CN111701427B - Process for removing NOx in waste gas generated by burning tetrachloroethylene residual liquid - Google Patents
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
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Abstract
The invention relates to the technical field of tetrachloroethylene raffinate treatment, in particular to a process for removing NOx in waste gas generated by burning tetrachloroethylene raffinate, which comprises the following steps: when the tetrachloroethylene residual liquid is burnt, the adding amount of the hydrogen-containing fuel is controlled, so that chlorine can be generated in the tetrachloroethylene residual liquid in the burning process; and sequentially cooling, falling film absorption and water washing the generated waste gas, then carrying out alkali washing treatment, adding a strong oxidant into alkali washing liquid subjected to the alkali washing treatment, and finally discharging the waste gas to finish the process of removing NOx in the waste gas generated by burning the tetrachloroethylene residual liquid. The invention keeps the burning process in a hydrogen deficiency state by controlling the introduction amount of hydrogen-containing fuel in the burning process of the tetrachloroethylene residual liquid, so that chlorine with strong oxidizing property is generated by chlorine element in the residual liquid in the hydrogen deficiency environment, namely, strong oxidizer is prepared during the burning process, and the strong oxidizer can oxidize NO in the waste gas into NO2Thereby achieving the purpose of reducing the NO content in the waste gas at the outlet of the incinerator.
Description
Technical Field
The invention relates to the technical field of tetrachloroethylene residual liquid treatment, and particularly relates to a process for removing NOx in waste gas generated by burning tetrachloroethylene residual liquid.
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.
NOx purification is the most difficult and expensive technique. This is due to the inert (chemical reaction does not occur easily) and water-insoluble nature of NO, which makes it difficult for NO to be absorbed efficiently during alkaline cleaning. NOx in the incinerator flue gas is predominantly NO, with levels as high as 95% or more. At present, the removal of NOx in the waste gas of a tetrachloroethylene raffinate incinerator mostly adopts an SNCR method (refer to the attached figure 1 in the specification), and the method is to spray reducing agent carbamide (urea) at an outlet of the incinerator and reduce the NOx into nitrogen by using the carbamide (urea) under the condition of high temperature (800-1000 ℃).
However, the inventor researches and discovers that: the prior SNCR method is used for denitration of waste gas of a tetrachloroethylene raffinate incinerator and has the main defects that: firstly, the equipment investment is large, secondly, the denitration efficiency is low, the gas phase reaction is difficult to ensure the full mixing, and the consumption of ammonia liquid is large; strict requirements on temperature, low temperature and low NOx conversion rate; excessive temperature, NH3It is easily oxidized into NOx to cancel NH3The removal efficiency of (2).
Disclosure of Invention
Aiming at the problems, the invention provides a process for removing NOx in waste gas generated by burning tetrachloroethylene residual liquid, which not only overcomes the bottleneck problems of large equipment investment and harsh control conditions in an SNCR method, but also can more efficiently and thoroughly remove the nitrogen oxides in the waste gas. In order to achieve the purpose, the technical scheme of the invention is as follows.
A process for removing NOx in waste gas generated by burning tetrachloroethylene residual liquid comprises the following steps:
(1) when the tetrachloroethylene residual liquid is burnt, the adding amount of the hydrogen-containing fuel is controlled, so that chlorine can be generated in the tetrachloroethylene residual liquid in the burning process.
(2) And (2) sequentially cooling, falling film absorption and water washing the waste gas generated in the step (1), then performing alkali washing treatment, adding a strong oxidant into alkali washing liquid subjected to the alkali washing treatment, and finally discharging the waste gas to finish the process of removing NOx in the waste gas generated by burning the tetrachloroethylene residual liquid.
Further, in the step (1), the adding proportion of the hydrogen-containing fuel is as follows: the chlorine/hydrogen ratio was controlled at 12:21, molar ratio. The hydrogen-containing fuel feeding amount in the incinerator is controlled to ensure that the incinerator maintains the incineration environment with insufficient hydrogen element, chlorine element in residual liquid generates trace chlorine in the hydrogen-deficient environment, and the chlorine is a strong oxidant and can oxidize NO in waste gas into NO2And the NO content in the smoke of the incinerator is reduced. In addition, maintaining a trace amount of chlorine gas can help to avoid causing secondary pollution as well.
Optionally, the hydrogen-containing fuel comprises any one of hydrogen, propane, water gas, and the like.
Further, in the step (2), the cooling method includes: and (2) introducing the waste gas generated in the step (1) into heat exchange equipment to exchange heat with a refrigerant in the heat exchange equipment, and chilling, so that the temperature of the waste gas is reduced. Optionally, the heat exchange device comprises any one of a waste heat boiler, a heat exchanger and the like.
Further, in the step (2), the alkaline solution includes any one of sodium hydroxide, sodium carbonate solution and the like. Optionally, the mass concentration (%) ranges from 10% to 15%
Further, the strong oxidant is hypochlorite, including any one or more of sodium hypochlorite, potassium hypochlorite, calcium hypochlorite and the like. Optionally, the adding proportion ranges from 1% to 2%, and the mass is concentrated.
Further, in the step (2), the alkali washing treatment is carried out in an alkali washing tower, the alkali washing liquid is in countercurrent contact with the exhaust gas in a circulating spraying mode, and the NO remained in the exhaust gas is further oxidized into NO by a strong oxidant2，NO2And then absorbed and removed by alkaline washing liquid.
Further, step (2) further comprises a metering pump, and the adding amount of the strong oxidant is controlled according to the change of the NOx content in the exhaust gas.
Compared with the prior art, the invention has the following beneficial effects:
(1) the invention controls the introduction amount of hydrogen-containing fuel in the combustion process of the tetrachloroethylene residual liquid to keep the incineration process in a hydrogen deficiency state, so that chlorine with strong oxidizing property is generated by chlorine element in the residual liquid in the hydrogen deficiency environment, which is equivalent to preparing a strong oxidizer during combustion, and the strong oxidizer can oxidize NO in waste gas into NO2 under the joint participation of moisture provided in a falling film absorption process, thereby achieving the purpose of reducing the NO content in the waste gas at the outlet of the incinerator.
(2) The strong oxidant is added in the alkali washing treatment process, so that residual NO in the waste gas can be further oxidized into NO2，NO2Then absorbed by alkali liquor and removed, and then effectively reduces NO in the waste gas at the outlet of the incinerator, and finally more efficiently and thoroughly removes the nitrogen oxides in the waste gas.
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 without unduly limiting the invention.
FIG. 1 is a flow chart of a process for removing NOx from waste gas generated by burning tetrachloroethylene raffinate in the prior art.
FIG. 2 is a flow chart of a process for removing NOx from waste gas generated by burning tetrachloroethylene raffinate in the embodiment of the present invention.
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. The experimental procedures, in which specific conditions are not noted in the following examples, are generally carried out according to conventional conditions or according to conditions recommended by the manufacturers.
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. The reagents or starting materials used in the present invention can be purchased from conventional sources, and unless otherwise specified, the reagents or starting materials used in the present invention can be used in a conventional manner in the art or in accordance with the product specifications. In addition, any methods and materials similar or equivalent to those described herein can be used in the methods of the present invention. The preferred methods and materials described in this invention are exemplary only.
As described above, the conventional SNCR method for denitration c of waste gas from a tetrachloroethylene raffinate incinerator has the disadvantages of large equipment investment, low denitration efficiency, difficulty in ensuring sufficient mixing in gas phase reaction, large ammonia liquid consumption, strict requirement on temperature, and the like. Therefore, the invention provides a process for removing NOx in waste gas generated by burning tetrachloroethylene residual liquid, and the invention is further explained by combining the attached drawings and the specific embodiment of the specification.
First embodiment
A process for removing NOx in waste gas generated by burning tetrachloroethylene raffinate refers to FIG. 2, and comprises the following steps:
the tetrachloroethylene residual liquid and the propane enter the incinerator through the combustor, are combusted at about 1200 ℃ in the incineration hearth, and can participate in combustion in a hydrogen deficiency environment by controlling the feeding proportion (the chlorine/hydrogen molar ratio is 12:21) of the tetrachloroethylene residual liquid and the propane to generate trace chlorine in the hearth.
Leading high-temperature flue gas out of the incinerator, then entering a waste heat boiler, reducing the temperature of the flue gas to about 550 ℃, then reducing the temperature of the flue gas to about 60 ℃ through a chilling tower, then entering a falling film absorber, reducing the temperature of the falling film absorber to 30 ℃, and reacting trace chlorine in the flue gas with water to generate hypochlorous acid which has strong oxidizing property and can oxidize NO into NO2(NO+Cl2+H2O＝2NO2+HCl)。
NO in cooled flue gas2Continuously contacts with alkali liquor (sodium hydroxide solution with the mass concentration of about 10%) in the alkali washing tower in a reverse direction, and is absorbed and removed by the alkali liquor. Adding strong oxidant (sodium hypochlorite, the mass concentration of the added strong oxidant in the alkali liquor is about 1.5%) in the alkali washing treatment process according to the content of NOx at the outlet of the chimney, and further oxidizing residual NO in the waste gas into NO2，NO2Then absorbed and removed by lye. And finally, the content of NOx in the discharged flue gas is reduced to below 50ppm by controlling the chlorine/hydrogen ratio.
Second embodiment
A process for removing NOx in waste gas generated by burning tetrachloroethylene raffinate refers to FIG. 2, and comprises the following steps:
the tetrachloroethylene residual liquid and the water gas enter the incinerator through the combustor to be combusted at about 1200 ℃ in an incineration hearth, and the tetrachloroethylene residual liquid and the water gas can participate in combustion in a hydrogen deficiency environment by controlling the feeding proportion (the chlorine/hydrogen molar ratio is 12:21) to generate trace chlorine in the hearth.
Leading high-temperature flue gas out of the incinerator, then entering a waste heat boiler, reducing the temperature of the flue gas to about 550 ℃, then reducing the temperature of the flue gas to about 60 ℃ through a chilling tower, then entering a falling film absorber, reducing the temperature of the falling film absorber to 30 ℃, and reacting trace chlorine in the flue gas with water to generate hypochlorous acid which has strong oxidizing property and can oxidize NO into NO2(NO+Cl2+H2O＝2NO2+HCl)。
NO in cooled flue gas2Continuously contacts with alkali liquor (sodium carbonate solution with the mass concentration of about 15%) in the alkali washing tower in a reverse direction, and is absorbed and removed by the alkali liquor. Adding strong oxidant (sodium hypochlorite, the mass concentration of the added sodium hypochlorite in the alkali liquor is about 2.0%) in the alkali washing treatment process according to the content of NOx at the outlet of the chimney, and further oxidizing residual NO in the waste gas into NO2，NO2Then absorbed and removed by lye. By controlling the chlorine/hydrogen ratio, the content of NOx in the discharged flue gas is finally reduced to be below 38 ppm.
Third embodiment
A process for removing NOx in waste gas generated by burning tetrachloroethylene raffinate refers to FIG. 2, and comprises the following steps:
the tetrachloroethylene residual liquid and the propane enter the incinerator through the combustor to be combusted at about 1200 ℃ in an incineration hearth, and the tetrachloroethylene residual liquid and the propane can participate in combustion in a hydrogen deficiency environment by controlling the feeding proportion (the chlorine/hydrogen molar ratio is 12:21) to generate trace chlorine in the hearth.
Leading high-temperature flue gas out of the incinerator, then feeding the high-temperature flue gas into a waste heat boiler, cooling the temperature of the flue gas to about 550 ℃, then cooling the temperature of the flue gas to about 60 ℃ through a chilling tower, then feeding the flue gas into a falling film absorber, cooling the temperature of the falling film absorber to 30 ℃, and reacting trace chlorine and water in the flue gas to generate secondary chlorineChloric acid, hypochlorous acid having strong oxidizing properties capable of oxidizing NO to NO2(NO+Cl2+H2O＝2NO2+HCl)。
NO in cooled flue gas2Continuously contacts with alkali liquor (sodium hydroxide solution with the mass concentration of about 13%) in the alkali washing tower in a reverse direction, and is absorbed and removed by the alkali liquor. Adding strong oxidant (sodium hypochlorite, the mass concentration of the added sodium hypochlorite in the alkali liquor is about 1.0%) in the alkali washing treatment process according to the content of NOx at the outlet of the chimney, and further oxidizing residual NO in the waste gas into NO2，NO2Then absorbed and removed by lye. And finally, the content of NOx in the discharged flue gas is reduced to be lower than 43ppm by controlling the chlorine/hydrogen ratio.
Fourth embodiment
A process for removing NOx in waste gas generated by burning tetrachloroethylene raffinate refers to FIG. 2, and comprises the following steps:
the tetrachloroethylene residual liquid and sufficient propane enter the incinerator through the combustor, are combusted at about 1200 ℃ in an incineration hearth, high-temperature flue gas is led out from the incinerator and then enters a waste heat boiler, the temperature of the flue gas is reduced to about 550 ℃ after being cooled, then the temperature of the flue gas is reduced to about 60 ℃ through a chilling tower, and then the flue gas enters a falling film absorber and the temperature of the falling film absorber is reduced to 30 ℃.
NO in cooled flue gas2Continuously contacts with alkali liquor (sodium hydroxide solution with the mass concentration of about 10%) in the alkali washing tower in a reverse direction, and is absorbed and removed by the alkali liquor. Adding strong oxidant (sodium hypochlorite, the mass concentration of the added sodium hypochlorite in the alkali liquor is about 1.5%) in the alkali washing treatment process according to the content of NOx at the outlet of the chimney, and further oxidizing residual NO in the waste gas into NO2，NO2Then absorbed and removed by alkali liquor, and finally the NOx content in the discharged flue gas is measured to be more than 739 ppm.
Fifth embodiment
A process for removing NOx in waste gas generated by burning tetrachloroethylene raffinate refers to FIG. 2, and comprises the following steps:
the tetrachloroethylene residual liquid and water gas (enough) enter an incinerator through a burner, are combusted at about 1200 ℃ in an incineration hearth, high-temperature flue gas is led out from the incinerator and then enters a waste heat boiler, the temperature of the flue gas is reduced to about 550 ℃, then the temperature of the flue gas is reduced to about 60 ℃ through a chilling tower, and then the flue gas enters a falling film absorber and the temperature of the falling film absorber is reduced to 30 ℃.
NO in cooled flue gas2The alkaline washing tower is in reverse contact with alkali liquor (sodium carbonate solution with the mass concentration of about 15%) and is absorbed and removed by the alkali liquor. Adding strong oxidant (sodium hypochlorite, the mass concentration of the added sodium hypochlorite in the alkali liquor is about 2.0%) in the alkali washing treatment process according to the content of NOx at the outlet of the chimney, and further oxidizing residual NO in the waste gas into NO2，NO2Then absorbed and removed by lye. Finally, the content of NOx in the discharged flue gas is measured to be above 641 ppm.
Sixth embodiment
A process for removing NOx in waste gas generated by burning tetrachloroethylene raffinate refers to FIG. 2, and comprises the following steps:
the tetrachloroethylene residual liquid and sufficient propane enter the incinerator through the combustor, are combusted at about 1200 ℃ in an incineration hearth, high-temperature flue gas is led out from the incinerator and then enters a waste heat boiler, the temperature of the flue gas is reduced to about 550 ℃ after being cooled, then the temperature of the flue gas is reduced to about 60 ℃ through a chilling tower, and then the flue gas enters a falling film absorber and the temperature of the falling film absorber is reduced to 30 ℃.
NO in cooled flue gas2Continuously contacts with alkali liquor (sodium hydroxide solution with the mass concentration of about 13%) in the alkali washing tower in a reverse direction, and is absorbed and removed by the alkali liquor. Adding strong oxidant (sodium hypochlorite, the mass concentration of the added sodium hypochlorite in the alkali liquor is about 1.0%) in the alkali washing treatment process according to the content of NOx at the outlet of the chimney, and further oxidizing residual NO in the waste gas into NO2，NO2Then absorbed and removed by lye. Finally, the content of NOx in the discharged smoke is measured to be higher than 686 ppm.
Although the present invention has been described in detail with reference to the foregoing embodiments, it will be apparent to those skilled in the art that changes may be made in the embodiments and/or equivalents thereof without departing from the spirit and scope of the invention. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (11)
1. A process for removing NOx in waste gas generated by burning tetrachloroethylene raffinate is characterized by comprising the following steps:
(1) when the tetrachloroethylene residual liquid is burnt, the adding amount of the hydrogen-containing fuel is controlled, and the adding proportion of the hydrogen-containing fuel is as follows: controlling the chlorine/hydrogen ratio at 12:21, keeping the burning process in a hydrogen deficiency state, so that chlorine with strong oxidizing property is generated by chlorine elements in the residual liquid in the hydrogen deficiency environment, equivalently, strong oxidizing agent is prepared at the same time of combustion, and NO in the waste gas can be oxidized into NO under the joint participation of moisture provided by the falling film absorption process2The purpose of reducing the NO content in the waste gas at the outlet of the incinerator is achieved;
(2) and (2) sequentially cooling, falling film absorption and water washing the waste gas generated in the step (1), then performing alkali washing treatment, adding a strong oxidant into alkali washing liquid subjected to the alkali washing treatment, and finally discharging the waste gas to finish the process of removing NOx in the waste gas generated by the incineration of the tetrachloroethylene residual liquid.
2. The process of claim 1, wherein the fuel containing hydrogen comprises any one of hydrogen, propane and water gas.
3. The process for removing NOx from waste gas generated by burning tetrachloroethylene raffinate according to claim 1, wherein in the step (2), the temperature reduction method comprises the following steps: introducing the waste gas generated in the step (1) into heat exchange equipment to exchange heat with a refrigerant in the heat exchange equipment, and chilling.
4. The process for removing NOx from waste gas generated in the incineration of tetrachloroethylene raffinate according to claim 3, wherein the heat exchange equipment comprises any one of a waste heat boiler and a heat exchanger.
5. The process for removing NOx from waste gas generated by incinerating tetrachloroethylene residue according to claim 1, wherein in the step (2), the alkaline solution comprises any one of sodium hydroxide and sodium carbonate solution.
6. The process for removing NOx from waste gas generated by burning tetrachloroethylene raffinate according to claim 5, wherein the mass concentration of the alkaline wash liquid is in the range of 10 to 15%.
7. The process for removing NOx from a tetrachloroethylene raffinate incineration exhaust gas according to claim 1, wherein the strong oxidant is hypochlorite.
8. The process for removing NOx from a tetrachloroethylene residue incineration exhaust gas according to claim 7, wherein the strong oxidizer comprises any one or more of sodium hypochlorite, potassium hypochlorite and calcium hypochlorite.
9. The process for removing NOx from waste gas generated by burning tetrachloroethylene raffinate according to claim 1, wherein the addition ratio of the strong oxidant in the alkaline washing solution is in the range of 1-2% by mass concentration.
10. The process for removing NOx from waste gas from the incineration of tetrachloroethylene raffinate according to claim 1, wherein in the step (2), the alkali washing treatment is carried out in an alkali washing tower, and the alkali washing liquid is brought into counter-current contact with the waste gas by means of circulating spraying.
11. The process for removing NOx from a waste gas from the incineration of tetrachloroethylene residue according to any one of claims 1 to 10, wherein the step (2) further comprises a metering pump for controlling the amount of the strong oxidizer to be added according to the change of the NOx content in the waste gas.
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