CN211987926U - Ozone oxidation's integrated purification system of flue gas - Google Patents
Ozone oxidation's integrated purification system of flue gas Download PDFInfo
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- CN211987926U CN211987926U CN202020215831.1U CN202020215831U CN211987926U CN 211987926 U CN211987926 U CN 211987926U CN 202020215831 U CN202020215831 U CN 202020215831U CN 211987926 U CN211987926 U CN 211987926U
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Abstract
The utility model provides an ozone oxidation comprehensive flue gas purification system, which comprises an ozone generating device, a spraying absorption device and a urea reduction device; the ozone generatorThe outlet of the generating device is divided into two independent pipelines which are respectively marked as an ozone injection pipeline outside the tower and an ozone injection pipeline inside the tower; the outlet end of the ozone injection pipeline outside the tower is connected to an air inlet flue of the spraying absorption device; the outlet end of the ozone injection pipeline in the tower extends into the spraying absorption device; the spraying absorption device is circularly connected with the urea reduction device. The utility model combines the gas phase oxidation and the liquid phase oxidation of ozone, thereby strengthening NO in the flue gasxThe oxidation absorption effect of (1). Reducing nitrite in absorption liquid to N by reducing property of urea2The recycling of the spraying liquid is realized, the treatment cost is saved, and the environmental problem caused by emission is also avoided.
Description
Technical Field
The utility model belongs to the technical field of the flue gas is handled, a clean system is synthesized to flue gas is related to, especially relate to a clean system is synthesized to ozone oxidation's flue gas.
Background
Along with the increasing attention on environmental protection, the emission standards of flue gas pollutants in multiple industries in China are becoming strict, and the desulfurization and dust removal facilities are basically popularized, compared with the nitrogen oxide NOxThe treatment becomes the key for restricting the environmental protection and upgrading. NO for steel industry of ChinaxThe discharge amount is second to power station boilers and cement kilns and is third in the industry. NO in the iron and steel industryxOf the emissions, 50% or more come from the sintering process. The sintering flue gas has large flow (100 ten thousand m3/h), low flue gas temperature (120 ℃ -xThe large concentration fluctuation (180-600mg/m3) becomes a difficult point for environmental management. In recent years, NOxParticular emissions limits have been mentioned from 300mg/m3 to 100mg/m3, and some enterprises have even proposed an ultra-low emission standard of 50mg/m 3. Thus, a large amount of NO in the sintering machinexThe standard is not reached. Therefore, the development of the sintering flue gas low-temperature denitration technology is urgent.
The existing sintering flue gas denitration technology mainly comprises an activated carbon technology, a Selective Catalytic Reduction (SCR) technology and an oxidation denitration technology. The activated carbon technology is practicalThe existing sulfur and nitrate integrated control, but the existing sintering flue gas activated carbon engineering case shows that a lower airspeed needs to be adopted during operation, so that the using amount of activated carbon is very large, and the activated carbon needs to be heated and regenerated, so that the operation cost is very high. The SCR denitration technology is to spray a reducing agent into flue gas and add NO in the presence of a catalystxReduction to N2The operating temperature of the medium-high temperature SCR is generally 280-320 ℃, the operating temperature of the medium-low temperature SCR is generally 220-280 ℃, and the two denitration technologies need to reheat the flue gas of the sintering flue gas, so that the operating cost of the existing SCR technology is higher, the existing catalyst is basically a vanadium-based catalyst, and the waste catalyst is dangerous waste and is difficult to treat. The oxidation denitration technology is that before the flue gas enters the desulfurizing tower, ozone or other oxidant is sprayed to oxidize NO in the flue gas into NO2Or N2O5And the high-valence nitrogen oxides can realize synchronous desulfurization and denitrification in the desulfurization tower.
CN103977679A discloses a method and a system for simultaneously desulfurizing and denitrating sintering flue gas by a graded oxidation absorption method, wherein sodium hypochlorite and potassium permanganate solution are used for carrying out spray oxidation on the sintering flue gas in a first-level oxidation tower, and NO is subjected to spray oxidationxAnd SO2By oxidation to NO2And SO3(ii) a Spraying and absorbing the sintered flue gas after spraying and oxidizing by using an absorbent solution in a secondary absorption tower to remove NO2And SO3Absorbing; and finally, discharging the sintering flue gas after spray oxidation and spray absorption. The method needs sodium hypochlorite and potassium permanganate chemicals as oxidants and can only oxidize NO in the flue gas into NO2And NO2Limited intrinsic absorption capacity, initial NOxYellow smoke is likely to appear at higher concentrations. Further, SO is added2Oxidation to SO3A large amount of oxidant is also consumed.
With the gradual maturity of ozone generators, ozone becomes the oxidant most widely applied in oxidation and denitration technologies. For example, CN105854554A discloses an ozone low-temperature oxidation denitration system, which includes a flue, an ozone generator, and a scrubber, wherein an ozone distributor is installed in the flue, an outlet of the ozone generator supplies ozone into an ozone channel of the ozone distributor through a pipeline, the ozone is sprayed into the flue through the ozone distributor, and an outlet of the flue is connected to the scrubber, so that a mixed gas of ozone and flue gas in the flue enters the scrubber. CN205461724U discloses a high-efficient reaction unit for ozone denitration process, including flue gas pipeline and ozone injection mechanism, be provided with ozone reaction platform in the flue gas pipeline, be provided with a plurality of spoilers in the ozone reaction platform, ozone injection mechanism sets up the flue gas entry end of flue gas pipeline. CN201832548U discloses a denitration treatment device for purifying flue gas, including the denitration absorber, the denitration absorber includes that both ends are equipped with flue gas inlet and exhanst gas outlet's casing respectively, bottom in the casing includes alkali lye holding district, alkali lye holding district top is equipped with the multilayer and sprays the shower nozzle, still includes flue blender and ozone generator, the flue blender with the flue gas entry of taking off the round pin absorber links to each other, the flue blender include that ozone leads to the mouth, and with the mixing reaction chamber of ozone access mouth intercommunication, ozone lead to the mouth with ozone generator pipe connection.
In the application of ozone oxidation denitration engineering, the problems of incomplete oxidation of NO in flue gas, complex byproduct components and the like exist, and the popularization and application of an ozone oxidation method are limited.
SUMMERY OF THE UTILITY MODEL
To the deficiency that exists of the prior art, the utility model aims to provide an ozone oxidation's comprehensive clean system of flue gas, the utility model discloses combine together ozone's gas phase oxidation and liquid phase oxidation, strengthened NO in to the flue gasxThe oxidation absorption effect of (1). Reducing nitrite in absorption liquid to N by reducing property of urea2The recycling of the spraying liquid is realized, the treatment cost is saved, and the environmental problem caused by emission is also avoided.
To achieve the purpose, the utility model adopts the following technical proposal:
the utility model provides a clean system is synthesized to ozone oxidation's flue gas, the clean system is synthesized to flue gas include ozone generating device, spray absorbing device and urea reduction device.
The outlet of the ozone generating device is divided into two independent pipelines which are respectively marked as an ozone spraying pipeline outside the tower and an ozone spraying pipeline inside the tower; the outlet end of the ozone injection pipeline outside the tower is connected to an air inlet flue of the spraying absorption device; the outlet end of the ozone injection pipeline in the tower extends into the spraying absorption device.
The spraying absorption device is circularly connected with the urea reduction device.
The utility model combines the gas phase oxidation and the liquid phase oxidation of ozone, thereby strengthening NO in the flue gasxThe oxidation absorption effect of (1). A part of the ozone generated by the ozone generating device is mixed with the flue gas before entering the spray absorption device through an ozone injection pipeline outside the tower, so that the NO in the flue gas is fully subjected to gas phase oxidation; simultaneously, the rest ozone is mixed with the absorption liquid in the spray absorption device through the ozone injection pipeline in the tower, SO that SO dissolved in water can be treated during spraying2Liquid phase oxidation is carried out, and the oxidation product is SO4 2-. The ozone can oxidize SO in liquid phase2The oxidation is directly carried out to the high-valence compound, an additional oxidation device is not required to be added, the oxidation effect is more sufficient, and the problem of incomplete oxidation in the prior art is effectively solved. In addition, contain nitrite in the absorption liquid after spraying the absorption, if this absorption liquid direct discharge not only can cause the increase of treatment cost, more importantly can cause serious destruction to soil environment, consequently the utility model provides a clean system is synthesized to flue gas adds at the rear end that sprays absorbing device and has established urea reduction device, through the reductibility of urea with the nitrite reduction in the absorption liquid for N2The recycling of the spraying liquid is realized, the treatment cost is saved, and the environmental problem caused by emission is also avoided.
It should be noted that the ozone generator of the present invention belongs to the technical field of ozone application, and the structure thereof is well known to those skilled in the art, and can be a discharge type generator or an electrolyzed water generator. The discharge type generator generates ozone by electrolyzing air or pure oxygen, but the content of impurity gas therein is high. The ozone generated by the electrolyzed water generating device is dissolved in the water to form the ozoneCan be used for producing ozone with high purity, and is widely applied to the fields of beverages, precision part cleaning, surface treatment and the like. The utility model discloses the preferred discharge type generating device that adopts. Exemplarily, the ozone generating device of the utility model mainly comprises a liquid oxygen storage tank, a vaporizer and an ozone generator, wherein the liquid oxygen storage tank is a low-temperature storage tank for storing liquid oxygen, can replace the multiple round trip transportation of a gas cylinder, saves manpower and cost, and is the first choice for centralized gas supply; the vaporizer is an industrial and civil energy-saving device and is used for converting liquid gas into gaseous gas; the ozone generator is used for producing ozone gas (O)3) The apparatus of (1). Ozone is easy to decompose and cannot be stored, and the ozone needs to be prepared on site for use (the ozone can be stored for a short time under special conditions), so that an ozone generator is needed to be used in all places where the ozone can be used. When in use, the liquid oxygen in the liquid oxygen storage tank is changed into gaseous oxygen through the vaporizer, and then ozone is obtained through the ozone generator.
As a preferred technical proposal of the utility model, the outlet end of the ozone injection pipeline in the tower is provided with at least one nozzle.
And independently controlled valves are respectively arranged on the ozone injection pipeline outside the tower and the ozone injection pipeline inside the tower.
In the utility model, the flue gas is mixed with a part of ozone before entering the spray absorption device to carry out gas phase oxidation. The other part of ozone is sprayed into the spraying absorption device through an ozone spraying pipeline in the tower and is mixed with the spraying liquid to form ozone-water mixed absorption liquid, the flue gas enters the spraying absorption device after gas phase oxidation and is in countercurrent contact absorption with the ozone-water mixed absorption liquid, and the flue gas is sprayed through a spraying layer to perform liquid phase oxidation on the flue gas and simultaneously complete flue gas denitration.
As an optimized technical scheme, the external at least circulation pipeline in absorption device bottom spray, circulation pipeline's exit end stretch into inside spraying absorption device, the absorption liquid that sprays the absorption device bottom and store sprays through the circulation pipeline circulation.
As a preferred technical scheme of the utility model, the exit end of circulation pipeline set up at least one nozzle.
And the circulating pipeline is provided with a circulating pump.
As an optimal technical scheme, spray absorbing device bottom and pass through the external urea of fluid-discharge line and restore the device, urea restore the leakage fluid dram of device and connect through absorption liquid return line and spray absorbing device, spray the absorption liquid after the absorption and restore the backward flow to spraying absorbing device cyclic utilization through urea.
In the comprehensive flue gas purification system provided by the utility model, the oxidability of ozone oxidizes NO into NO2NO and NO2The nitrite is converted under the alkaline condition, the nitrous acid solution and the urea solution are mixed in liquid phase, and the reaction is easier than the gas-gas mixing reaction of NO and ammonia, and NO is converted into nitrite under the alkaline conditionxThe removal rate of the urea is greatly improved, and the absorption liquid after urea reduction is regenerated and recycled.
The liquid discharge pipeline is provided with an electromagnetic valve, and the outlet end of the absorption liquid return pipeline extends into the spraying absorption device.
As an optimized technical proposal of the utility model, the outlet end of the absorption liquid return pipeline is provided with at least one nozzle.
As an optimized technical scheme, the absorbing device bottom that sprays built-in pH detection device, pH detection device be used for real-time detection to spray the absorption liquid pH value after absorbing.
As an optimal technical scheme, the fume outlet department that sprays absorbing device still be provided with the defogging device.
As an optimal technical scheme, the comprehensive purification system of flue gas still include feedback control device, feedback control device be used for receiving the pH value data of pH detection device transmission, according to opening of the result control solenoid valve of logic judgement.
As an optimized technical proposal, the comprehensive flue gas purification system also comprises a chimney connected with a flue gas outlet of the spray absorption device.
The system refers to an equipment system, or a production equipment.
The utility model provides an ozone oxidation's integrated purification system of flue gas's operation process includes following step:
(1) after the flue gas is introduced into the air inlet flue, the flue gas is fully mixed with one path of ozone gas from the ozone generating device, NO gas in the flue gas is oxidized into high-valence nitrogen oxide, and then the high-valence nitrogen oxide enters the spray absorption device;
(2) in the spray absorption device, the spray liquid stored at the bottom of the spray absorption device is circularly sprayed by a circulating pipeline, the flue gas is in countercurrent contact with another path of ozone gas from an ozone generation device and the circularly sprayed absorption liquid, and NO is generatedxAfter being absorbed by the absorbent and oxidized by ozone, the nitrite is converted into nitrite and falls back to the bottom of the spraying absorption device. The flue gas is desulfurized and denitrated, then passes through a demisting device for demisting and drying, and enters a urea reduction device;
(3) in a urea reduction device, absorption liquid waste water containing nitrite is mixed with urea and reduced into N2The absorption liquid is regenerated and flows back to the spraying absorption device for cyclic utilization.
(4) The flue gas is discharged from the urea reduction device and is exhausted through a chimney.
Compared with the prior art, the beneficial effects of the utility model are that:
(1) the utility model combines the gas phase oxidation and the liquid phase oxidation of ozone, thereby strengthening NO in the flue gasxThe oxidation absorption effect of (1). A part of the ozone generated by the ozone generating device is mixed with the flue gas before entering the spray absorption device through an ozone injection pipeline outside the tower, so that the NO in the flue gas is fully subjected to gas phase oxidation; simultaneously, the rest ozone is mixed with the absorption liquid in the spray absorption device through the ozone injection pipeline in the tower, SO that SO dissolved in water can be treated during spraying2Liquid phase oxidation is carried out, and the oxidation product is SO4 2-. The ozone can oxidize SO in liquid phase2The oxidation is directly carried out to the high-valence compound, an additional oxidation device is not required to be added, the oxidation effect is more sufficient, and the problem of incomplete oxidation in the prior art is effectively solved.
(2) The utility model provides a clean system is synthesized to flue gas adds in the rear end that sprays absorbing device and has established urea reduction device, and the reductibility through urea reduces the nitrite in the absorption liquid to N2The recycling of the spraying liquid is realized, the treatment cost is saved, and the environmental problem caused by emission is also avoided.
Drawings
Fig. 1 is a schematic structural diagram of a comprehensive flue gas purification system according to an embodiment of the present invention.
Wherein, 1-an ozone generating device; 2-a spray absorption device; 3-urea reduction unit; 4-a demisting device; 5-chimney.
Detailed Description
It is to be understood that in the description of the present invention, the terms "central," "longitudinal," "lateral," "upper," "lower," "front," "rear," "left," "right," "vertical," "horizontal," "top," "bottom," "inner," "outer," and the like are used in the orientation or positional relationship indicated in the drawings for the purpose of convenience and simplicity of description, and are not intended to indicate or imply that the referenced device or element must have a particular orientation, be constructed and operated in a particular orientation, and are not to be construed as limiting the present invention.
It should be noted that, unless explicitly stated or limited otherwise, the terms "disposed," "connected" and "connected" in the description of the present invention are to be construed broadly, and may for example be fixedly connected, detachably connected or integrally connected; can be mechanically or electrically connected; they may be connected directly or indirectly through intervening media, or they may be interconnected between two elements. The specific meaning of the above terms in the present invention can be understood by those of ordinary skill in the art through specific situations.
The technical solution of the present invention is further explained by the following embodiments with reference to the accompanying drawings.
In a specific embodiment, the utility model provides an ozone oxidation comprehensive purification system for flue gas, which comprises an ozone generating device 1, a spray absorbing device 2 and a urea reducing device 3; the outlet of the ozone generating device 1 is divided into two independent pipelines which are respectively marked as an ozone spraying pipeline outside the tower and an ozone spraying pipeline inside the tower. Wherein, the outlet end of the ozone injection pipeline outside the tower is connected to the air inlet flue of the spray absorption device 2; the outlet end of the ozone injection pipeline in the tower extends into the spraying absorption device 2, and the spraying absorption device 2 is circularly connected with the urea reduction device 3.
The outlet end of the ozone injection pipeline in the tower is provided with at least one nozzle, and the ozone injection pipeline outside the tower and the ozone injection pipeline in the tower are respectively provided with independently controlled valves. The bottom of the spraying absorption device 2 is externally connected with at least one circulation pipeline, the outlet end of the circulation pipeline extends into the spraying absorption device 2, and the absorption liquid stored at the bottom of the spraying absorption device 2 is circularly sprayed through the circulation pipeline. The outlet end of the circulating pipeline is provided with at least one nozzle, and the circulating pipeline is provided with a circulating pump.
The bottom of the spraying absorption device 2 is externally connected with a urea reduction device 3 through a liquid discharge pipeline, a liquid discharge port of the urea reduction device 3 is connected with the spraying absorption device 2 through an absorption liquid return pipeline, absorption liquid after being sprayed and absorbed is reduced and flows back to the spraying absorption device 2 through urea, an electromagnetic valve is arranged on the liquid discharge pipeline for cyclic utilization, and the outlet end of the absorption liquid return pipeline extends into the spraying absorption device 2. The outlet end of the absorption liquid return pipeline is provided with at least one nozzle.
And a pH detection device is arranged in the bottom of the spraying absorption device 2 and is used for detecting the pH value of the absorption liquid after spraying absorption in real time. The comprehensive flue gas purification system also comprises a feedback control device, wherein the feedback control device is used for receiving the pH value data transmitted by the pH detection device and controlling the opening of the electromagnetic valve according to the logical judgment result.
And a demisting device 4 is also arranged at the flue gas outlet of the spraying absorption device 2.
The comprehensive flue gas purification system also comprises a chimney 5 connected with the flue gas outlet of the spray absorption device 2.
The flue gas comprehensive purification system provided by the specific implementation mode is adopted to carry out denitration treatment on flue gas, and the method specifically comprises the following steps:
(1) after the flue gas is introduced into the air inlet flue, the flue gas is fully mixed with one path of ozone gas from the ozone generating device 1, NO gas in the flue gas is oxidized into high-valence nitrogen oxide, and then the high-valence nitrogen oxide enters the spraying absorption device 2; the molar ratio of the introduced path of ozone to NO in the flue gas is 0.8-1.2;
the reaction taking place is NO + O3→NO2+O2
(2) In the spray absorption device 2, spray liquid stored at the bottom of the spray absorption device 2 is circularly sprayed through a circulating pipeline, the flue gas is in countercurrent contact with another path of ozone gas from the ozone generation device 1 and absorption liquid which is circularly sprayed, the mole ratio of the introduced another path of ozone to NO in the flue gas is 0.8-1.2, and the liquid-gas ratio in the spray absorption device 2 is 7-10L/m3；NO2And residual NO is circularly sprayed and absorbed by absorption liquid (alkali liquor) and then is converted into nitrite;
the reactions that take place mainly include:
NO+O3→NO2+O2
NO+NO2+H2O→2HNO2
NO+NO2+2NaOH→2NaNO2+H2O。
in the circulating spraying process, the pH detection device detects the pH value of the absorption liquid in real time and transmits data to the feedback control device, once the feedback control device receives that the pH value is less than 5, the electromagnetic valve is controlled to be opened, and the spraying liquid at the bottom of the spraying absorption device 2 is discharged into the urea reduction device 3;
(3) in a urea reduction device 3, the absorption liquid waste water containing nitrite is mixed with urea and reduced into N2The absorption liquid is regenerated and flows back to the spraying absorption device 2 for cyclic utilization.
The reactions that take place mainly include:
2NaNO2+CO(NH2)2→Na2CO3+2N2↑+2H2O
Na2CO3+Ca(OH)2→CaCO3↓+2NaOH
(4) the flue gas is discharged from the spraying and is exhausted through a chimney 5.
The applicant states that the above description is only a specific embodiment of the present invention, but the protection scope of the present invention is not limited thereto, and those skilled in the art should understand that any changes or substitutions easily conceivable by those skilled in the art within the technical scope of the present invention are within the protection scope and the disclosure scope of the present invention.
Claims (10)
1. The comprehensive purification system for the ozone-oxidized flue gas is characterized by comprising an ozone generating device, a spraying and absorbing device and a urea reducing device;
the outlet of the ozone generating device is divided into two independent pipelines which are respectively marked as an ozone spraying pipeline outside the tower and an ozone spraying pipeline inside the tower; the outlet end of the ozone injection pipeline outside the tower is connected to an air inlet flue of the spraying absorption device; the outlet end of the ozone injection pipeline in the tower extends into the spraying absorption device;
the spraying absorption device is circularly connected with the urea reduction device.
2. The comprehensive flue gas purification system of claim 1, wherein the outlet end of the in-tower ozone injection pipeline is provided with at least one nozzle;
and independently controlled valves are respectively arranged on the ozone injection pipeline outside the tower and the ozone injection pipeline inside the tower.
3. The comprehensive flue gas purification system of claim 2, wherein the bottom of the spray absorption device is externally connected with at least one circulation pipeline, the outlet end of the circulation pipeline extends into the spray absorption device, and the absorption liquid stored at the bottom of the spray absorption device is sprayed by the circulation pipeline in a circulating manner.
4. The integrated flue gas purification system according to claim 3, wherein at least one nozzle is arranged at the outlet end of the circulation pipeline;
and the circulating pipeline is provided with a circulating pump.
5. The comprehensive flue gas purification system of claim 4, wherein the bottom of the spray absorption device is externally connected with a urea reduction device through a liquid discharge pipeline, a liquid discharge port of the urea reduction device is connected with the spray absorption device through an absorption liquid return pipeline, and the absorption liquid after spray absorption is reduced and returned to the spray absorption device through urea for recycling;
the liquid discharge pipeline is provided with an electromagnetic valve, and the outlet end of the absorption liquid return pipeline extends into the spraying absorption device.
6. The integrated flue gas purification system according to claim 5, wherein the outlet end of the absorption liquid return line is provided with at least one nozzle.
7. The comprehensive flue gas purification system according to claim 6, wherein a pH detection device is arranged in the bottom of the spray absorption device, and the pH detection device is used for detecting the pH value of the absorption liquid after spray absorption in real time.
8. The integrated flue gas purification system according to claim 7, wherein a demister is further disposed at the flue gas outlet of the spray absorption device.
9. The comprehensive flue gas purification system according to claim 8, further comprising a feedback control device for receiving the pH value data transmitted by the pH detection device and controlling the opening of the solenoid valve according to the logical judgment result.
10. The integrated flue gas purification system of claim 9, further comprising a chimney connected to the flue gas outlet of the spray absorber.
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