CN212262854U - Single-tower double-circulation desulfurization and denitrification system with cooperation of oxidant and ozone oxidation - Google Patents
Single-tower double-circulation desulfurization and denitrification system with cooperation of oxidant and ozone oxidation Download PDFInfo
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- CN212262854U CN212262854U CN202020667562.2U CN202020667562U CN212262854U CN 212262854 U CN212262854 U CN 212262854U CN 202020667562 U CN202020667562 U CN 202020667562U CN 212262854 U CN212262854 U CN 212262854U
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Abstract
The utility model provides an oxidant is single tower dual cycle SOx/NOx control system of ozone oxidation in coordination, SOx/NOx control system include SOx/NOx control device, the desulfurization take offThe interior of the denitration device is sequentially divided into a desulfurization area, an ozone oxidation area and a denitration area which are communicated along the flow direction of flue gas; and an inlet flue of the desulfurization and denitrification device is sequentially connected with an oxidant supply device and an ozone generating device along the flow direction of flue gas. The utility model discloses based on the synergistic oxidation of oxidant and ozone, low valence state nitrogen oxide and sulfur dioxide in to the flue gas oxidize, and after the flue gas after the oxidation got into SOx/NOx control device, realized single-tower dual cycle SOx/NOx control technology through syllogic's tower body structure, with SO2Absorption process and NOxThe absorption process is isolated, the competitive reaction of the absorption process and the absorption process is reduced, the investment and the operation cost are greatly reduced, and the process is simple and reliable.
Description
Technical Field
The utility model belongs to the technical field of flue gas desulfurization denitration, a single tower dual cycle SOx/NOx control system is related to, especially, relate to a single tower dual cycle SOx/NOx control system of oxidant in coordination with ozonation.
Background
Nitrogen Oxides (NO)x) Is one of the main pollution sources of the atmosphere and is also a difficult problem in the treatment of the atmospheric pollution at present. Known as Nitrogen Oxides (NO)x) Comprising N2O、NO、NO2And N2O3Etc., wherein the atmosphere is contaminated primarily with NO and NO2。
NO emitted by human activitiesxAlthough only about 1/10 for naturally occurring NOx, the emissions are concentrated and hazardous due to high concentrations. NOxThe harm to the natural environment and the production and life of human beings caused by the emission mainly comprises: NOxHas toxic effect on human body; damaging effects on plants: NOxIs the main reason for forming acid rain and acid mist; NOxAnd the carbon dioxide and the hydrocarbon form chemical smog to cause secondary pollution. Therefore, the countries have formulated the content of NOxExhaust emission index, for NOxThe amount and concentration of the emissions are limited. With the increasing requirement of human on environmental protection, NO is addedxWill become more and more demandingIs strict.
Typical processes of the flue gas simultaneous desulfurization and denitrification technology include a dry process and a wet process. At present, SNCR and SCR denitration technologies are generally adopted in China, but NH is adopted in the SCR method3The reducing gas has the disadvantages of difficult transportation, high investment and operation cost, easy inactivation of the catalyst and N emission2O and NH3Secondary pollutants, narrow operation temperature range, complex process and the like; the SNCR method has the defects of low denitration efficiency, high operation temperature, ammonia leakage and the like, and has high investment and operation cost. Therefore, a new dry-method simultaneous desulfurization and denitrification process appears, which comprises the following steps: activated carbon absorption, high-energy electron activation oxidation, and the like.
At present, the wet desulphurization device has high desulphurization efficiency, but the denitration efficiency is almost negligible. This is mainly because the flue gas contains more than 95% of NO, is insoluble in water, and is difficult to be absorbed by the absorbent. Therefore, the development of an economical and feasible flue gas denitration technology is imperative. Research and development of efficient and economical desulfurization and denitrification integrated technology has become a focus of attention of a plurality of research institutions at home and abroad.
But if it is possible to oxidize NO to NO2Higher valence state NO which is readily absorbedxTherefore, denitration can be realized, and the effects of simple process equipment, energy consumption reduction, low treatment cost, space saving and the like are achieved.
The current NO oxidation technologies mainly comprise ozone oxidation, plasma oxidation, chemical additive oxidation and the like. The oxidation absorption process of the chemical additive is relatively simpler and more mature. The sodium-alkali combined desulfurization and denitrification can use the product of NaOH desulfurization to become a reactant for denitrification, and can realize denitrification on the basis of the original desulfurization device, so that the method is economical and feasible, and the integral desulfurization and denitrification system is greatly simplified. Compared with other processes, the method is simple and mature, and can be used for the reconstruction of the original wet desulphurization device. Therefore, the method is undoubtedly an ideal denitration choice for many small and medium-sized enterprises.
SUMMERY OF THE UTILITY MODEL
To the deficiency that prior art exists, the utility model aims to provide an oxidant is ozone oxidation's single tower dual cycle SOx/NOx control in coordinationThe system, the utility model discloses based on the synergistic oxidation of oxidant and ozone, low valence state nitrogen oxide (especially NO), sulfur dioxide and carbon monoxide in to the flue gas oxidize, through the proportion between adjustment oxidant and the ozone, enable the flue gas to reach more than 85% denitration rate and more than 95% desulfurization rate; after the oxidized flue gas enters the desulfurization and denitrification device, the single-tower double-circulation desulfurization and denitrification process is realized through a three-section type tower body structure, and SO is removed2Absorption process and NOxThe absorption process is isolated, the competitive reaction of the absorption process and the absorption process is reduced, the investment and the operation cost are greatly reduced, and the process is simple and reliable.
To achieve the purpose, the utility model adopts the following technical proposal:
in a first aspect, the utility model provides an oxidant is ozone oxidation's single tower dual cycle SOx/NOx control system in coordination, SOx/NOx control system include SOx/NOx control device, SOx/NOx control device inside divide into communicating desulfurization district, ozone oxidation district and denitration district along the flue gas flow direction in proper order.
And an inlet flue of the desulfurization and denitrification device is sequentially connected with an oxidant supply device and an ozone generating device along the flow direction of flue gas.
The utility model is based on the synergistic oxidation of the oxidant and the ozone, the low-valence nitrogen oxides (especially NO) and the sulfur dioxide in the flue gas are oxidized, and the flue gas can reach the denitration rate of more than 85 percent and the desulfurization rate of more than 95 percent by adjusting the proportion between the oxidant and the ozone; after the oxidized flue gas enters the desulfurization and denitrification device, the single-tower double-circulation desulfurization and denitrification process is realized through a three-section type tower body structure, and SO is removed2Absorption process and NOxThe absorption process is isolated, the competitive reaction of the absorption process and the absorption process is reduced, the investment and the operation cost are greatly reduced, and the process is simple and reliable.
As an optimized technical scheme, the oxidant feeding device pass through the import flue that the oxidant supply line inserted SOx/NOx control device.
The outlet end of the oxidant supply pipeline faces to the flue gas inlet direction.
And an atomizing nozzle is arranged at the outlet end of the oxidant supply pipeline.
As an optimal technical scheme, the ozone generating device insert the import flue of SOx/NOx control device through ozone pipeline.
The outlet end of the ozone conveying pipeline faces the smoke gas inlet direction.
The outlet end of the ozone conveying pipeline is provided with an ozone distributor.
The ozone conveying pipeline is provided with an ozone branch pipeline connected into the ozone oxidation area.
As an optimal technical scheme, the import flue of SOx/NOx control device on still be provided with dust collector.
Along the flow direction of the flue gas, the dust removal device is arranged on an inlet flue at the front end of the oxidant supply device.
As an optimized technical proposal of the utility model, the dust removing device is a bag-type dust remover.
As an optimal technical scheme, desulfurization district include desulfurization liquid circulation tank and be located the desulfurization liquid of desulfurization liquid circulation tank top and spray the layer, desulfurization and denitrification device collect at the bottom of the tower and form behind the desulfurization liquid that sprays desulfurization liquid circulation tank, desulfurization liquid circulation tank through the desulfurization liquid circulation pipe connection desulfurization liquid of peripheral hardware spray the layer.
The desulfurization liquid spraying layer comprises a desulfurization liquid spraying main pipe connected with a desulfurization liquid circulating pipeline and at least one desulfurization liquid atomizing nozzle arranged on the desulfurization liquid spraying main pipe.
The desulfurization liquid circulating tank is externally connected with a desulfurization liquid supply device.
The desulfurization liquid circulating tank is sequentially connected with the purifying device and the crystallizing device along the liquid discharge direction.
As a preferred technical proposal of the utility model, the ozone oxidation area comprises an ozone injection component positioned above the desulfurization liquid spraying layer.
The ozone injection assembly comprises an ozone injection main pipe and at least one ozone injection device arranged on the ozone injection main pipe, and the ozone injection main pipe is connected with the ozone branch pipeline.
The spraying direction of the ozone spraying device is the same as the flow direction of the flue gas.
As an optimal technical scheme, denitration district include that the liquid collecting device and the deNOx liquid that is located liquid collecting device top spray the layer, liquid collecting device be used for supplying the ascending flue gas to pass and collect the deNOx liquid that sprays, liquid collecting device collect and form the deNOx liquid circulation pond behind the deNOx liquid that sprays, the deNOx liquid circulation pond through the deNOx liquid circulation pipe connection deNOx liquid of peripheral hardware spray the layer.
The denitration liquid spraying layer comprises a denitration liquid spraying main pipe connected with the denitration liquid circulating pipeline and at least one denitration liquid atomizing nozzle arranged on the denitration liquid spraying main pipe.
It should be further explained that the utility model discloses well liquid collecting device's structure includes the collecting tank of foraminiferous structure, and the flue gas from top to bottom passes the pore structure of collecting tank and rises to get into denitration district, is provided with umbrella type structure hood above the pore structure of collecting tank, sprays the guide inflow collecting tank of liquid through umbrella type structure hood after falling and can not flow into below ozone oxidation district through the pore structure in the spray liquid falls down. Thereby realized that the flue gas passes collection liquid device and rises, and the effect that the liquid that sprays can be separated and collect.
As an optimal technical scheme, the denitration liquid spray layer top still be provided with the absorption liquid and spray the layer, the desulfurization liquid circulation pond connect the absorption liquid through the absorption liquid circulation pipeline of peripheral hardware and spray the layer.
The absorption liquid spraying layer comprises a desulfurization liquid spraying main pipe connected with the absorption liquid circulating pipeline and at least one desulfurization liquid atomizing nozzle arranged on the desulfurization liquid spraying main pipe.
As an optimal technical scheme, along the flue gas flow direction, SOx/NOx control device top of the tower connect fume extractor.
Preferably, the fume extractor is a chimney.
Exemplarily, adopt the utility model provides a single tower dual cycle SOx/NOx control method carries out SOx/NOx control to the flue gas and handles, SOx/NOx control method include oxidant and ozone collaborative oxidation process, desulfurization process, degree of depth oxidation process and denitration process, particularly:
(1) the oxidant and ozone are used for a synergistic oxidation process: the oxidant supply device and the ozone generating device respectively spray oxidant and ozone into the inlet flue, the flue gas is sequentially contacted with the oxidant and the ozone for preliminary oxidation after being introduced into the inlet flue, and NO in the flue gas is oxidized into NO2The mol ratio of the oxidant sprayed into the inlet flue to NO in the flue gas is more than or equal to 0.5, and the contact time of the oxidant and the flue gas is more than or equal to 0.5 s; the molar ratio of the ozone sprayed into the inlet flue to NO in the flue gas is (0.5-1) to 1, and the contact time of the ozone and the flue gas is more than or equal to 0.3 s;
(2) and (3) desulfurization process: the flue gas is deeply dedusted and then input into a desulfurization area through an inlet flue, NaOH solution stored in a desulfurization solution circulating pool is sent into a desulfurization solution spraying layer through a desulfurization solution circulating pipeline, the desulfurization solution spraying layer sprays the NaOH solution, the flue gas and the NaOH solution are in countercurrent contact and absorbed to finish high-efficiency desulfurization, and the NaOH and SO in the flue gas2The molar ratio of (2-3) to (1), and the liquid-gas ratio of the NaOH solution to the flue gas is (8-10) to (1); SO in flue gas2And carrying out absorption reaction with NaOH: 2NaOH + SO2＝Na2SO3+H2O; na produced by the reaction2SO3Returning to the desulfurization liquid circulating pool, and continuously rising the desulfurized flue gas to enter an ozone oxidation zone; when the concentration of the desulfurization absorption liquid generated after desulfurization reaches more than 40 wt%, discharging the desulfurization absorption liquid, allowing the desulfurization absorption liquid to enter a purification device for standing and settling, and introducing the supernatant after settling into a crystallization device for concentration and crystallization;
(3) deep oxidation process: the desulfurized flue gas continuously rises to enter an ozone oxidation zone, ozone generated by an ozone generating device is atomized by an ozone spraying device, the ozone is in downstream contact with the desulfurized flue gas, the molar ratio of the ozone introduced into the ozone oxidation zone to NO in the flue gas is (0.5-1): 1, and the NO which is not completely oxidized in the flue gas is oxidized into NO2：NO+O3＝NO2+O2(ii) a The oxidized smoke continuously rises to pass through the liquid collecting device to enterA denitration zone;
(4) and (3) denitration process: the desulfurization absorption liquid (including Na generated by reaction) stored in the desulfurization liquid circulating pool2SO3And unreacted NaOH) is directly fed into the absorption liquid spraying layer from the desulfurization liquid circulating tank through an absorption liquid circulating pipeline, and Na is added2SO3The solution is sprayed by an absorption liquid spraying layer to be in countercurrent contact with the flue gas, and Na2SO3And NO2The molar ratio of (1-2) to (1), the liquid-gas ratio of the desulfurization absorption liquid to the flue gas is (5-8): 1; na (Na)2SO3NO in solution and flue gas2Carrying out redox reaction to complete denitration; the reacted denitration absorption liquid falls back into the denitration liquid circulating pool, is sent into the denitration spraying absorption layer through the denitration liquid circulating pipeline and is continuously sprayed; NO and NO in flue gas2Spraying an absorption layer and Na in denitration2SO3In full contact with, Na2SO3And NO2The following redox reactions occur: 4Na2SO3+2NO2＝4Na2SO4+N2Finally, efficient denitration is completed; simultaneously incompletely reacted NaOH and NOxThe following reactions occur: 2NaOH + NO2＝2NaNO2+H2O and 2NaOH +2NO2＝NaNO2+NaNO3+H2O。
The system refers to an equipment system, or a production equipment.
Compared with the prior art, the beneficial effects of the utility model are that:
(1) the utility model is based on the synergistic oxidation of the oxidant and the ozone, the low-valence nitrogen oxides (especially NO) and the sulfur dioxide in the flue gas are oxidized, and the flue gas can reach the denitration rate of more than 85 percent and the desulfurization rate of more than 95 percent by adjusting the proportion between the oxidant and the ozone;
(2) the utility model provides a SOx/NOx control system has realized single tower dual cycle SOx/NOx control technology, syllogic tower body structure, with SO2Absorption process and NOxThe absorption process is isolated, so that the competitive reaction of the absorption process and the absorption process is reduced, the investment and the operation cost are greatly reduced, and the process is simple and reliable;
(3) the utility model discloses a sodium-based solution carries out the desulfurization as the desulfurizer, utilizes reaction product to continue to use as the denitration absorbent, has effectively utilized desulfurization product.
Drawings
Fig. 1 is a schematic structural diagram of a desulfurization and denitrification system provided by an embodiment of the present invention.
Wherein, 1-a dust removal device; 2-inlet flue; 3-an oxidant supply; 4-an ozone generating device; 5-a desulfurization and denitrification device; 6-a desulfurization zone; 7-an ozone oxidation zone; 8-a denitration area; 9-desulfurization liquid spraying layer; 10-a desulfurization liquid circulation pipeline; 11-absorption liquid circulation pipeline; 12-a liquid collection device; 13-a denitration liquid spraying layer; 14-an absorption liquid spray layer; 15-denitration liquid circulation pipeline; 16-an ozone spray assembly; 17-a smoke exhaust; 18-a purification device; 19-crystallization device.
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. Furthermore, the terms "first", "second", etc. are used for descriptive purposes only and are not to be construed as indicating or implying relative importance or implicitly indicating the number of technical features indicated. Thus, a feature defined as "first," "second," etc. may explicitly or implicitly include one or more of that feature. In the description of the present invention, "a plurality" means two or more unless otherwise specified.
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 oxidant is single tower dual cycle SOx/NOx control system of ozone oxidation in coordination, SOx/NOx control system as shown in FIG. 1, including SOx/NOx control device 5, SOx/NOx control device 5 inside along flue gas flow direction divide into communicating desulfurization district 6, ozonation district 7 and denitration district 8 in proper order. An inlet flue 2 of the desulfurization and denitrification device 5 is sequentially connected with an oxidant supply device 3 and an ozone generating device 4 along the flow direction of flue gas.
The oxidant supply device 3 is connected to the inlet flue 2 of the desulfurization and denitrification device 5 through an oxidant supply pipeline, the outlet end of the oxidant supply pipeline faces the flue gas inlet direction, and the outlet end of the oxidant supply pipeline is provided with an atomizing nozzle. Ozone generating device 4 inserts SOx/NOx control device 5's import flue 2 through ozone conveying line, and ozone conveying line's exit end is provided with ozone equipartition ware towards flue gas direction of admitting air, ozone conveying line's exit end, is equipped with ozone branch pipeline on the ozone conveying line and inserts ozone oxidation district 7. The inlet flue 2 of the desulfurization and denitrification device 5 is also provided with a dust removal device 1, the dust removal device 1 is arranged on the inlet flue 2 at the front end of the oxidant supply device 3 along the flow direction of flue gas, and the dust removal device 1 is a bag-type dust remover.
The desulfurization zone 6 comprises a desulfurization liquid circulating tank and a desulfurization liquid spraying layer 9 positioned above the desulfurization liquid circulating tank, the sprayed desulfurization liquid is collected at the bottom of the desulfurization and denitrification device 5 to form the desulfurization liquid circulating tank, and the desulfurization liquid circulating tank is connected with the desulfurization liquid spraying layer 9 through an external desulfurization liquid circulating pipeline 10. The desulfurization liquid spraying layer 9 comprises a desulfurization liquid spraying main pipe connected with the desulfurization liquid circulating pipeline 10 and at least one desulfurization liquid atomizing nozzle arranged on the desulfurization liquid spraying main pipe. The desulfurization liquid circulating tank is externally connected with a desulfurization liquid supply device, and the desulfurization liquid circulating tank is sequentially connected with a purifying device 18 and a crystallizing device 19 along the liquid discharge direction.
Ozone oxidation district 7 includes that the doctor solution sprays the ozone injection subassembly 16 of layer 9 top, and ozone injection subassembly 16 includes that the ozone that is connected with ozone branch pipeline sprays the main pipe and sets up at least one ozone injection device on the ozone sprays the main pipe, and ozone injection device's injection direction is the same with the flue gas flow direction.
Denitration district 8 sprays layer 13 including liquid collecting device 12 and the denitration liquid that is located liquid collecting device 12 top, and liquid collecting device 12 is used for supplying the ascending flue gas to pass and collects and sprays the liquid, and liquid collecting device 12 collects and forms denitration liquid circulation pond behind the liquid that sprays, and denitration liquid circulation pond sprays layer 13 through denitration liquid circulation pipeline 15 connection peripheral hardware. The denitration liquid spray layer 13 includes a denitration liquid spray main pipe connected to the denitration liquid circulation pipeline 15 and at least one denitration liquid atomization nozzle provided on the denitration liquid spray main pipe. An absorption liquid spraying layer 14 is further arranged above the denitration liquid spraying layer 13, the desulfurization liquid circulating tank is connected with the absorption liquid spraying layer 14 through an external absorption liquid circulating pipeline 11, and the absorption liquid spraying layer 14 comprises a desulfurization liquid spraying main pipe connected with the absorption liquid circulating pipeline 11 and at least one desulfurization liquid atomizing nozzle arranged on the desulfurization liquid spraying main pipe.
Along the flue gas flow direction, the top of the desulfurization and denitrification device 5 is connected with a smoke exhaust device 17, and the smoke exhaust device 17 is a chimney.
Example 1
The embodiment provides a single-tower double-cycle desulfurization and denitrification method for oxidizing an oxidant in cooperation with ozone, and the method is used for performing desulfurization and denitrification treatment on flue gas; the desulfurization and denitrification method comprises an oxidant and ozone synergistic oxidation process, a desulfurization process, a deep oxidation process and a denitrification process, and specifically comprises the following steps:
(1) the oxidant and ozone are used for a synergistic oxidation process: the oxidant supply device 3 and the ozone generating device 4 respectively spray oxidant (hydrogen peroxide) and ozone into the inlet flue 2, after the flue gas is introduced into the inlet flue 2,sequentially contacted with oxidant and ozone for primary oxidation, NO in the flue gas is oxidized into NO2The mol ratio of the oxidant sprayed into the inlet flue 2 to NO in the flue gas is 0.5, and the contact time of the oxidant and the flue gas is 1.5 s; the mol ratio of the ozone sprayed into the inlet flue 2 to NO in the flue gas is 1:1, and the contact time of the ozone and the flue gas is 0.3 s;
(2) and (3) desulfurization process: the flue gas is deeply dedusted and then is input into a desulfurization area 6 through an inlet flue 2, NaOH solution stored in a desulfurization solution circulating pool is sent into a desulfurization solution spraying layer 9 through a desulfurization solution circulating pipeline 10, the desulfurization solution spraying layer 9 sprays the NaOH solution, the flue gas and the NaOH solution are in countercurrent contact and absorbed to finish high-efficiency desulfurization, and the NaOH and SO in the flue gas2The molar ratio of the NaOH solution to the flue gas is 2:1, and the liquid-gas ratio of the NaOH solution to the flue gas is 10: 1; SO in flue gas2And carrying out absorption reaction with NaOH: 2NaOH + SO2＝Na2SO3+H2O; na produced by the reaction2SO3Returning to the desulfurization liquid circulating pool, and continuously rising the desulfurized flue gas to enter an ozone oxidation zone 7; when the concentration of the desulfurization absorption liquid generated after desulfurization reaches 40 wt%, discharging the desulfurization absorption liquid, allowing the desulfurization absorption liquid to enter a purification device 18 for standing and settling, and introducing the supernatant after settling into a crystallization device 19 for concentration and crystallization;
(3) deep oxidation process: the desulfurized flue gas continuously rises to enter an ozone oxidation zone 7, ozone generated by an ozone generating device 4 is atomized by an ozone spraying device, the ozone is in downstream contact with the desulfurized flue gas, the molar ratio of the ozone introduced into the ozone oxidation zone 7 to NO in the flue gas is 0.5:1, and the NO which is not completely oxidized in the flue gas is oxidized into NO2：NO+O3＝NO2+O2(ii) a The oxidized flue gas continuously rises and passes through the liquid collecting device 12 to enter the denitration area 8;
(4) and (3) denitration process: the desulfurization absorption liquid (including Na generated by reaction) stored in the desulfurization liquid circulating pool2SO3And unreacted NaOH) is directly fed from the desulfurization solution circulation tank into the absorption solution spray layer 14 through the absorption solution circulation pipeline 11, and Na is added2SO3The solution is sprayed by the absorption liquid spraying layer 14 to be in countercurrent contact with the flue gas, Na2SO3And NO2The molar ratio of the desulfurization absorption liquid to the flue gas is 1:1, and the liquid-gas ratio of the desulfurization absorption liquid to the flue gas is 8: 1; na (Na)2SO3NO in solution and flue gas2Carrying out redox reaction to complete denitration; the reacted denitration absorption liquid falls back into the denitration liquid circulating pool, is sent into the denitration spraying absorption layer through the denitration liquid circulating pipeline 15 and is continuously sprayed; NO and NO in flue gas2Spraying an absorption layer and Na in denitration2SO3In full contact with, Na2SO3And NO2The following redox reactions occur: 4Na2SO3+2NO2＝4Na2SO4+N2Finally, efficient denitration is completed; simultaneously incompletely reacted NaOH and NOxThe following reactions occur: 2NaOH + NO2＝2NaNO2+H2O and 2NaOH +2NO2＝NaNO2+NaNO3+H2O。
The flue gas is discharged from the top of the desulfurization and denitrification device 5 through the smoke discharge device 17, and the desulfurization rate and the denitrification rate are calculated by sampling and detecting the discharged flue gas, wherein the desulfurization rate is 96.8 percent, and the denitrification rate is 86.3 percent.
Example 2
The embodiment provides a single-tower double-cycle desulfurization and denitrification method for oxidizing an oxidant in cooperation with ozone, and the method is used for performing desulfurization and denitrification treatment on flue gas; the desulfurization and denitrification method comprises an oxidant and ozone synergistic oxidation process, a desulfurization process, a deep oxidation process and a denitrification process, and specifically comprises the following steps:
(1) the oxidant and ozone are used for a synergistic oxidation process: the oxidant supply device 3 and the ozone generating device 4 respectively spray oxidant (hydrogen peroxide) and ozone into the inlet flue 2, after the flue gas is introduced into the inlet flue 2, the flue gas is sequentially contacted with the oxidant and the ozone for preliminary oxidation, and NO in the flue gas is oxidized into NO2The mol ratio of the oxidant sprayed into the inlet flue 2 to NO in the flue gas is 0.6, and the contact time of the oxidant and the flue gas is 1.2 s; the mol ratio of the ozone sprayed into the inlet flue 2 to NO in the flue gas is 0.9:1, and the contact time of the ozone and the flue gas is 0.4 s;
(2) and (3) desulfurization process: the flue gas is deeply dedusted and then input into a desulfurization area 6 through an inlet flue 2, and NaOH stored in a desulfurization liquid circulation tankThe solution is sent into a desulfurization solution spraying layer 9 through a desulfurization solution circulating pipeline 10, NaOH solution is sprayed by the desulfurization solution spraying layer 9, the flue gas and the NaOH solution are in countercurrent contact and absorbed, the high-efficiency desulfurization is completed, and the NaOH and SO in the flue gas2The molar ratio of the NaOH solution to the flue gas is 2.3:1, and the liquid-gas ratio of the NaOH solution to the flue gas is 9.5: 1; SO in flue gas2And carrying out absorption reaction with NaOH: 2NaOH + SO2＝Na2SO3+H2O; na produced by the reaction2SO3Returning to the desulfurization liquid circulating pool, and continuously rising the desulfurized flue gas to enter an ozone oxidation zone 7; when the concentration of the desulfurization absorption liquid generated after desulfurization reaches 42 wt%, discharging the desulfurization absorption liquid, allowing the desulfurization absorption liquid to enter a purification device 18 for standing and settling, and introducing the supernatant after settling into a crystallization device 19 for concentration and crystallization;
(3) deep oxidation process: the desulfurized flue gas continuously rises to enter an ozone oxidation zone 7, ozone generated by an ozone generating device 4 is atomized by an ozone spraying device, the ozone is in downstream contact with the desulfurized flue gas, the molar ratio of the ozone introduced into the ozone oxidation zone 7 to NO in the flue gas is 0.7:1, and the NO which is not completely oxidized in the flue gas is oxidized into NO2：NO+O3＝NO2+O2(ii) a The oxidized flue gas continuously rises and passes through the liquid collecting device 12 to enter the denitration area 8;
(4) and (3) denitration process: the desulfurization absorption liquid (including Na generated by reaction) stored in the desulfurization liquid circulating pool2SO3And unreacted NaOH) is directly fed from the desulfurization solution circulation tank into the absorption solution spray layer 14 through the absorption solution circulation pipeline 11, and Na is added2SO3The solution is sprayed by the absorption liquid spraying layer 14 to be in countercurrent contact with the flue gas, Na2SO3And NO2The molar ratio of the desulfurization absorption liquid to the flue gas is 1.3:1, and the liquid-gas ratio of the desulfurization absorption liquid to the flue gas is 7: 1; na (Na)2SO3NO in solution and flue gas2Carrying out redox reaction to complete denitration; the reacted denitration absorption liquid falls back into the denitration liquid circulating pool, is sent into the denitration spraying absorption layer through the denitration liquid circulating pipeline 15 and is continuously sprayed; NO and NO in flue gas2Spraying an absorption layer and Na in denitration2SO3In full contact with, Na2SO3And NO2The following redox reactions occur: 4Na2SO3+2NO2＝4Na2SO4+N2Finally, efficient denitration is completed; simultaneously incompletely reacted NaOH and NOxThe following reactions occur: 2NaOH + NO2＝2NaNO2+H2O and 2NaOH +2NO2＝NaNO2+NaNO3+H2O。
The flue gas is discharged from the top of the desulfurization and denitrification device 5 through the smoke discharge device 17, and the desulfurization rate and the denitrification rate are calculated by sampling and detecting the discharged flue gas, wherein the desulfurization rate is 97.2 percent, and the denitrification rate is 89.5 percent.
Example 3
The embodiment provides a single-tower double-cycle desulfurization and denitrification method for oxidizing an oxidant in cooperation with ozone, and the method is used for performing desulfurization and denitrification treatment on flue gas; the desulfurization and denitrification method comprises an oxidant and ozone synergistic oxidation process, a desulfurization process, a deep oxidation process and a denitrification process, and specifically comprises the following steps:
(1) the oxidant and ozone are used for a synergistic oxidation process: the oxidant supply device 3 and the ozone generating device 4 respectively spray oxidant (hydrogen peroxide) and ozone into the inlet flue 2, after the flue gas is introduced into the inlet flue 2, the flue gas is sequentially contacted with the oxidant and the ozone for preliminary oxidation, and NO in the flue gas is oxidized into NO2The mol ratio of the oxidant sprayed into the inlet flue 2 to NO in the flue gas is 0.8, and the contact time of the oxidant and the flue gas is 1 s; the mol ratio of the ozone sprayed into the inlet flue 2 to NO in the flue gas is 0.8:1, and the contact time of the ozone and the flue gas is 0.5 s;
(2) and (3) desulfurization process: the flue gas is deeply dedusted and then is input into a desulfurization area 6 through an inlet flue 2, NaOH solution stored in a desulfurization solution circulating pool is sent into a desulfurization solution spraying layer 9 through a desulfurization solution circulating pipeline 10, the desulfurization solution spraying layer 9 sprays the NaOH solution, the flue gas and the NaOH solution are in countercurrent contact and absorbed to finish high-efficiency desulfurization, and the NaOH and SO in the flue gas2The molar ratio of the NaOH solution to the flue gas is 2.5:1, and the liquid-gas ratio of the NaOH solution to the flue gas is 9: 1; SO in flue gas2And carrying out absorption reaction with NaOH: 2NaOH + SO2＝Na2SO3+H2O; na produced by the reaction2SO3Returning to the desulfurization liquid circulating pool, and desulfurizingThe flue gas continuously rises and enters an ozone oxidation zone 7; when the concentration of the desulfurization absorption liquid generated after desulfurization reaches 45 wt%, discharging the desulfurization absorption liquid, allowing the desulfurization absorption liquid to enter a purification device 18 for standing and settling, and introducing the supernatant after settling into a crystallization device 19 for concentration and crystallization;
(3) deep oxidation process: the desulfurized flue gas continuously rises to enter an ozone oxidation zone 7, ozone generated by an ozone generating device 4 is atomized by an ozone spraying device, the ozone is in downstream contact with the desulfurized flue gas, the molar ratio of the ozone introduced into the ozone oxidation zone 7 to NO in the flue gas is 0.8:1, and the NO which is not completely oxidized in the flue gas is oxidized into NO2：NO+O3＝NO2+O2(ii) a The oxidized flue gas continuously rises and passes through the liquid collecting device 12 to enter the denitration area 8;
(4) and (3) denitration process: the desulfurization absorption liquid (including Na generated by reaction) stored in the desulfurization liquid circulating pool2SO3And unreacted NaOH) is directly fed from the desulfurization solution circulation tank into the absorption solution spray layer 14 through the absorption solution circulation pipeline 11, and Na is added2SO3The solution is sprayed by the absorption liquid spraying layer 14 to be in countercurrent contact with the flue gas, Na2SO3And NO2The molar ratio of the desulfurization absorption liquid to the flue gas is 1.5:1, and the liquid-gas ratio of the desulfurization absorption liquid to the flue gas is 6: 1; na (Na)2SO3NO in solution and flue gas2Carrying out redox reaction to complete denitration; the reacted denitration absorption liquid falls back into the denitration liquid circulating pool, is sent into the denitration spraying absorption layer through the denitration liquid circulating pipeline 15 and is continuously sprayed; NO and NO in flue gas2Spraying an absorption layer and Na in denitration2SO3In full contact with, Na2SO3And NO2The following redox reactions occur: 4Na2SO3+2NO2＝4Na2SO4+N2Finally, efficient denitration is completed; simultaneously incompletely reacted NaOH and NOxThe following reactions occur: 2NaOH + NO2＝2NaNO2+H2O and 2NaOH +2NO2＝NaNO2+NaNO3+H2O。
The flue gas is discharged from the top of the desulfurization and denitrification device 5 through the smoke discharge device 17, and the desulfurization rate and the denitrification rate are calculated by sampling and detecting the discharged flue gas, wherein the desulfurization rate is 98.5 percent, and the denitrification rate is 92.3 percent.
Example 4
The embodiment provides a single-tower double-cycle desulfurization and denitrification method for oxidizing an oxidant in cooperation with ozone, and the method is used for performing desulfurization and denitrification treatment on flue gas; the desulfurization and denitrification method comprises an oxidant and ozone synergistic oxidation process, a desulfurization process, a deep oxidation process and a denitrification process, and specifically comprises the following steps:
(1) the oxidant and ozone are used for a synergistic oxidation process: the oxidant supply device 3 and the ozone generating device 4 respectively spray oxidant (potassium permanganate) and ozone into the inlet flue 2, the flue gas is sequentially contacted with the oxidant and the ozone for preliminary oxidation after being introduced into the inlet flue 2, and NO in the flue gas is oxidized into NO2The mol ratio of the oxidant sprayed into the inlet flue 2 to NO in the flue gas is 0.9, and the contact time of the oxidant and the flue gas is 0.8 s; the mol ratio of the ozone sprayed into the inlet flue 2 to NO in the flue gas is 0.7:1, and the contact time of the ozone and the flue gas is 0.6 s;
(2) and (3) desulfurization process: the flue gas is deeply dedusted and then is input into a desulfurization area 6 through an inlet flue 2, NaOH solution stored in a desulfurization solution circulating pool is sent into a desulfurization solution spraying layer 9 through a desulfurization solution circulating pipeline 10, the desulfurization solution spraying layer 9 sprays the NaOH solution, the flue gas and the NaOH solution are in countercurrent contact and absorbed to finish high-efficiency desulfurization, and the NaOH and SO in the flue gas2The molar ratio of the NaOH solution to the flue gas is 2.8:1, and the liquid-gas ratio of the NaOH solution to the flue gas is 8.5: 1; SO in flue gas2And carrying out absorption reaction with NaOH: 2NaOH + SO2＝Na2SO3+H2O; na produced by the reaction2SO3Returning to the desulfurization liquid circulating pool, and continuously rising the desulfurized flue gas to enter an ozone oxidation zone 7; when the concentration of the desulfurization absorption liquid generated after desulfurization reaches 48 wt%, discharging the desulfurization absorption liquid, allowing the desulfurization absorption liquid to enter a purification device 18 for standing and settling, and introducing the supernatant after settling into a crystallization device 19 for concentration and crystallization;
(3) deep oxidation process: the desulfurized flue gas continuously rises to enter the ozone oxidation zone 7, the ozone generated by the ozone generating device 4 is atomized by the ozone spraying device, the ozone is in downstream contact with the desulfurized flue gas, and the ozone is introduced into the ozone oxidation zone 7The molar ratio of the NO to the NO in the flue gas is 0.9:1, and the NO which is not completely oxidized in the flue gas is oxidized into NO2：NO+O3＝NO2+O2(ii) a The oxidized flue gas continuously rises and passes through the liquid collecting device 12 to enter the denitration area 8;
(4) and (3) denitration process: the desulfurization absorption liquid (including Na generated by reaction) stored in the desulfurization liquid circulating pool2SO3And unreacted NaOH) is directly fed from the desulfurization solution circulation tank into the absorption solution spray layer 14 through the absorption solution circulation pipeline 11, and Na is added2SO3The solution is sprayed by the absorption liquid spraying layer 14 to be in countercurrent contact with the flue gas, Na2SO3And NO2The molar ratio of the desulfurization absorption liquid to the flue gas is 1.8:1, and the liquid-gas ratio of the desulfurization absorption liquid to the flue gas is 5.5: 1; na (Na)2SO3NO in solution and flue gas2Carrying out redox reaction to complete denitration; the reacted denitration absorption liquid falls back into the denitration liquid circulating pool, is sent into the denitration spraying absorption layer through the denitration liquid circulating pipeline 15 and is continuously sprayed; NO and NO in flue gas2Spraying an absorption layer and Na in denitration2SO3In full contact with, Na2SO3And NO2The following redox reactions occur: 4Na2SO3+2NO2＝4Na2SO4+N2Finally, efficient denitration is completed; simultaneously incompletely reacted NaOH and NOxThe following reactions occur: 2NaOH + NO2＝2NaNO2+H2O and 2NaOH +2NO2＝NaNO2+NaNO3+H2O。
The flue gas is discharged from the top of the desulfurization and denitrification device 5 through the smoke discharge device 17, and the desulfurization rate and the denitrification rate are calculated by sampling and detecting the discharged flue gas, wherein the desulfurization rate is 97.3 percent, and the denitrification rate is 90.3 percent.
Example 5
The embodiment provides a single-tower double-cycle desulfurization and denitrification method for oxidizing an oxidant in cooperation with ozone, and the method is used for performing desulfurization and denitrification treatment on flue gas; the desulfurization and denitrification method comprises an oxidant and ozone synergistic oxidation process, a desulfurization process, a deep oxidation process and a denitrification process, and specifically comprises the following steps:
(1) the oxidant and ozone are used for a synergistic oxidation process: the oxidant supply device 3 and the ozone generating device 4 respectively spray oxidant (potassium permanganate) and ozone into the inlet flue 2, the flue gas is sequentially contacted with the oxidant and the ozone for preliminary oxidation after being introduced into the inlet flue 2, and NO in the flue gas is oxidized into NO2The mol ratio of the oxidant sprayed into the inlet flue 2 to NO in the flue gas is 1, and the contact time of the oxidant and the flue gas is 0.5 s; the mol ratio of the ozone sprayed into the inlet flue 2 to NO in the flue gas is 0.5:1, and the contact time of the ozone and the flue gas is 0.8 s;
(2) and (3) desulfurization process: the flue gas is deeply dedusted and then is input into a desulfurization area 6 through an inlet flue 2, NaOH solution stored in a desulfurization solution circulating pool is sent into a desulfurization solution spraying layer 9 through a desulfurization solution circulating pipeline 10, the desulfurization solution spraying layer 9 sprays the NaOH solution, the flue gas and the NaOH solution are in countercurrent contact and absorbed to finish high-efficiency desulfurization, and the NaOH and SO in the flue gas2The molar ratio of the NaOH solution to the flue gas is 3:1, and the liquid-gas ratio of the NaOH solution to the flue gas is 8: 1; SO in flue gas2And carrying out absorption reaction with NaOH: 2NaOH + SO2＝Na2SO3+H2O; na produced by the reaction2SO3Returning to the desulfurization liquid circulating pool, and continuously rising the desulfurized flue gas to enter an ozone oxidation zone 7; when the concentration of the desulfurization absorption liquid generated after desulfurization reaches 50 wt%, discharging the desulfurization absorption liquid, allowing the desulfurization absorption liquid to enter a purification device 18 for standing and settling, and introducing the supernatant after settling into a crystallization device 19 for concentration and crystallization;
(3) deep oxidation process: the desulfurized flue gas continuously rises to enter an ozone oxidation zone 7, ozone generated by an ozone generating device 4 is atomized by an ozone spraying device, the ozone is in downstream contact with the desulfurized flue gas, the molar ratio of the ozone introduced into the ozone oxidation zone 7 to NO in the flue gas is 1:1, and the NO which is not completely oxidized in the flue gas is oxidized into NO2：NO+O3＝NO2+O2(ii) a The oxidized flue gas continuously rises and passes through the liquid collecting device 12 to enter the denitration area 8;
(4) and (3) denitration process: the desulfurization absorption liquid (including Na generated by reaction) stored in the desulfurization liquid circulating pool2SO3And unreacted NaOH) is directly fed into the absorption liquid spray from the desulfurization liquid circulating tank through the absorption liquid circulating pipeline 11Layer 14, Na2SO3The solution is sprayed by the absorption liquid spraying layer 14 to be in countercurrent contact with the flue gas, Na2SO3And NO2The molar ratio of the desulfurization absorption liquid to the flue gas is 2:1, and the liquid-gas ratio of the desulfurization absorption liquid to the flue gas is 5: 1; na (Na)2SO3NO in solution and flue gas2Carrying out redox reaction to complete denitration; the reacted denitration absorption liquid falls back into the denitration liquid circulating pool, is sent into the denitration spraying absorption layer through the denitration liquid circulating pipeline 15 and is continuously sprayed; NO and NO in flue gas2Spraying an absorption layer and Na in denitration2SO3In full contact with, Na2SO3And NO2The following redox reactions occur: 4Na2SO3+2NO2＝4Na2SO4+N2Finally, efficient denitration is completed; simultaneously incompletely reacted NaOH and NOxThe following reactions occur: 2NaOH + NO2＝2NaNO2+H2O and 2NaOH +2NO2＝NaNO2+NaNO3+H2O。
The flue gas is discharged from the top of the desulfurization and denitrification device 5 through the smoke discharge device 17, and the desulfurization rate and the denitrification rate are calculated by sampling and detecting the discharged flue gas, wherein the desulfurization rate is 95.4 percent, and the denitrification rate is 88.6 percent.
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 single-tower double-circulation desulfurization and denitrification system with the cooperation of the oxidant and the ozone for oxidation is characterized by comprising a desulfurization and denitrification device, wherein the interior of the desulfurization and denitrification device is sequentially divided into a desulfurization area, an ozone oxidation area and a denitrification area which are communicated with each other along the flow direction of flue gas;
and an inlet flue of the desulfurization and denitrification device is sequentially connected with an oxidant supply device and an ozone generating device along the flow direction of flue gas.
2. The single-tower double-cycle desulfurization and denitrification system according to claim 1, wherein the oxidant supply device is connected to an inlet flue of the desulfurization and denitrification device through an oxidant supply pipeline;
the outlet end of the oxidant supply pipeline faces the flue gas inlet direction;
and an atomizing nozzle is arranged at the outlet end of the oxidant supply pipeline.
3. The single-tower double-cycle desulfurization and denitrification system according to claim 2, wherein the ozone generating device is connected to an inlet flue of the desulfurization and denitrification device through an ozone conveying pipeline;
the outlet end of the ozone conveying pipeline faces the flue gas inlet direction;
the outlet end of the ozone conveying pipeline is provided with an ozone distributor;
the ozone conveying pipeline is provided with an ozone branch pipeline connected into the ozone oxidation area.
4. The single-tower double-cycle desulfurization and denitrification system according to claim 3, wherein a dust removal device is further arranged on an inlet flue of the desulfurization and denitrification device;
along the flow direction of the flue gas, the dust removal device is arranged on an inlet flue at the front end of the oxidant supply device.
5. The single-tower double-cycle desulfurization and denitrification system according to claim 4, wherein the dust removal device is a bag-type dust remover.
6. The single-tower double-cycle desulfurization and denitrification system according to claim 5, wherein the desulfurization zone comprises a desulfurization solution circulation tank and a desulfurization solution spray layer positioned above the desulfurization solution circulation tank, the desulfurization solution circulation tank is formed after the sprayed desulfurization solution is collected at the bottom of the desulfurization and denitrification device, and the desulfurization solution circulation tank is connected with the desulfurization solution spray layer through an external desulfurization solution circulation pipeline;
the desulfurization solution spraying layer comprises a desulfurization solution spraying main pipe connected with a desulfurization solution circulating pipeline and at least one desulfurization solution atomizing nozzle arranged on the desulfurization solution spraying main pipe;
the desulfurization liquid circulating tank is externally connected with a desulfurization liquid supply device;
the desulfurization liquid circulating tank is sequentially connected with the purifying device and the crystallizing device along the liquid discharge direction.
7. The system of claim 6, wherein the ozone oxidation zone comprises an ozone injection assembly located above the desulfurization solution spray layer;
the ozone injection assembly comprises an ozone injection main pipe and at least one ozone injection device arranged on the ozone injection main pipe, and the ozone injection main pipe is connected with an ozone branch pipeline;
the spraying direction of the ozone spraying device is the same as the flow direction of the flue gas.
8. The single-tower double-cycle desulfurization and denitrification system according to claim 7, wherein the denitrification zone comprises a liquid collecting device and a denitrification liquid spraying layer positioned above the liquid collecting device, the liquid collecting device is used for allowing the ascending flue gas to pass through and collecting the sprayed denitrification liquid, the liquid collecting device collects the sprayed denitrification liquid to form a denitrification liquid circulating pool, and the denitrification liquid circulating pool is connected with the denitrification liquid spraying layer through an external denitrification liquid circulating pipeline;
the denitration liquid spraying layer comprises a denitration liquid spraying main pipe connected with the denitration liquid circulating pipeline and at least one denitration liquid atomizing nozzle arranged on the denitration liquid spraying main pipe.
9. The single-tower double-cycle desulfurization and denitrification system according to claim 8, wherein an absorption liquid spraying layer is further arranged above the denitrification liquid spraying layer, and the desulfurization liquid circulating tank is connected with the absorption liquid spraying layer through an external absorption liquid circulating pipeline;
the absorption liquid spraying layer comprises a desulfurization liquid spraying main pipe connected with the absorption liquid circulating pipeline and at least one desulfurization liquid atomizing nozzle arranged on the desulfurization liquid spraying main pipe.
10. The system according to claim 9, wherein the top of the desulfurization and denitrification device is connected with a smoke exhaust device along the flow direction of flue gas;
the fume extractor is a chimney.
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| CN113577933A (en) * | 2021-09-28 | 2021-11-02 | 江苏绿叶环境工程集团有限公司 | Flue gas desulfurization and denitrification system |
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| CN111467943A (en) * | 2020-04-27 | 2020-07-31 | 广东佳德环保科技有限公司 | Single-tower double-cycle desulfurization and denitrification system and method with cooperation of oxidant and ozone oxidation |
| CN113577933A (en) * | 2021-09-28 | 2021-11-02 | 江苏绿叶环境工程集团有限公司 | Flue gas desulfurization and denitrification system |
| CN113577933B (en) * | 2021-09-28 | 2021-12-03 | 江苏绿叶环境工程集团有限公司 | Flue gas desulfurization and denitrification system |
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