CN112426877B - Method and equipment for treating nitrogen oxide waste gas in sodium metabisulfite production - Google Patents
Method and equipment for treating nitrogen oxide waste gas in sodium metabisulfite production Download PDFInfo
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Abstract
The invention discloses a method and equipment for treating nitrogen oxide waste gas in sodium metabisulfite production, which relate to the technical field of chemical production and comprise the following steps: (1) flushing the waste nitrogen oxide and oxygen into a reaction kettle for oxidation reaction; (2) putting the activated carbon into a reaction kettle, raising the temperature, and carrying out oxidation reaction on the activated carbon; (3) carrying out reduction reaction on the nitrogen oxide under the action of a catalyst, and obtaining mixed gas after the reduction reaction is finished; (4) and (4) reducing the mixed gas at high temperature and high pressure to flush the mixed gas into the alkaline solution to obtain nitrogen, and collecting the nitrogen. The treatment method of the invention has high removal rate of nitrogen oxide, and the finally obtained gas only contains nitrogen, and can be directly put into other industrial production after purification, thereby realizing the cyclic utilization and income creation of resources; the provided equipment can fully improve the contact between gas and gas, gas and solid, improve the reaction efficiency and avoid resource waste and harmful gas generation caused by incomplete reaction.
Description
Technical Field
The invention relates to the technical field of chemical production, in particular to a method and equipment for treating nitrogen oxide waste gas in sodium metabisulfite production.
Background
With the progress of global industrialization, environmental problems are becoming more severe, and even more so, atmospheric pollution, which is one of the major environmental problems, poses a great threat to human health and ecological environment. Nitrogen oxides are one of the most major sources of atmospheric pollution. China is in the high-speed industrial development stage, the total emission amount of nitrogen oxides is in a rapid increasing trend year by year, and the nitrogen oxides are not only one of main sources of acid rain, but also carcinogens, can cause generation of photochemical smog, and can also cause damage to the ozone layer. Therefore, the treatment of nitrogen oxide exhaust gas becomes a problem that nitrogen oxide exhaust gas emission enterprises have to face.
The nitrogen-containing oxide diffuses into the atmosphere and is combined with water vapor in the atmosphere to easily generate acid mist, acid rain and photochemical smog, thereby seriously affecting the normal growth of animals and plants, destroying the ecological balance and threatening the life safety of human beings
Therefore, the national environmental protection department extremely attaches importance to the treatment of the waste gas containing NO, strictly monitors enterprises with NO exhaust emission, and protects the safety of the atmospheric environment.
The gas generated in the production process of sodium metabisulfite contains a large amount of nitrogen oxides, which must be treated and cannot be directly discharged. The waste generated in the production process of sodium metabisulfite can be simply purified to remove the gas except the nitrogen oxide, and then the nitrogen oxide is treated.
The method for treating the nitrogen oxide waste gas mainly comprises a catalytic decomposition method, a solid adsorption method, a microbiological method and a liquid absorption method. The catalytic decomposition method is a method of directly decomposing nitrogen oxides into nitrogen and oxygen by using a catalyst, but this method uses noble metal platinum as a catalyst and is expensive. The solid adsorption method has the advantages of high denitrification efficiency, low cost and simple equipment, but the adsorbent has limited adsorption capacity, needs to be replaced periodically, has short service life and can generate primary pollution. The microbiological method is not high in nitrogen oxide purification efficiency, and the method is still in a test stage at present and needs to be further developed. The liquid absorption method mainly utilizes the principle of dissolution and absorption to purify the nitrogen oxide waste gas, but the liquid absorption method in the prior art has low absorption efficiency of the nitrogen oxide and has insignificant treatment effect.
Chinese published patent application No. CN201080012257.9 discloses a combined waste gas treatment of waste gas streams containing ammonia and nitrogen oxides in industrial plants. Method for combined removal of ammonia in one or more ammonia-containing waste gas streams and also of nitrogen oxides in one or more waste gas streams additionally containing nitrogen oxides in a combined ammonia-urea synthesis plant, with a decomposition rate of up to 80% of the nitrogen oxides being achieved after selective non-catalytic reduction in the temperature range from 850 ℃ to 1100 ℃ or up to 99% of the nitrogen oxides being achieved after selective catalytic reduction in the temperature range from 150 ℃ to 550 ℃, with ammonia and nitrogen oxides reacting with one another and being converted into nitrogen and water, characterized in that the ammonia-containing waste gas stream to be treated in an atmospheric absorber from a low-pressure absorber and/or from a urea synthesis assembly is mixed with the nitrogen oxide-containing waste gas stream to be treated in the flue gas duct of a primary reformer from the combined ammonia-urea synthesis assembly, and a selective non-catalytic reduction or a selective catalytic reduction is carried out depending on the temperature of the mixture and depending on the target decomposition rate of the nitrogen oxides, wherein not only ammonia but also nitrogen oxides in the mixed exhaust gas stream are decomposed simultaneously in the same process step. The catalytic reduction preparation process has high difficulty and high equipment requirement.
In the prior art, other pollution gases are often mixed in the gas finally generated by the treatment of the nitrogen oxide, the obtained nitrogen is impure, and the production cost is high. The most important is that the reaction is not complete due to uneven mixing between gas and solid during the reaction, and the reaction rate is reduced.
Disclosure of Invention
The invention provides a method and equipment for treating nitrogen oxide waste gas in sodium metabisulfite production, wherein the nitrogen oxide removal rate in the treatment method is high, and the finally obtained gas only contains nitrogen and can be directly put into other industrial production after purification, so that the cyclic utilization and income creation of resources are realized; the provided equipment can fully improve the contact between gas and gas, gas and solid, improve the reaction efficiency and avoid resource waste and harmful gas generation caused by incomplete reaction.
The invention relates to a method for treating nitrogen oxide waste gas in sodium metabisulfite production, which comprises the following steps:
(1) the method comprises the following steps of flushing waste nitrogen oxides and oxygen into a reaction kettle, and carrying out oxidation reaction after a period of time, wherein the process is mainly used for firstly oxidizing nitric oxide in the nitrogen oxides into nitrogen dioxide and improving the removal rate of nitrogen in subsequent reaction;
(2) putting activated carbon into a reaction kettle, raising the temperature to 400 ℃ for oxidation reaction of the activated carbon, wherein the mass ratio of the oxygen to the activated carbon is less than or equal to 4:3, and after the activated carbon is added, the activated carbon reacts with insufficient oxygen to generate carbon monoxide;
(3) the nitrogen oxide is subjected to reduction reaction under the action of a catalyst, mixed gas is obtained after the reduction reaction is finished, carbon monoxide and nitrogen dioxide react under the action of the catalyst in the process to generate nitrogen and carbon dioxide, the specific reaction formula is as follows,
4 CO + 2NO2 = 4CO2 + N2 ；
(4) the mixed gas is flushed into the alkaline solution (absorbing nitrogen dioxide possibly remained, carbon monoxide possibly remained and generated carbon dioxide in the reaction) at high temperature and high pressure to obtain nitrogen, and the nitrogen is collected.
The alkaline solution is obtained by mixing potassium hydroxide, sodium hydroxide and ammonia water according to a molar ratio of 1:1: 1. An alkaline solution such as sodium hydroxide can react with carbon monoxide at high temperature and high pressure, and nitrogen dioxide and carbon dioxide which are acidic gases can be adsorbed by the alkaline solution.
Based on the equipment of nitrogen oxide waste gas in sodium metabisulfite production in the foregoing, including reation kettle, set up in the puddler of reation kettle bottom, with nitrogen oxide intake pipe, oxygen intake pipe, active carbon that reation kettle is linked together throw in pipe, outlet duct, reation kettle is equipped with an explosion-proof plug, the reation kettle inner wall is the concave-convex wall of dogleg shape for the cross section, because gas is the jet-propelled form can cause certain impact force to the inner wall after getting into reation kettle, set up to the concave-convex wall of dogleg shape and be favorable to reflecting gas or active carbon powder to different directions, be equivalent to like this between two kinds of gases, carried out even mixture between gas and the solid. When the reaction is carried out, the catalyst is firstly placed into the reaction kettle from the bottle opening of the reaction kettle, the reaction substance is placed into the reaction kettle through the nitrogen oxide air inlet pipe, the oxygen air inlet pipe and the activated carbon feeding pipe, and the reaction kettle can be directly placed under the corresponding high-temperature environment when the temperature is required to be raised.
The stirring rod is provided with a rotating main shaft connected with a micro motor (which can be a motor using a button cell, and the whole structure of the reaction kettle is a structure capable of being sealed and covered so as to replace the button cell in time), and a plurality of stirring supports which are fixedly connected with the rotating main shaft and the length of which is gradually increased from top to bottom. The stirring support is provided with two rows. The active carbon feeding pipe is arranged at the top of the reaction kettle, so that the active carbon falls on the stirring support when being charged, the stirring support rotates, the stirring support from top to bottom can impact the active carbon, the retention time of the active carbon in the space in the reaction kettle is prolonged, the gas accumulation speed is slowed, the contact with oxygen is accelerated, carbon dioxide is generated,
the explosion-proof stopper includes the elastic plug (fill in the stopper of reation kettle bottleneck through the spiro union mode, has fine plasticity elasticity, and the bottleneck is rotatory gone into with the stopper with strength, guarantees sealed in the reation kettle), one end and reation kettle's bottleneck rigid coupling other end with the elastic plug gets top rigid coupling elastic sleeve to can form sealed space in the reation kettle bottle, between elastic sleeve, the elastic plug when the elastic plug receives very big pressure and is bounced. The elastic sleeve is made of elastic resin with folds. The elastic sleeve can be a cylinder surrounded by elastic resin with a certain thickness, which is actually equivalent to a cylindrical side wall, but has good elasticity and can be compressed, then the bottom edge of the cylinder is fixedly connected with the bottle mouth of the reaction kettle, and the edge of the top is fixedly connected with the top of the elastic plug. The elastic plug is screwed with the bottle mouth, the elastic plug can be bounced when the pressure intensity in the bottle is large, gas enters a sealed space between the elastic sleeve and the elastic plug, and the elastic sleeve can be supported to be swelled, so that the explosion-proof purpose is achieved.
The treatment method of the invention has high removal rate of nitrogen oxide, and the finally obtained gas only contains nitrogen, and can be directly put into other industrial production after purification, thereby realizing the cyclic utilization and income creation of resources; the provided equipment can fully improve gas and gas, contact between gas and solid, improve reaction efficiency, and avoid resource waste and harmful gas generation caused by incomplete reaction.
Drawings
FIG. 1 is a schematic structural diagram of a method for treating nitrogen oxide waste gas in the production of sodium metabisulfite according to an embodiment of the present invention.
Wherein: the device comprises a reaction kettle 1, a stirring rod 2, a rotating main shaft 21, a stirring support 22, a nitrogen oxide inlet pipe 3, an oxygen inlet pipe 4, an activated carbon feeding pipe 5, an air outlet pipe 6, an explosion-proof plug 7, an elastic plug 71, an elastic sleeve 72 and a concave-convex wall 8.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present application clearer, the technical solutions in the embodiments of the present application will be clearly and completely described below with reference to the drawings in the embodiments of the present application, and it is obvious that the described embodiments are some embodiments of the present application, but not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present application.
Example 1
A method for treating nitrogen oxide waste gas in sodium metabisulfite production comprises the following steps:
(1) the waste nitrogen oxides and oxygen are flushed into the reaction kettle 1, and oxidation reaction is carried out after a period of time, wherein the process is mainly used for firstly oxidizing nitric oxide in the nitrogen oxides into nitrogen dioxide and improving the removal rate of nitrogen in subsequent reaction;
(2) putting activated carbon into a reaction kettle 1, raising the temperature to 400 ℃ for oxidation reaction of the activated carbon, wherein the mass ratio of the oxygen to the activated carbon is less than or equal to 4:3, and after the activated carbon is added, the activated carbon reacts with insufficient oxygen to generate carbon monoxide;
(3) the nitrogen oxide is subjected to reduction reaction under the action of a catalyst, mixed gas is obtained after the reduction reaction is finished, carbon monoxide and nitrogen dioxide react under the action of the catalyst in the process to generate nitrogen and carbon dioxide, the specific reaction formula is as follows,
4 CO + 2NO2 = 4CO2 + N2 ；
(4) and (4) dropping the mixed gas at high temperature and high pressure to flush the mixed gas into the alkaline solution to obtain nitrogen, and collecting the nitrogen.
The alkaline solution is obtained by mixing potassium hydroxide, sodium hydroxide and ammonia water according to a molar ratio of 1:1: 1.
Example 2
A method for treating nitrogen oxide waste gas in sodium metabisulfite production comprises the following steps:
(1) the waste nitrogen oxides and oxygen are flushed into the reaction kettle 1, and oxidation reaction is carried out after a period of time, wherein the process is mainly used for firstly oxidizing nitric oxide in the nitrogen oxides into nitrogen dioxide and improving the removal rate of nitrogen in subsequent reaction;
(2) putting activated carbon into a reaction kettle 1, raising the temperature to 300-400 ℃, carrying out oxidation reaction on the activated carbon, wherein the mass ratio of the oxygen to the activated carbon is less than or equal to 4:3, and after the activated carbon is added, reacting the activated carbon with insufficient oxygen to generate carbon monoxide;
(3) the nitrogen oxide is subjected to reduction reaction under the action of a catalyst, mixed gas is obtained after the reduction reaction is finished, carbon monoxide and nitrogen dioxide react under the action of the catalyst to generate nitrogen and carbon dioxide in the process, and the specific reaction formula is as follows,
4 CO + 2NO2 = 4CO2 + N2 ；
(4) and (4) reducing the mixed gas at high temperature and high pressure to flush the mixed gas into the alkaline solution to obtain nitrogen, and collecting the nitrogen.
The alkaline solution is obtained by mixing potassium hydroxide, sodium hydroxide and ammonia water according to a molar ratio of 1:1: 1.
Example 3
A method for treating nitrogen oxide waste gas in sodium metabisulfite production comprises the following steps:
(1) the waste nitrogen oxides and oxygen are flushed into the reaction kettle 1, and oxidation reaction is carried out after a period of time, wherein the process is mainly used for firstly oxidizing nitric oxide in the nitrogen oxides into nitrogen dioxide and improving the removal rate of nitrogen in subsequent reaction;
(2) putting activated carbon into a reaction kettle 1, raising the temperature to 400 ℃ for oxidation reaction of the activated carbon, wherein the mass ratio of the oxygen to the activated carbon is less than or equal to 4:3, and after the activated carbon is added, the activated carbon reacts with insufficient oxygen to generate carbon monoxide;
(3) the nitrogen oxide is subjected to reduction reaction under the action of a catalyst, mixed gas is obtained after the reduction reaction is finished, carbon monoxide and nitrogen dioxide react under the action of the catalyst in the process to generate nitrogen and carbon dioxide, the specific reaction formula is as follows,
4 CO + 2NO2 = 4CO2 + N2 ；
(4) and (4) reducing the mixed gas at high temperature and high pressure to flush the mixed gas into the alkaline solution to obtain nitrogen, and collecting the nitrogen.
The alkaline solution is obtained by mixing potassium hydroxide, sodium hydroxide and ammonia water according to a molar ratio of 1:1: 1.
Based on the article a nitrogen oxide waste gas's in sodium metabisulfite production equipment, including reation kettle 1, set up in the puddler 2 of reation kettle 1 bottom, with nitrogen oxide intake pipe 3, oxygen intake pipe 4, active carbon input pipe 5, outlet duct 6 that reation kettle 1 is linked together, reation kettle 1 is equipped with an explosion- proof plug 7, 1 inner wall of reation kettle is zigzag's unsmooth wall 8 for the cross section.
The stirring rod 2 is provided with a micro motor which can be a motor using a button cell, the whole structure of the reaction kettle 1 is a structure which can be sealed and covered so as to replace the button cell in time, and the connected rotating main shaft 21, a plurality of stirring supports 22 are fixedly connected with the rotating main shaft 21 and the length of each stirring support is gradually increased from top to bottom. The stirring supports 22 are provided in two rows. Active carbon input tube 5 should set up at reation kettle 1's top, can drop on stirring support 22 when filling active carbon like this, and stirring support 22 rotates, and stirring support 22 from top to bottom can strike the active carbon, improves the time that the active carbon stops in reation kettle 1's space, slows down the speed that gas is piled up for contact with oxygen, the formation carbon dioxide.
The explosion-proof plug 7 comprises an elastic plug 71, and an elastic sleeve 72 with one end fixedly connected with the mouth of the reaction kettle 1 and the other end fixedly connected with the top of the elastic plug 71, so that a sealed space can be formed in the reaction kettle 1 when the elastic plug 71 receives a large pressure and is bounced, and the elastic sleeve 72 and the elastic plug 71 are arranged in the bottle. The elastic sleeve 72 is an elastic resin with wrinkles.
The elastic plug 71 is screwed with the bottle mouth, the elastic plug 71 can be bounced when the pressure in the bottle is high, and gas enters the space between the elastic sleeve 72 and the elastic plug 71 to form a sealed space, so that the elastic sleeve 72 can be supported to be bulged, and the explosion-proof purpose is achieved.
The treatment method of the invention has high removal rate of nitrogen oxide, and the finally obtained gas only contains nitrogen, and can be directly put into other industrial production after purification, thereby realizing the cyclic utilization and income creation of resources; the provided equipment can fully improve the contact between gas and gas, gas and solid, improve the reaction efficiency and avoid resource waste and harmful gas generation caused by incomplete reaction.
The present invention is not limited to the above-described specific embodiments, and various modifications and variations are possible. Any modifications, equivalent substitutions, improvements and the like of the above embodiments according to the technical essence of the present invention should be included in the scope of protection of the present invention.
Claims (7)
1. A method for treating nitrogen oxide waste gas in sodium metabisulfite production is characterized by comprising the following steps:
(1) filling nitrogen oxide waste gas and oxygen into a reaction kettle for oxidation reaction;
(2) putting activated carbon into a reaction kettle, raising the temperature to 400 ℃, and carrying out oxidation reaction on the activated carbon, wherein the mass ratio of the oxygen to the activated carbon is less than or equal to 4: 3;
(3) carrying out reduction reaction on the nitrogen oxides under the action of a catalyst to generate carbon dioxide and nitrogen, and obtaining mixed gas after the reduction reaction is finished;
(4) and (3) filling the mixed gas into an alkaline solution at high temperature and high pressure, so that residual nitrogen dioxide, carbon monoxide and generated carbon dioxide are absorbed by the alkaline solution to obtain nitrogen, and collecting the nitrogen.
2. The method for treating nitrogen oxide waste gas in sodium metabisulfite production according to claim 1, wherein the alkaline solution is obtained by mixing potassium hydroxide, sodium hydroxide and ammonia water according to a molar ratio of 1:1: 1.
3. The method for treating the nitrogen oxide waste gas in the production of the sodium metabisulfite as claimed in claim 1 or 2, characterized in that the used equipment comprises a reaction kettle, a stirring rod arranged at the bottom of the reaction kettle, a nitrogen oxide inlet pipe, an oxygen inlet pipe, an activated carbon feeding pipe and an air outlet pipe which are communicated with the reaction kettle, the reaction kettle is provided with an explosion-proof plug, and the inner wall of the reaction kettle is a concave-convex wall with a cross section in a fold line shape.
4. The method for treating nitrogen oxide waste gas in the production of sodium metabisulfite as claimed in claim 3, wherein said stirring rod has a rotating main shaft connected with a micro motor, and a plurality of stirring supports fixedly connected with said rotating main shaft and gradually increasing in length from top to bottom.
5. The method for treating nitrogen oxide waste gas in the production of sodium metabisulfite as claimed in claim 4, characterized in that two rows of stirring supports are provided.
6. The method for treating the nitrogen oxide waste gas in the production of the sodium metabisulfite as recited in claim 5, wherein the explosion-proof plug comprises an elastic plug, one end of which is fixedly connected with the mouth of the reaction kettle, and the other end of which is fixedly connected with the top of the elastic plug.
7. The method for treating nitrogen oxide waste gas in the production of sodium metabisulfite as claimed in claim 6, wherein said elastic sleeve is elastic resin with wrinkles.
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| US4704084A (en) * | 1979-12-26 | 1987-11-03 | Battelle Development Corporation | NOX reduction in multisolid fluidized bed combustors |
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