual working condition requirement, a part of ammonia gas in the ammonia storage tank (8) is sent into the boiler (10) to be combusted with the pulverized coal.
7. The method for storing energy and denitrating ammonia generated in the thermal power plant according to claim 6, wherein in the step 2, the flow of the ammonia gas entering the boiler (10) is controlled through the first control valve (9) according to the unit load, and when the boiler (10) is in peak shaving operation, the first control valve (9) is opened to feed the ammonia gas into the boiler (10) to be combusted with the pulverized coal; when the boiler (10) operates in a stable load mode, closing the first control valve (9);
the flow of the ammonia gas entering the tail flue of the boiler (10) is controlled by a second control valve (17).
8. The method for storing energy and denitrating ammonia generated in the thermal power plant as claimed in claim 6, wherein in step 1, the water vapor extracted from the boiler (10) by the pass/reheater (13) in the power supply assembly is sent to the turbine (15) through the water vapor pipeline (14), so as to drive the turbine (15) to rotate and drive the generator (16) to generate electricity; when the boiler (10) operates under a stable load, the heat required for heating the water vapor is provided by burning the pulverized coal.
9. The method for storing energy and denitrating ammonia generated by a thermal power plant according to claim 8, wherein in the step 1, the generator (16) provides reaction energy, when the boiler (10) is in peak-shaving operation, surplus electricity is fed into the power supply (6), the ammonia production amount of the electrochemical ammonia generating device is increased, and the generated ammonia gas (7) is stored in the ammonia storage tank (8) and is used as energy storage fuel; during steady load operation of the boiler (10), the current density of the power supply (6) is determined by the ammonia production rate required for denitration.
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| CN113603114A (en) * | 2021-08-10 | 2021-11-05 | 西安热工研究院有限公司 | Power generation method for eliminating wind and light abandoning and realizing carbon-free emission |
| CN113944940A (en) * | 2021-10-12 | 2022-01-18 | 中国矿业大学 | Ammonia combustion utilization system |
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