CN113041837A - Process for denitration of flue gas generated after incineration of fluorine-containing waste liquid of fluorine material - Google Patents
Process for denitration of flue gas generated after incineration of fluorine-containing waste liquid of fluorine material Download PDFInfo
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- CN113041837A CN113041837A CN202110251606.2A CN202110251606A CN113041837A CN 113041837 A CN113041837 A CN 113041837A CN 202110251606 A CN202110251606 A CN 202110251606A CN 113041837 A CN113041837 A CN 113041837A
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- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/86—Catalytic processes
- B01D53/8621—Removing nitrogen compounds
- B01D53/8625—Nitrogen oxides
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
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Abstract
The invention belongs to the technical field of energy-saving production, and particularly relates to a process for flue gas denitration after incineration of fluorine-containing waste liquid of a fluorine material. In the traditional SNCR denitration process, a large amount of reducing agents are needed, liquid urea is introduced into a gasifier to be gasified into ammonia gas, the storage and transportation risks are reduced, the utilization rate of the reducing agents is improved, heat is recovered through a waste heat boiler and is used for the gasifier, a heater and energy comprehensive utilization, the ammonia gas escaping from flue gas is fully utilized through an SCR denitration reactor, the denitration efficiency is improved, and the auxiliary material consumption is saved; the waste heat boiler and the quencher are used for reducing the generation of carcinogens such as dioxin in the flue gas.
Description
Technical Field
The invention belongs to the technical field of energy-saving production, and particularly relates to a process for flue gas denitration after incineration of fluorine-containing waste liquid of a fluorine material.
Background
The information in this background section is only for enhancement of understanding of the general background of the invention and is not necessarily to be construed as an admission or any form of suggestion that this information forms the prior art that is already known to a person of ordinary skill in the art.
The Selective Catalytic Reduction (SCR) and selective non-catalytic reduction (SNCR) technologies in the current flue gas denitration technology are the most widely-used denitration technologies in the market and the most mature technologies. The SCR denitration technology is a selective reduction method, ammonia gas or other suitable reducing agents are added into flue gas on a catalyst, and NOx in the flue gas is converted into nitrogen gas and water by the catalyst. The SNCR denitration technology is a clean denitration technology which does not use a catalyst, sprays reducing agents (such as water, urea solution and the like) containing amino into a furnace at the temperature of 850-1100 ℃, reduces and removes NOx in flue gas and generates nitrogen and water. The SNCR denitration technology has the advantages and disadvantages that 1.SCR uses catalyst, and SNCR does not use catalyst. The reduction of SNCR in the reaction may be carried out using urea in addition to ammonia. And the SCR flue gas temperature is lower, and urea can be added into the flue gas after being prepared into ammonia. SNCR has no catalysis, strict requirements on temperature, low temperature and narrow NOx conversion; excessive temperature, NH3Is easily oxidized into NOx to counteract NH3The removal efficiency of (2); on the other hand, the amount and cost of the reducing agent are increased. SNCR because of the high reaction temperature, the reaction time and the setting and switching of the ammonia injection point are limited by the boiler and/or the heating surface arrangement. 5. In order to meet the requirement of reaction temperature, the requirement of ammonia injection control is high. The ammonia injection control is the key of the SNCR technology, and is the biggest obstacle for limiting the SNCR denitration rate and the operation stability and reliability. And 6, the SNCR ammonia has large leakage amount and pollutes the atmosphere. The denitration efficiency of SNCR is generally 30-50% due to the high reaction temperature and the limitation of ammonia leakage, while the denitration efficiency of SCR has almost no upper limit technically, and is only considered from the cost performance.
Therefore, how to design a process for flue gas denitration after incineration of fluorine-containing waste liquid of fluorine materials, so as to reduce energy consumption, reduce consumption of reducing agents and improve denitration efficiency, is a problem that needs to be solved by technical personnel in the field.
Disclosure of Invention
In view of the above-mentioned shortcomings of the prior art, the present invention is directed to a fluorine-containing materialA flue gas denitration process after waste liquid incineration. In the traditional denitration process, ammonia belongs to dangerous chemicals and is difficult to store and transport, and SNCR has no catalysis, so that the requirements on temperature are strict, the temperature is too low, and the NOx conversion is narrow and low; excessive temperature, NH3Is easily oxidized into NOx to counteract NH3The removal efficiency of (2). On one hand, the SNCR increases the dosage and cost of a reducing agent, on the other hand, because of the limitation of high reaction temperature and ammonia leakage, the denitration efficiency is lower than usual, the investment and operating cost of SCR are high, and the catalyst is easy to be poisoned. The invention is improved aiming at the process, and the denitration in the high-temperature furnace is carried out firstly, and then the waste heat of the flue gas is utilized to heat and gasify the reducing agent for catalytic reduction denitration.
The invention is realized by the following technical scheme:
the invention provides a process for flue gas denitration after incineration of fluorine-containing waste liquid of fluorine materials, which comprises the steps of waste heat recovery, quenching and cooling, and heating and gasifying a reducing agent by utilizing flue gas waste heat to perform catalytic reduction denitration; wherein the waste heat boiler is connected and matched with the quencher through a pipeline and is used as a quenching cooling device to reduce the temperature of the flue gas. The waste heat boiler supplies heat to the gasifier and the heater, so that the urea in the gasifier is vaporized into the reducing agent of the denitration stripping supply system.
The waste heat boiler generates steam, and the flue gas is controllably heated again to meet the temperature requirement of catalytic reaction; the quencher reduces the temperature of the flue gas, reduces the residence time of the flue gas in a dangerous temperature area and prevents the generation of dioxin; in addition, the SCR reactor utilizes the escaped ammonia gas of the SNCR denitration device as a raw material for catalytic reaction denitration, so that the ammonia gas escaped in the whole system is below 5%.
In the existing denitration process, ammonia water and urea are selected as reducing agents for denitration, the utilization rate of the reducing agents is low, and the denitration efficiency is only 20-30%.
The invention improves the original denitration process, adopts liquid ammonia or ammonia water as the denitration liquid, adopts a pulse pump for conveying, and causes the problems of incomplete reduction reaction and ammonia escape because the denitration liquid and the flue gas are not uniformly mixed, and the urea liquid is heated by steam generated by a waste heat boiler at present, and after the urea liquid is atomized by a gasifier, steam and a spray gun, fine vaporous liquid drops (denitrified gas) formed by crushing the urea liquid are sprayed into an incinerator, so that the mixing degree of the flue gas and the denitration gas is effectively improved, the reduction reaction is more sufficient, and the denitration efficiency of the SNCR denitration device reaches 60 percent. Through the heat exchange mode provided by the invention, the mixing degree can be improved, the denitration rate can be improved, the waste heat can be fully utilized, the electric energy and the heat are saved, and the heat exchange device has important significance for energy-saving production.
One or more technical schemes that this application provided have following advantage or beneficial effect:
(1) the waste heat recovery quenching cooling and the utilization of the flue gas waste heat to heat and gasify the reducing agent for catalytic reduction denitration reduce the energy consumption in the production process, and have important economic significance. The waste heat is fully utilized, the denitration efficiency is improved, the generation of dioxin is reduced, and the escape of ammonia gas is reduced.
(2) Compared with the existing denitration process, the flue gas denitration efficiency is further improved, and the ecological environment is protected.
Drawings
The accompanying drawings, which are incorporated in and constitute a part of this specification, are included to provide a further understanding of the invention, and are incorporated in and constitute a part of this specification, illustrate exemplary embodiments of the invention and together with the description serve to explain the invention and not to limit the invention. FIG. 1 is a schematic view of a system related to a flue gas denitration process after incineration of a fluorine-containing waste liquid of a fluorine material in example 1;
wherein, 1 is a storage tank, 2 is a pressure pump, 3 is a regulating valve, 4 is a gasifier, 5 is an incinerator, 6 is a waste heat boiler, 7 is a quencher, 8 is a heater, 9 is an SCR reactor, and 10 is an induced draft fan.
Detailed Description
It should be noted that the following detailed description is exemplary and is intended to provide further explanation of the disclosure. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this application belongs.
It is noted that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of example embodiments according to the present application. As used herein, the singular forms "a", "an" and "the" are intended to include the plural forms as well, and it should be understood that when the terms "comprises" and/or "comprising" are used in this specification, they specify the presence of stated features, steps, operations, devices, components, and/or combinations thereof, unless the context clearly indicates otherwise.
As introduced in the background art, due to SNCR denitration, the utilization rate of a reducing agent in the production process is low, and the denitration efficiency is poor, in order to solve the technical problems, the invention provides the production process for flue gas denitration after incineration of the fluorine-containing waste liquid of the fluorine material, which can effectively reduce the consumption of auxiliary materials in the flue gas denitration production process after incineration of the fluorine-containing waste liquid of the fluorine material, improve the utilization rate of the reducing agent, and increase the denitration efficiency.
A flue gas denitration process after burning fluorine-containing waste liquid of fluorine materials comprises waste heat recovery, quenching and cooling, and catalytic reduction denitration by heating and gasifying a reducing agent by using flue gas waste heat; the waste heat boiler is matched with the quencher to be used as a quenching cooling device to reduce the temperature of the flue gas; the waste heat boiler supplies heat to the gasifier and the heater, so that the urea in the gasifier is vaporized into the reducing agent of the denitration stripping supply system. The waste heat boiler is connected with the quencher through a pipeline to reduce the temperature of the flue gas. Thereby reducing the retention time of the flue gas in a dangerous temperature area and reducing the generation of dioxin. In addition, the waste heat boiler supplies heat to the gasifier and the heater through pipelines, so that the urea in the gasifier is gasified into ammonia gas and supplied to the reducing agent of the system. The steam that utilizes waste heat boiler to produce carries out controllable heating to the flue gas in order to satisfy catalytic reaction temperature demand, can make full use of above-mentioned denitrification facility's escape ammonia simultaneously, makes entire system ammonia escape below 5%.
Further, the pressure of the waste heat boiler is 0.2-0.4 MPa.
Further, the quencher outlet temperature is <75 ℃.
Furthermore, the urea solution is used as the denitration solution, the urea solution is heated by the steam generated by the waste heat boiler, and is sprayed into the incinerator after being atomized by the gasifier, the steam atomization and the spray gun, so that the mixing degree of the flue gas and the denitration gas is effectively improved, the reduction reaction is more sufficient, and the denitration efficiency of the SNCR denitration device reaches 60%.
Further, the process is based on the following system, and the system sequentially comprises a storage tank, a pressure pump, a regulating valve, a gasifier, an incinerator, a waste heat boiler, a quencher, a heater, an SCR reactor and an induced draft fan according to the sequence of pipeline connection. The urea solution is heated by steam generated by a waste heat boiler, the denitration solution is atomized and sprayed into the incinerator through the spray head, the spray head drives the denitration solution to move by utilizing pressure difference generated by high-speed flow of the steam, and the denitration solution impacts on the impact piece at the front part of the spray head to generate fine and vaporous liquid drops, so that the mixing degree is improved, the reaction is more sufficient, and the denitration efficiency reaches 60%. Through the heat exchange mode provided by the invention, the mixing degree can be improved, the denitration rate can be improved, the waste heat can be fully utilized, the electric energy and the heat are saved, and the heat exchange device has important significance for energy-saving production.
Further, the waste heat boiler and the gasifier are connected by a pipeline, and the pipeline is provided with a regulating valve. The waste heat boiler fully utilizes waste heat and provides energy for the gasifier.
Further, the incinerator comprises an air blowing system, a fuel system and a fluoride material fluoride waste liquid incineration system, the incineration system is connected with a waste heat boiler, preferably, the waste heat boiler is connected with a water source, and preferably, the waste heat boiler is supplemented with pure water.
Further, the SCR reactor is connected with a heater through a fan; preferably, the SCR reactor has a catalyst module and a spare catalyst layer.
Further, liquid urea is stored in a storage tank, a pressure pump is started, the urea is conveyed into the gasifier through a pipeline, and an adjusting valve is used for controlling the dosage of the denitration gas entering the incinerator; the waste heat boiler provides heat for the gasifier and the heater, so that urea in the gasifier is vaporized and supplied to the incinerator and the SCR reactor to be used as reducing agents, and the waste heat boiler and the quencher are used as rapid cooling facilities.
In order to make the technical solutions of the present disclosure more clearly understood by those skilled in the art, the technical solutions of the present disclosure will be described in detail below with reference to specific examples and comparative examples.
Example 1:
the application provides a flue gas denitration's technology after fluoride material fluoride waste liquid burns, as shown in figure 1, flue gas denitration production technology does, stores liquid urea in storage tank 1 for subsequent use, keeps the liquid level position to reach 50 ~ 80% of storage tank inner wall height, starts the force pump, carries the urea to vaporizer 4 in through the pipeline, and governing valve 3 is used for controlling the ammonia dose that gets into incinerator 5. The waste heat boiler 6 provides steam for the gasifier 4 and provides heat for the heater 8, so that urea in the gasifier 4 is vaporized into denitration steam and is supplied to the incinerator 5 to be used as a reducing agent, the waste heat boiler 6 and the quencher 7 are used as quenching cooling facilities, the temperature range of 500 ℃ is avoided as much as possible by using the waste heat boiler 6 and the quencher 7, carcinogens such as dioxin are prevented from being generated, waste heat is recovered as much as possible, and energy is saved; the heater 8 and the SCR reactor 9 are used for further removing nitrogen oxides in the flue gas, escaping ammonia gas in the flue gas is fully utilized, the denitration efficiency is improved, and auxiliary material consumption is saved; the waste heat boiler and the quencher are used for reducing the generation of carcinogens such as dioxin in the flue gas.
The production process relates to a system which comprises a storage tank 1, a booster pump 2, a gasifier 4, a regulating valve 3, an incinerator 5, a waste heat boiler 6, a quencher 7, a heater 8, an SCR reactor 9 and an induced draft fan 10 which are connected in sequence through pipelines.
Example 2:
the application still provides a flue gas denitration's technology after fluoride material fluorine-containing waste liquid burns, based on the system in embodiment 1, wherein, 1 bottom in storage tank has pipeline and force (forcing) pump 2 intercommunication, and urea in the storage tank 1 passes through force (forcing) pump 2 and carries to vaporizer 4, still has governing valve 3 before vaporizer 4 for the control gets into the denitration tolerance that burns burning furnace 5. The side wall of the storage tank 1 is also provided with a return pipe which is communicated with the gasifier 4 and can flow back to the storage tank 1 when the gasifier is in excessive vaporization.
The waste heat boiler 6 is provided with an outer wall and an inner pipeline structure, a certain gap is formed between the outer wall and the inner pipeline, the inner pipeline is communicated with a pipeline communicated with the waste heat boiler 6 at the top of the incinerator 5, the inner wall of the waste heat boiler 6 is provided with a pipeline connected with the quencher 7, the outer wall is also provided with a pipeline connected with the gasifier 4, the pipeline connected with the waste heat boiler 6 and the gasifier 4 is connected with the heater 8 through a pipeline, the pipeline connected with the gasifier 4 and the waste heat boiler 6 and the pipeline connected with the waste heat boiler 6 and the heater 8 are communicated with the gap in the waste heat boiler 6, and after the fluorine-containing waste liquid is incinerated, smoke does not contact with substances in the outer pipeline.
The heater 8 is provided with an external steam or electric heating measure for supplementary heating.
The SCR reactor 9 is provided with a pipeline communicated with the gasifier 4, and is mixed with the burned flue gas through a gas mixing device to flow into the SCR reactor 9, and the SCR reactor 9 comprises a guide grid, a rectification grid, a catalyst module, a standby catalyst layer and other basic structures.
It should be noted that the above examples are only used to illustrate the technical solutions of the present invention and not to limit them. Although the present invention has been described in detail with reference to the examples given, those skilled in the art can modify the technical solution of the present invention as needed or equivalent substitutions without departing from the spirit and scope of the technical solution of the present invention.
Claims (10)
1. A process for denitration of flue gas generated after incineration of fluorine-containing waste liquid of fluorine materials is characterized by comprising waste heat recovery, quenching and cooling, and catalytic reduction denitration by heating and gasifying a reducing agent by using flue gas waste heat; the waste heat boiler is matched with the quencher to be used as a quenching cooling device to reduce the temperature of the flue gas; the waste heat boiler supplies heat to the gasifier and the heater, so that the urea in the gasifier is vaporized into the reducing agent of the denitration stripping supply system.
2. The process for denitration of flue gas generated after incineration of fluorine-containing waste liquid of fluorine material of claim 1, wherein the pressure of the waste heat boiler is 0.2-0.4 MPa.
3. The process for denitration of flue gas generated after incineration of fluorine-containing waste liquid of fluorine material according to claim 1, wherein the waste heat boiler is connected with a quencher through a pipeline, and the outlet temperature of the quencher is less than 75 ℃.
4. The process for denitration of flue gas generated after incineration of fluorine-containing waste liquid of fluorine material as claimed in claim 1, wherein the denitration liquid is urea liquid.
5. The process for denitration of flue gas after incineration of fluorine-containing waste liquid of fluorine material as claimed in claim 1, wherein the urea solution is heated by steam generated from a waste heat boiler, and is sprayed into the incinerator after being atomized by a gasifier, steam atomization and a spray gun.
6. The process for denitration of flue gas after incineration of fluorine-containing waste liquid of fluorine material according to claim 1, wherein the process is based on a system comprising a storage tank, a pressure pump, a gasifier, a regulating valve, an incinerator, a waste heat boiler, a quencher, a heater, an SCR reactor and an induced draft fan in sequence according to a pipeline connection sequence.
7. The process for denitration of flue gas after incineration of fluorine-containing waste liquid of fluorine material of claim 4, wherein the waste heat boiler and the gasifier are connected through a pipeline, and the pipeline is provided with a regulating valve.
8. The process for denitration of flue gas after incineration of fluorine-containing waste liquid of fluorine material according to claim 4, wherein the incinerator comprises an air blowing system, a fuel system and a fluorine-containing waste liquid incineration system, the incineration system is connected with a waste heat boiler, preferably, the waste heat boiler is connected with a water source, preferably, the waste heat boiler is provided with a pure water supplement.
9. The process for denitration of flue gas after incineration of fluorine-containing waste liquid of fluorine material according to claim 4, wherein the SCR reactor is connected with the heater through a fan; preferably, the SCR reactor has a catalyst module and a spare catalyst layer.
10. The process for denitration of flue gas after incineration of fluorine-containing waste liquid of fluorine material according to claim 4, wherein liquid urea is stored in a storage tank, a pressure pump is started to convey the urea to the gasifier through a pipeline, and a regulating valve is used for controlling the amount of denitration gas entering the incinerator; the waste heat boiler provides heat for the gasifier and the heater, so that urea in the gasifier is vaporized into denitration steam, the denitration steam is supplied to the incinerator and the SCR reactor to be used as a reducing agent, and the waste heat boiler and the quencher are used as a rapid cooling facility.
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