CN106731585B - Coke oven flue gas dry-type desulfurization device, coke oven flue gas dry-type desulfurization and dust removal integrated system and method - Google Patents
Coke oven flue gas dry-type desulfurization device, coke oven flue gas dry-type desulfurization and dust removal integrated system and method Download PDFInfo
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Abstract
The invention provides a dry-type desulfurization device for coke oven flue gas, a desulfurization and dust removal integrated system and a method thereof, wherein the desulfurization device comprises an air inlet flue, a primary fluidized bed section, a Venturi section, a conical section and a secondary fluidized bed section which are sequentially communicated from the bottom to the top; the first-stage fluidized bed section is provided with a solid sodium-based absorbent supply unit; a solid calcium-based absorbent supply unit is arranged at the joint of the first-stage fluidized bed section and the Venturi section; the secondary fluidized bed section has an outlet. The integrated desulfurization and dust removal system provided by the invention takes a novel desulfurization device and a dust removal device as a core, and mainly comprises a high-temperature first-stage fluidized bed section, a low-temperature high-turbulence second-stage fluidized bed section, a solid absorbent supply unit and the like. Through the system, the invention can efficiently remove SO X The removal efficiency is up to more than 98 percent, and SO in the coke oven flue gas can be removed X And hydrogen sulfide, tar and ultrafine dust particles are removed in a package, so that the national environmental protection emission standard is met, and the coke oven smoke treatment is realized.
Description
Technical Field
The invention relates to the technical field of coke oven flue gas treatment, in particular to a coke oven flue gas dry-type desulfurization device, a coke oven flue gas dry-type desulfurization and dust removal integrated system and a method thereof.
Background
The coke oven being coke-making from coalThe kiln can generate a large amount of smoke in the processes of coal charging, coke pushing, coke quenching and production. The coke oven smoke contains H 2 S, the front end gas desulfurization device can not completely remove H 2 S, coke oven gas participates in combustion to supply heat to generate SO 2 The concentration is 80-450 mg/m 3 . Compared with the flue gas parameters of a power plant, the flue gas of the coke oven has the following characteristics:
1) The coke oven flue gas temperature is relatively low. The flue gas temperature of the power plant is between 300 and 400 ℃, the flue gas temperature of the coke oven of the coke-oven plant is relatively low and is generally lower than 250 ℃, and if the blast furnace gas is adopted to heat the coke oven, the flue gas temperature is lower (generally lower than 200 ℃). Under the condition that the flue gas temperature is lower than 250 ℃, if the denitration is carried out by adopting the catalyst adopted by the flue gas denitration of the power plant, the denitration efficiency is very low, and the requirement of the flue gas emission standard can not be met.
2) The coke oven chimney must always be in a hot standby state. Compared with the flue gas of a power plant, the flue gas of the coke oven must return to the coke oven chimney after being desulfurized and denitrated, and is discharged to the atmosphere after being heated by the coke oven chimney, so that the coke oven chimney is always in a hot standby state. The temperature of the flue gas after desulfurization and denitrification must be higher than the dew point temperature of the flue gas, and the temperature of the flue gas must not be lower than 130 ℃.
3)SO 2 Influence of content on low-temperature denitration: under the action of a Selective Catalytic Reduction (SCR) catalyst, part of SO in the coke oven flue gas 2 Will be converted into SO 3 . Ammonia gas and SO at 180-230 deg.C 3 The reaction is easy to generate ammonium bisulfate. The ammonium bisulfate is extremely easy to deliquesce, the melting point temperature is 147 ℃, and the boiling point is 350 ℃. Ammonium bisulfate is very viscous and difficult to remove, adheres to the surface of the catalyst, and seriously affects the use efficiency of the catalyst.
In the aspect of coke oven flue gas treatment, an independent coking plant is heated by self-produced high-calorific-value coke oven gas, and the temperature of a combustion chamber is higher when the operation is not strict, so that nitrogen oxide is easily generated. Although the coke oven gas for the return heating is purified, the coke oven gas still contains high content of sulfur compounds (inorganic sulfur and organic sulfur) and nitrogen-containing components such as ammonia, HCN, pyridine, quinoline and the like relative to the blast furnace gas, and SO is finally formed 2 And NO X . The independent coking plants in China are almost heated for one time, and a combustion chamber is easy to generate local high temperature to form NO X . Therefore, SO in flue gas of independent coke-oven plant 2 And NO X Higher, difficult to reach the standard, and need to take post-treatment measures.
At present, in the field of coking at home and abroad, the technology for desulfurization and denitrification of coke oven flue gas is still in the research and development stage. The Chinese patent document with application publication number CN 105107349A discloses a coke oven flue gas desulfurization and denitrification combined purification process and a device, wherein the purification process firstly carries out desulfurization before flue gas denitrification, a desulfurization system of the purification process consists of a desulfurization tower, a desulfurizer solution preparation unit, a circulating ash solution preparation unit and a solution conveying unit, sodium carbonate solution prepared by the desulfurizer solution preparation unit is conveyed to a top tank at the top of the desulfurization tower through the solution conveying unit, then the desulfurizer solution automatically flows into an atomizer, and the atomizer atomizes the desulfurizer solution into particles of 50-100 micrometers; the coke oven flue gas is uniformly distributed in the desulfurizing tower through a flue gas distributor at the top of the desulfurizing tower, the coke oven flue gas and atomized desulfurizing agent particles are fully mixed in the desulfurizing tower, the sulfur dioxide and the desulfurizing particles are subjected to material chemical reaction to generate sodium sulfite, the sulfur dioxide in the coke oven flue gas is removed, and the powdery sodium sulfite enters a dedusting and denitrification system along with the flue gas desulfurized by the coke oven flue gas.
The technology adopts a rotary spraying semi-dry method for desulfurization, but has poor removal effect on sulfur dioxide and sulfur trioxide.
Disclosure of Invention
In view of this, the present application provides a dry desulfurization device for coke oven flue gas, a dry desulfurization and dust removal integrated system for coke oven flue gas and a method thereof, wherein the desulfurization device provided by the present invention is used for purifying coke oven flue gas and SO X The removal effect is better.
The invention provides a dry-type desulphurization device for coke oven flue gas, which comprises:
the gas inlet flue, the first-stage fluidized bed section, the Venturi section, the conical section and the second-stage fluidized bed section are sequentially communicated from the bottom to the top; the first-stage fluidized bed section is provided with a solid sodium-based absorbent supply unit; a solid calcium-based absorbent supply unit is arranged at the joint of the first-stage fluidized bed section and the Venturi section; the secondary fluidized bed section has an outlet.
Preferably, the conical section is provided with a humidifying and cooling unit.
Preferably, the air inlet flue is further provided with an airflow uniform distribution unit.
In the invention, the high-temperature coke oven flue gas is firstly introduced into a first-stage fluidized bed section through an air inlet flue and is mixed and reacted with a solid sodium-based absorbent added at the first-stage fluidized bed section to primarily absorb SO in the flue gas X . The flue gas after reaction and the solid calcium-based absorbent added subsequently are sent into a second-stage fluidized bed section through the acceleration of a Venturi section, a large amount of calcium-based and sodium-based absorbent particles form a violent turbulent material bed layer with large specific surface, and further SO in the flue gas is removed X And (5) absorbing and removing. Meanwhile, the high-turbulence secondary fluidized bed section can enable ultrafine dust carried in the coke oven flue gas in the secondary fluidized bed section to be aggregated, condensed and enlarged to form coarse particles, and is more beneficial to removing the smoke dust by a subsequent dust remover. In addition, the coke oven smoke also contains pollutants such as hydrogen sulfide and tar, in the secondary fluidized bed section with high turbulence in the low-temperature section, gas-solid phases generate violent turbulence and mixing due to the action of air flow, and the hydrogen sulfide and the tar are fully contacted with the absorbent, so that efficient removal is realized.
Compared with the prior art, the invention adopts the novel reactor which combines the high-temperature first-stage fluidized bed section and the low-temperature high-turbulence second-stage fluidized bed section, and can improve the desulfurization efficiency of coke oven flue gas to the maximum extent. And the low-temperature high-turbulence secondary fluidized bed section has a turbulence environment with high-efficiency mass transfer and heat transfer, which is beneficial to the coagulation of the ultrafine dust and the increase of dust particles, thereby realizing the high-efficiency removal of the ultrafine dust in the coke oven flue gas.
In addition, the conical section of the desulfurization device is preferably provided with a humidifying and cooling unit, and the temperature is reduced through atomization and water spraying, so that the temperature of the flue gas discharged from the inlet of the chimney is controlled to be not lower than 130 ℃, and the desulfurization is facilitated, the energy consumption is reduced, and the like.
The application provides a coke oven flue gas dry-type desulfurization dust removal integration system includes:
the desulfurization unit described above;
the feed inlet is connected with the outlet of the secondary fluidized bed section in the desulfurization device;
and the draught fan is connected with the gas outlet of the dust removal device and used for leading out clean flue gas.
Preferably, the system further comprises: and the circulating flue is connected with an outlet of the induced draft fan, the circulating flue is connected with an air inlet flue in the desulfurization device, and the circulating flue is provided with a flue gas load adjusting device.
Preferably, the dust removal device is a bag-type dust remover; the lower end of the bag-type dust collector is connected with the joint of the first-stage fluidized bed section and the Venturi section in the desulfurization device and/or is connected with the middle of the first-stage fluidized bed section in the desulfurization device through an air chute.
Preferably, the bag-type dust collector is also provided with a byproduct outlet which is connected with the byproduct storage bin.
The invention also provides a dry desulfurization and dust removal integrated method for the coke oven flue gas, which comprises the following steps:
1) Reacting the high-temperature coke oven flue gas with a solid sodium-based absorbent in a solid fluidization manner to obtain primary desulfurized flue gas;
2) Mixing the primary desulfurized flue gas with a solid calcium-based absorbent, accelerating the mixture by a Venturi, and reacting the mixture in a solid fluidization mode to obtain desulfurized flue gas;
3) And removing dust from the desulfurized flue gas to obtain clean flue gas.
Preferably, the reaction in the step 2) is carried out under the condition of humidification and temperature reduction, and the humidification and temperature reduction is controlled to be that the flue gas temperature at the inlet of a chimney is not lower than 130 ℃.
Preferably, the step 3) is carried out by cloth bag filtration and dust removal to obtain clean flue gas and unreacted solid materials;
introducing a portion of said clean flue gas back to step 1) to adjust the flue gas load; returning the unreacted solid material to the step 1) and/or the step 2).
Compared with the prior art, the integrated system for desulfurization and dust removal provided by the invention takes a novel desulfurization device and a dust removal device as the core and mainly comprises high temperatureThe first-stage fluidized bed section, the low-temperature high-turbulence second-stage fluidized bed section, the solid absorbent supply unit and the like. Through the system, the invention can efficiently remove SO 2 And SO 3 The removal efficiency is up to more than 98 percent, and SO in the coke oven flue gas can be removed X Hydrogen sulfide, tar and ultrafine dust particles are removed in a package to realize SO 2 Controlled at 30mg/m 3 The smoke is controlled at 10mg/m 3 The following environmental protection ultra-low emission indexes.
Drawings
FIG. 1 is a schematic view of an integrated dry desulfurization and dust removal process for coke oven flue gas provided by the embodiment of the application.
Detailed Description
The technical solutions in the embodiments of the present invention are clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and 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 invention.
The invention provides a dry-type desulphurization device for coke oven flue gas, which comprises:
the gas inlet flue, the first-stage fluidized bed section, the Venturi section, the conical section and the second-stage fluidized bed section are sequentially communicated from the bottom to the top; the first-stage fluidized bed section is provided with a solid sodium-based absorbent supply unit; a solid calcium-based absorbent supply unit is arranged at the joint of the first-stage fluidized bed section and the Venturi section; the secondary fluidized bed section has an outlet.
The application provides a novel desulfurization reaction device, and the desulfurization device provided by the invention can be used for purifying coke oven flue gas and obtaining better SO X The removal effect is good, and the subsequent high-efficiency removal of dust and the like is facilitated.
The bottom of the desulfurization device provided by the application comprises an air inlet flue used for introducing coke oven flue gas. The desulfurization device can have a venturi hollow tower structure; in the desulfurization device of the embodiment of the application, a first-stage fluidized bed section is connected and communicated with the air inlet flue.
The temperature range of the coke oven flue gas is wide, and the temperature change is 190-280 ℃. The high-temperature coke oven flue gas (200-280 ℃) can be recycled by the heat of a waste heat boiler or not. The coke oven flue gas (200-280 ℃) is firstly introduced into a first-stage fluidized bed section through an air inlet flue, and the first-stage fluidized bed section is a high-temperature section first-stage reactor (reaction bed) and serves as a first-stage absorption reaction site. In which a mass of solid particles is suspended in a moving fluid so that the particles have certain apparent characteristics of the fluid, this state of flow-solid contact is called solid fluidization, i.e. a fluidized bed, also called transport bed.
In the present invention, the first fluidized bed section is provided with a solid sodium-based absorbent supply unit for supplying solid sodium-based absorbent, generally comprising a sodium-based absorbent silo and a feeder connected thereto. In an embodiment of the invention, the supply unit for the solid sodium based absorbent is arranged at the front end of the first fluidized bed section. In the embodiment of the invention, a solid sodium-based absorbent such as NaHCO is added into a first-stage reactor at a high-temperature section by a feeder 3 And the like.
In the preferred embodiment of the invention, the air inlet flue is also provided with an airflow uniform distribution unit, SO that the flue gas entering the high-temperature-section first-stage reactor is uniformly distributed, and the sodium-based absorbent and SO in the flue gas are ensured X And (4) fully mixing and reacting. Meanwhile, according to SO in the flue gas X The concentration and the flue gas temperature after desulfurization are required, and the adding amount of the sodium-based absorbent is adjusted. In addition, in the embodiment of the invention, a large amount of calcium-based and sodium-based absorbent circulating materials in the high-temperature stage first-stage reactor can be collected by the rear-end dust remover and then are added from the middle part of the first-stage fluidized bed section through the large-flow air chute. According to the embodiment of the application, the newly added sodium-based absorbent and the circulating returning material are used for primarily absorbing SO in the flue gas X And finishing the desulfurization reaction of the first-stage reactor at the high-temperature section.
In a specific embodiment of the invention, sodium based absorbent (NaHCO) is added 3 ) Contacting with high-temperature flue gas of a coke oven, and decomposing into Na with smaller fineness, larger specific surface area and higher activity in the hot flue gas 2 CO 3 Simultaneous decomposition of H produced 2 O can increase the humidity of the flue gas, isAnd subsequent desulfurization reaction and the like. Sodium-based sorbent in high temperature stage first reactor and SO in flue gas X The reaction is fully mixed, and the main reaction formula is as follows:
2NaHCO 3 +SO 2 =Na 2 SO 3 +2CO 2 +H 2 O;
2NaHCO 3 +SO 3 =Na 2 SO 4 +2CO 2 +H 2 O;
Na 2 CO 3 +SO 2 =Na 2 SO 3 +CO 2 ;
Na 2 CO 3 +SO 3 =Na 2 SO 4 +CO 2 ;
Na 2 SO 3 +1/2O 2 =Na 2 SO 4 。
in the specific embodiment of the invention, the residence time of the flue gas of the first-stage fluidized bed section is 0.1 s-0.5 s.
In the desulfurization device of the embodiment of the application, the venturi section is connected and communicated with the first-stage fluidized bed section and is used for accelerating and introducing flue gas materials. The venturi section is part of a desulfurization unit well known to those skilled in the art, and a single or multi-orifice venturi acceleration section may be employed herein. In the present invention, a solid calcium-based absorbent supply unit for supplying a solid calcium-based absorbent such as Ca (OH) is provided at a junction of the primary fluidized bed section and the venturi section 2 Generally comprises a calcium-based absorbent bin and a feeder connected with the calcium-based absorbent bin.
The desulfurization device comprises a conical section and a secondary fluidized bed section; the small diameter end of the conical section is communicated with the Venturi section, and the large diameter end is communicated with the second-stage fluidized bed section. In an embodiment of the present application, the conical section is provided with a humidification cooling unit. The humidifying and cooling unit is not particularly limited, and an atomized water spraying device commonly used in the field can be adopted. The humidifying and cooling unit is preferably arranged at the conical section of the desulfurization device, and the temperature drop is controlled to be not lower than 130 ℃ at the exhaust gas temperature at the inlet of the chimney through atomization and water spraying for cooling, so that the desulfurization is facilitated, the energy consumption is reduced, and the like.
In the embodiment of the present application, the secondary fluidized bed section is located in the upper portion of the desulfurization unit and extends to the top. The second-stage fluidized bed section is a low-temperature section high-turbulence second-stage reaction bed (reactor) or a high-turbulence second-stage reactor, and the top of the second-stage fluidized bed section is provided with an outlet which can discharge desulfurization flue gas. In a specific embodiment of the invention, the residence time of the flue gas of the secondary fluidized bed section is 1s to 15s.
In the embodiment of the invention, the rear end of the high-temperature section first-stage reaction bed is connected with the low-temperature section high-turbulence second-stage reaction bed reactor, a large amount of sodium-based and calcium-based materials are fed into the low-temperature section high-turbulence second-stage reaction bed reactor through the Venturi acceleration section, the calcium-based absorbent is added into the low-temperature section high-turbulence second-stage reaction bed, a large amount of sodium-based and calcium-based material particles and the newly added calcium-based absorbent are mixed with flue gas in a violent and turbulent manner and are fully contacted, a violent and turbulent large-specific-surface material bed layer is formed, the ratio of (Ca + Na)/S at the highest material concentration part in the bed is up to more than 50, and the mass transfer and the heat transfer between gas and solid are greatly enhanced. In addition, the temperature can be reduced by atomizing and spraying water through the humidifying and cooling unit, the temperature is reduced to be not lower than 130 ℃ at the exhaust gas temperature at the inlet of the chimney, and further SO in the flue gas is reduced X And (5) absorbing and removing. Wherein, the main reaction formula in the high-turbulence secondary reaction bed is as follows:
Na 2 CO 3 +SO 2 =Na 2 SO 3 +CO 2 ;
Na 2 CO 3 +SO 3 =Na 2 SO 4 +CO 2 ;
Na 2 SO 3 +1/2O 2 =Na 2 SO 4 ;
Ca(OH) 2 +SO 2 =CaSO 3 ·1/2H 2 O+1/2H 2 O;
Ca(OH) 2 +SO 3 =CaSO 4 ·1/2H 2 O+1/2H 2 O;
CaSO 3 ·1/2H 2 O+1/2O 2 =CaSO 4 ·1/2H 2 O;
Ca(OH) 2 +H 2 S→CaSO 3 。
meanwhile, the high-turbulence secondary reactor is adopted, so that ultrafine dust carried in the coke oven flue gas can be aggregated, condensed and enlarged in the high-turbulence reactor to form coarse particles, and the dust can be removed by a subsequent dust remover. And the coke oven smoke also contains pollutants such as hydrogen sulfide and tar, gas-solid phases in the low-temperature section high-turbulence secondary reaction bed reactor generate violent turbulence and mixing due to the action of the gas flow, and the hydrogen sulfide and the tar are fully contacted with the absorbent, so that efficient removal is realized.
Therefore, the novel reactor combining the high-temperature-section first-stage reactor with the low-temperature-section high-turbulence second-stage reaction bed is adopted, and the desulfurization efficiency can be improved to the maximum extent. Meanwhile, according to the characteristics of the project, the reduction of the flue gas temperature can be well controlled, the temperature drop is controlled to be not lower than 130 ℃ at the flue gas exhaust temperature of the chimney inlet, and the high-turbulence secondary reaction bed at the low-temperature section has a turbulence environment with high-efficiency mass transfer and heat transfer, so that the coagulation of the ultrafine dust is facilitated, the dust particles are increased, and the efficient removal of the ultrafine dust in the coke oven flue gas is further realized.
The application provides a coke oven flue gas dry-type desulfurization dust removal integration system includes:
the desulfurization unit described above;
the feed inlet is connected with the outlet of the secondary fluidized bed section in the desulfurization device;
and the draught fan is connected with the gas outlet of the dust removal device and used for leading out clean flue gas.
By adopting the desulfurization and dust removal integrated purification system designed by the application, the effective treatment of the coke oven flue gas in the coking industry can be realized with lower investment and operation cost.
The desulfurization and dust removal integrated system provided by the invention comprises the desulfurization device, and the content of the desulfurization device is as described above. In the embodiment of the invention, the desulfurizing device of the integrated system comprises an air inlet flue which is provided with an airflow uniform distribution unit, SO that the flue gas entering a high-temperature stage primary reactor can be uniformly distributed, and the sodium-based absorbent and SO in the flue gas are ensured X And (4) fully mixing and reacting.
In the inventionIn the embodiment of the invention, the desulfurization device of the integrated system comprises a high-temperature-section first-stage reaction bed and a Venturi section, the high-temperature-section first-stage reaction bed is connected with a sodium-based absorbent bin through a feeder, and a calcium-based absorbent bin is connected at the joint of the high-temperature-section first-stage reaction bed and the Venturi section through a feeder. In the embodiment of the application, SO in the flue gas is primarily absorbed in the first-stage reactor at the high-temperature section mainly through the added sodium-based absorbent and the like X 。
In an embodiment of the invention, the desulfurization unit of the integrated system comprises a conical section and a low-temperature section high-turbulence secondary reaction bed, and an atomized water injection device is arranged in the conical section. In the embodiment of the invention, the rear end of the high-temperature section first-stage reaction bed is connected with the low-temperature section high-turbulence second-stage reaction bed, a large amount of sodium-based and calcium-based materials are fed into the low-temperature section high-turbulence second-stage reaction bed through the Venturi acceleration section, the calcium-based absorbent is added into the low-temperature section high-turbulence second-stage reaction bed, a large amount of sodium-based and calcium-based material particles and the newly added calcium-based absorbent are mixed with flue gas in a violent and turbulent manner and are fully contacted, a violent and turbulent large-specific-surface material bed layer is formed, the ratio of (Ca + Na)/S at the highest material concentration part in the bed is up to more than 50, and the mass transfer and the heat transfer between gas and solid are greatly enhanced. Moreover, the humidifying and cooling unit of the atomized water spraying equipment can be used for atomizing, spraying and cooling water, the temperature drop is controlled to be not lower than 130 ℃ at the smoke exhaust temperature at the inlet of a chimney, and further SO in the smoke is further reduced X And (5) absorbing and removing. Simultaneously, this application also does benefit to the high-efficient desorption of smoke and dust, hydrogen sulfide and tar etc..
The application provides a dry-type desulfurization dust removal integration system includes dust collector, and second grade fluidized bed section exit linkage in its feed inlet and the desulphurization unit to remove dust to the desulfurization flue gas. In the present application, the dust removing device is preferably a bag-type dust remover.
The bag-type dust collector is not particularly limited in the application, and can be used as usual in the field. In the embodiment of the application, the lower end of the bag-type dust remover is connected with the joint of the first-stage fluidized bed section and the Venturi section in the desulfurization device through the air chute and/or is connected with the middle of the first-stage fluidized bed section in the desulfurization device, so that material circulation is realized. The bottom of the bag-type dust collector in the embodiment of the application is provided with a byproduct outlet, namely a byproduct discharging port, which can be connected with a byproduct storage bin (desulfurization byproduct bin).
In the embodiment of the application, the outlet of the high-turbulence secondary reaction bed at the low-temperature section is directly connected with the bag-type dust remover, and the cake layer material on the filter bag also contains a certain amount of absorbent, SO that the SO in the flue gas can be further absorbed and removed while the dust in the flue gas is removed 2 . A large amount of unreacted absorbent returns to the conveying bed from the lower end of the cloth bag through the large-flow air chute for recycling; a small part of completely reacted byproducts are discharged to a byproduct storage bin.
The dry-type desulfurization dust removal integration system that this application embodiment provided includes the draught fan, and it is connected with dust collector gas outlet to draw out clean flue gas through discharging the flue toward the chimney. For example, coarse particles formed by agglomeration and coagulation in the final flue gas are purified by a bag-type dust collector and then discharged to a chimney through an induced draft fan.
In a preferred embodiment of the present application, the system further comprises: the circulating flue is connected with the outlet of the induced draft fan; and the circulating flue is connected with an air inlet flue in the desulfurization device, so that flue gas recirculation is realized. Preferably, the circulating flue is provided with a flue gas load adjusting device.
In the embodiment of the application, the fluctuation range of the coke oven flue gas load is 0-100%, in order to ensure that the novel reaction device of the high-temperature-section primary reactor and the low-temperature-section high-turbulence secondary reaction bed has good adaptability under various working conditions, the application can add a conventional load adjusting device, the inlet of the high-temperature-section primary reactor is negative pressure, and clean flue gas after an induced draft fan can be led back to the inlet of the reaction device through a connecting flue, so that the stable operation of the novel reactor under the low-load working condition is ensured.
Through the system, the invention can efficiently remove SO 2 And SO 3 And can remove SO in the coke oven flue gas X Hydrogen sulfide, tar and ultrafine dust particles are removed in a package. The system of the invention has lower investment and operation cost, can save 20 to 40 percent of investment cost and even more than 40 percent of operation cost compared with an SDA desulfurization route device, has obvious technical and economic application advantagesAnd (4) potential.
Correspondingly, the invention also provides a dry desulfurization and dust removal integrated method for the coke oven flue gas, which comprises the following steps:
1) Reacting the high-temperature coke oven flue gas with a solid sodium-based absorbent in a solid fluidization manner to obtain primary desulfurized flue gas;
2) Mixing the primary desulfurized flue gas with a solid calcium-based absorbent, accelerating the mixture by a Venturi, and reacting the mixture in a solid fluidization mode to obtain desulfurized flue gas;
3) And removing dust from the desulfurized flue gas to obtain clean flue gas.
The dry desulfurization and dust removal integrated technical method for the coke oven flue gas can realize effective treatment of the flue gas in the coking industry, meet the national environmental protection emission standard and realize ultralow emission of atmospheric pollutants. In addition, the invention has simple process flow and lower investment and operation cost.
Referring to fig. 1, fig. 1 is a schematic view of an integrated flow of dry desulfurization and dust removal of coke oven flue gas provided by the embodiment of the present application. The embodiment of the invention firstly introduces the coke oven flue gas of 190-280 ℃ into a high-temperature section first-stage reactor through a flue, solid sodium-based absorbent in an absorbent bin is added into the front end of a conveying bed reactor through a feeder, the high-temperature section first-stage reactor is used as a first-stage absorption reaction place, and the added sodium-based absorbent (NaHCO) is added 3 ) Contacting with high-temperature flue gas of a coke oven, reacting in a solid fluidization mode, and absorbing and removing SO in the flue gas X And obtaining the primary desulfurized flue gas.
Wherein NaHCO is added 3 The absorbent is decomposed into Na with smaller fineness, larger specific surface area and higher activity in hot smoke 2 CO 3 Simultaneous decomposition of H produced 2 O, increasing the humidity of the flue gas, namely the calcium-based absorbent and SO in the high-turbulence secondary reaction bed at the low-temperature section X The conditions are created. In addition, the feeder is controlled by frequency conversion and can be controlled according to SO in the flue gas X The concentration and the smoke temperature drop are required, and the adding amount of the sodium-based absorbent is adjusted. In an embodiment of the present invention, the molar ratio of the sodium-based sorbent to the (S) in the flue gas is preferably between 0.1 and 0.4, corresponding to a temperature drop of 30 to 0 ℃.
Meanwhile, the front end of the high-temperature stage first-stage reactor is provided with the airflow uniform distribution device, SO that the flue gas entering the conveying bed reactor is uniformly distributed, and the sodium-based absorbent of the high-temperature stage first-stage reactor and SO in the flue gas are ensured X And (4) fully mixing and reacting. The embodiment of the invention can also be designed with a flue gas adjusting device to ensure that the flow velocity of flue gas in the first-stage reactor at the high temperature section is over 18m/s under different coke oven loads, thereby being beneficial to the stable operation of the device.
After the primary desulfurized flue gas is obtained, the primary desulfurized flue gas is mixed with a solid calcium-based absorbent and accelerated by a Venturi, and then the added calcium-based absorbent reacts and absorbs and removes SO in the flue gas in a solid fluidization mode in a secondary absorption reaction site of a low-temperature high-turbulence secondary reactor X And obtaining the desulfurized flue gas. The embodiment of the application adopts a novel desulfurization reaction device combining a high-temperature-section first-stage reactor and a low-temperature Duan Gao turbulent second-stage reactor, and the novel desulfurization reaction device has two-stage absorption and removal of SO X The absorption and removal efficiency is higher.
In the specific embodiment of the application, the calcium-based and sodium-based absorbents which are collected by the rear-end bag-type dust remover and are not completely reacted can be added from the front end of the low-temperature-section high-turbulence secondary reactor through the large-flow air chute, and can also be added into the high-temperature-section primary reactor for recycling. The rear end of the high-temperature stage first-stage reactor is connected with the low-temperature stage high-turbulence second-stage reactor, and the calcium-based absorbent in the absorbent bin is Ca (OH) 2 Adding the mixture into the lower part of a high-turbulence secondary reactor at a low-temperature section through a feeder; the calcium-based absorbent feeder is controlled by frequency conversion according to the SO in the flue gas X The requirement of emission concentration adjusts the adding amount of the calcium-based absorbent, and the molar ratio of the added calcium-based absorbent to the (S) in the flue gas is preferably 1-1.2.
In the preferred embodiment of the invention, the added fresh calcium-based absorbent, the sodium-based material brought from the high-temperature stage primary reactor and the sodium-based and calcium-based materials recycled enter the low-temperature stage high-turbulence secondary reactor through Venturi acceleration, the water is atomized and sprayed for cooling through the humidification and cooling unit, the humidification and cooling unit adjusts the water spraying amount according to the humidity of the flue gas, the temperature of the flue gas at the inlet of a chimney is controlled to be not lower than 130 ℃, and SO is created X And Ca (OH) 2 Reaction of (2)Further processing SO in the flue gas for ionic reaction which can be completed instantly X And (4) absorbing and removing.
In the embodiment of the invention, the added fresh calcium-based absorbent, the sodium-based material brought from the high-temperature stage first-stage reactor and the sodium-based and calcium-based materials recycled back enter the low-temperature stage high-turbulence second-stage reactor through Venturi acceleration, a large amount of calcium-based and sodium-based absorbent particles are mixed with flue gas in a violent turbulence manner and fully contacted to form a violent-turbulence large-specific-surface material bed layer, the (Ca + Na)/S ratio of the highest-concentration part of the materials in the bed is up to more than 50, SO that the mass transfer and heat transfer between gas and solid are greatly enhanced, and the SO-solid separation and separation method realizes the mass transfer and heat transfer of SO and the heat transfer of SO X High-efficiency absorption and removal.
In addition, in the invention, the coke oven fine particles are always in a humidifying, agglomerating and coagulating environment in the low-temperature-section high-turbulence secondary reactor, and fine particle dust is agglomerated and coagulated and enlarged into coarser particles, so that the fine particle dust is more favorably removed by a subsequent bag-type dust collector.
After the desulfurized flue gas is obtained, the desulfurized flue gas is preferably dedusted by the bag-type dust remover, and the material of the powder cake layer on the filter bag of the bag-type dust remover also contains a certain amount of sodium-based and calcium-based absorbents, SO that the SO in the flue gas can be absorbed and removed again while the dust in the flue gas is removed X And the clean smoke and unreacted solid materials can be obtained. In the embodiment of the invention, the outlet of the low-temperature-section high-turbulence secondary reactor is connected with a bag-type dust remover, and the clean flue gas from the bag-type dust remover is discharged into a chimney through an induced draft fan.
In the preferred embodiment of the invention, the outlet of the induced draft fan is provided with a circulating flue which is connected with the front flue of the high-temperature stage first-stage reactor, and part of the clean flue gas is led back through flue gas recirculation; the connecting flue is provided with an adjusting device, the adjusting device is adjusted to adjust the flue gas load according to the change condition of the front end load flue gas volume, the flow velocity of the flue gas in the high-temperature section primary reactor is ensured to be more than 18m/s, and the stable operation of the reactor is ensured.
In the preferred embodiment of the invention, the bag-type dust collector collects unreacted materials, and most of the unreacted materials are added into the conveying bed reactor through the air chute to continuously participate in the reaction, so that the material circulation is realized; a small amount of by-products after reaction are discharged to a by-product storage bin and transported away by a sealed tanker.
In conclusion, the invention can adopt a novel desulfurization reaction device combining a high-temperature stage first-stage reactor and a low-temperature Duan Gao turbulent second-stage reactor, the reaction mechanism of two-stage absorption and removal, and SO X The absorption and removal efficiency is higher. SO (SO) 3 And SO 2 Can remove SO efficiently 3 And SO 2 The generated ammonium bisulfate has the problem of denitration efficiency of the denitration catalyst; the dry type desulfurization and dust removal can solve the problems of blockage, abrasion and caking of the atomizer, material waste and the like.
The invention realizes the integrated control of the desulfurization and the dust removal of the coke oven flue gas by the dry desulfurization and the dust removal integrated method and the dry desulfurization and the dust removal integrated system of the coke oven flue gas, and ensures that the SO of the coke oven flue gas is generated 2 The emission is controlled at 30mg/m 3 The smoke emission is controlled to 10mg/m 3 In the following, "ultra low emission" of atmospheric pollutants is achieved.
In the invention, the sodium-based absorbent contacts with the high-temperature flue gas of the coke oven and is decomposed in the hot flue gas to generate H 2 O, increasing the humidity of the flue gas, namely the calcium-based absorbent and SO in the high-turbulence secondary reaction bed at the low-temperature section X The reaction creates conditions, reduces the spraying of water in the low-temperature section high-turbulence secondary reactor, reduces the temperature reduction, and can control the flue gas temperature to be not lower than 130 ℃ at the inlet smoke exhaust temperature of a chimney. The temperature of the flue gas discharged by the chimney after desulfurization and dust removal is not lower than 130 ℃, the heat reserve of the chimney is met, and the coke oven flue gas can be smoothly discharged from the chimney by means of the self-pulling force of the chimney through a bypass when the desulfurization and dust removal system fails.
The invention realizes the integrated control of desulfurization and dust removal, has simple process flow, simple and convenient operation and stable operation, and can remove SO efficiently in a synergistic manner 3 Hydrogen sulfide and tar, no secondary pollution of waste water (slag), no need of antiseptic treatment and suitability for industrial popularization.
In order to further understand the present application, the coke oven flue gas dry desulfurization device, the coke oven flue gas dry desulfurization and dust removal integrated method and the system thereof provided by the present invention are specifically described below with reference to the embodiments.
Example 1:
2 x 40 million coke ovens in a certain coke plant use the flue gas desulfurization and dust removal process system of the coke oven, and the flue gas amount is 180000Nm 3 H (standard condition); the temperature of the inlet flue gas is 190 ℃, and the original flue gas SO 2 The concentration is 500mg/Nm 3 . Use of solid Ca (OH) 2 And solid NaHCO 3 As an absorbent, the Na/S ratio is 0.1, the Ca/S ratio is 1.2, the ratio of (Ca + Na)/S at the position with the highest material concentration is 50, and the temperature drop is 30 ℃.
The coke oven smoke to be purified enters a high-temperature-section first-stage reactor (the retention time is 0.1 s), and the flow velocity of the smoke is 18m/s; sodium-based absorbent is added into a high-temperature stage first-stage reactor through a feeder, and SO in flue gas X And fully mixing and reacting with the added sodium-based absorbent to obtain primary desulfurized flue gas. Adding calcium-based absorbent in the absorbent bin into the lower part of the low-temperature section high-turbulence secondary reactor through a feeder, accelerating sodium-based materials brought by the high-temperature section primary reactor and sodium-based and calcium-based materials circulated back through a Venturi, entering the low-temperature section high-turbulence secondary reactor (the retention time is 11 s), carrying out atomization water spraying cooling through an atomization water spraying device, controlling the temperature drop at 30 ℃, and further reducing SO in the flue gas X Absorbing and removing to obtain the desulfurized flue gas.
Because the high-turbulence secondary reactor at the low-temperature section is always in the environment of humidification, agglomeration and coalescence, fine particle dust is agglomerated and coalesced to form thicker particles, and the dust is more favorably removed by a subsequent bag-type dust collector. And (4) dedusting the desulfurized flue gas by using a rear-end bag-type dust collector to obtain clean flue gas, wherein the temperature of the flue gas discharged by a chimney is not lower than 130 ℃.
The bag-type dust collector at the rear end collects unreacted materials, and most of the materials return to the middle part of the conveying bed reactor through the air chute and continue to participate in the circulating reaction. The material of the powder cake layer on the filter bag of the bag-type dust collector also contains a certain amount of sodium-based and calcium-based absorbents which can absorb and remove SO in the flue gas again while removing the dust in the flue gas 2 . And discharging the purified flue gas subjected to multistage treatment to a chimney through a draught fan. The fluctuation range of the coke oven flue gas load is 30-100%, and when the coke oven load is reduced, the flue gas adjusting device is started to keep enough flue gas flow rate in the reactor.In addition, the solid by-product is mainly Na 2 SO 3 、Na 2 SO 4 、CaSO 3 、CaSO 4 And a small amount of unreacted Ca (OH) 2 And NaHCO 3 And a small amount of reacted byproducts are discharged to a byproduct storage bin and transported away through a sealed tank truck.
The desulfurization efficiency of the device is 98 percent, and the SO of the coke oven flue gas is ensured 2 The emission is controlled at 10mg/m 3 The smoke dust is controlled at 4.5mg/m 3 . The invention overcomes the defects of the traditional semidry method device, realizes integrated control, has simple process flow, simple and convenient operation and stable operation, and can remove SO efficiently in a synergistic way 3 、H 2 S and tar, no secondary pollution of waste water (slag) and no need of antiseptic treatment.
Example 2:
200 ten thousand tons of coke ovens in a certain coke plant use the desulfurization and dust removal process system for the flue gas of the coke oven. The smoke amount is 380000Nm 3 H (standard condition); the temperature of the inlet flue gas is 280 ℃, and the original flue gas SO 2 The concentration is 200mg/Nm 3 . Using solid Ca (OH) 2 And solid NaHCO 3 As an absorbent, the Na/S ratio is 0.4, the Ca/S ratio is 1.0, the ratio of (Ca + Na)/S at the position with the highest material concentration is 50, and the temperature drop is 0 ℃.
The coke oven smoke to be purified enters a high-temperature section first-stage reactor (the retention time is 0.2 s), and the flow velocity of the smoke is 18m/s; sodium-based absorbent is added into a high-temperature stage first-stage reactor through a feeder, and SO in flue gas X And fully mixing and reacting with the added sodium-based absorbent to obtain the primary desulfurized flue gas. Calcium-based absorbent in the absorbent bin is added at the lower part of the low-temperature-section high-turbulence secondary reactor through a feeder, sodium-based materials brought from the high-temperature-section primary reactor and sodium-based and calcium-based materials circulated back are accelerated through a Venturi and enter the low-temperature-section high-turbulence secondary reactor (the retention time is 6 s), atomization, water spraying and cooling are not carried out, and SO in the flue gas is further reduced X Absorbing and removing to obtain the desulfurized flue gas.
Because the high-turbulence secondary reactor at the low-temperature section is always in the environment of humidification, agglomeration and coalescence, fine particle dust is agglomerated and coalesced to form thicker particles, and the dust is more favorably removed by a subsequent bag-type dust collector. And (4) dedusting the desulfurized flue gas by using a rear-end bag-type dust collector to obtain clean flue gas, wherein the temperature of the flue gas is not lower than 130 ℃.
The bag-type dust collector at the rear end collects unreacted materials, and most of the materials return to the middle part of the conveying bed reactor through the air chute and continue to participate in the circulating reaction. The powder cake layer material on the filter bag of the bag-type dust collector also contains a certain amount of sodium-based and calcium-based absorbents, SO that SO in the flue gas is absorbed and removed again while the dust in the flue gas is removed 2 . And discharging the purified flue gas subjected to multistage treatment to a chimney through a draught fan. The fluctuation range of the coke oven flue gas load is 30-100%, and when the coke oven load is reduced, the flue gas adjusting device is started to keep enough flue gas flow rate in the reactor. In addition, the solid by-product is mainly Na 2 SO 3 、Na 2 SO 4 、CaSO 3 、CaSO 4 And a small amount of unreacted Ca (OH) 2 And NaHCO 3 And discharging a small amount of the reacted by-product to a by-product storage bin, and transporting away by a sealed tank truck.
The desulfurization efficiency of the device is 97.5 percent, and the SO of the coke oven flue gas is ensured 2 The emission is controlled at 5mg/m 3 The smoke dust is controlled at 4mg/m 3 . The invention overcomes the defects of the traditional semidry method device, realizes integrated control, has simple process flow, simple and convenient operation and stable operation, and can remove SO efficiently in a synergistic way 3 、H 2 S and tar, no secondary pollution of waste water (slag) and no need of antiseptic treatment.
The above description is only a preferred embodiment of the present invention, and it should be noted that various modifications to these embodiments can be implemented by those skilled in the art without departing from the technical principle of the present invention, and these modifications should be construed as the scope of the present invention.
Claims (7)
1. A coke oven flue gas dry desulfurization device comprises:
the high-temperature first-stage fluidized bed section, the Venturi section, the conical section and the second-stage fluidized bed section are sequentially communicated from the bottom to the top; the high-temperature first-stage fluidized bed section is provided with solidsA sodium-based absorbent supply unit; a solid calcium-based absorbent supply unit is arranged at the joint of the high-temperature first-stage fluidized bed section and the Venturi section, sodium-based and calcium-based material particles, a newly added calcium-based absorbent and flue gas are mixed vigorously and turbulently, and the ratio of (Ca + Na)/S at the highest concentration part of the formed materials in the bed layer is more than 50; the secondary fluidized bed section having an outlet; the solid sodium-based absorbent is NaHCO 3 (ii) a The solid calcium-based absorbent is Ca (OH) 2 ;
The air inlet flue is used for introducing the coke oven smoke with the high temperature of 200-280 ℃; the conical section is provided with a humidifying and cooling unit, and the temperature of the flue gas discharged from the inlet of the chimney is controlled to be not lower than 130 ℃; the air inlet flue is also provided with an airflow uniform distribution unit, the residence time of the smoke of the high-temperature first-stage fluidized bed section is 0.1s-0.5s, and the residence time of the smoke of the second-stage fluidized bed section is 1s-15s.
2. A coke oven flue gas dry type desulfurization and dust removal integrated system comprises:
the desulfurization unit of claim 1;
the feed inlet is connected with the outlet of the second-stage fluidized bed section in the desulfurization device;
and the draught fan is connected with the gas outlet of the dust removal device and used for leading out clean flue gas.
3. The coke oven flue gas dry desulfurization and dust removal integrated system of claim 2, further comprising: and the circulating flue is connected with an outlet of the induced draft fan, the circulating flue is connected with an air inlet flue in the desulfurization device, and the circulating flue is provided with a flue gas load adjusting device.
4. The coke oven flue gas dry desulfurization and dust removal integrated system as claimed in claim 2 or 3, wherein the dust removal device is a bag-type dust remover; the lower end of the bag-type dust collector is connected with the joint of the high-temperature first-stage fluidized bed section and the Venturi section in the desulfurization device through an air chute, and/or is connected with the middle part of the first-stage fluidized bed section in the desulfurization device.
5. The coke oven flue gas dry desulfurization and dust removal integrated system as claimed in claim 4, wherein the bag-type dust remover further has a byproduct outlet connected with a byproduct storage bin.
6. A dry desulfurization and dust removal integrated method for coke oven flue gas comprises the following steps:
1) Reacting the high-temperature coke oven flue gas with a solid sodium-based absorbent at a high temperature in a solid fluidization mode to obtain primary desulfurized flue gas;
2) Mixing the primary desulfurized flue gas with a solid calcium-based absorbent, accelerating the mixture by a Venturi, reacting the mixture in a solid fluidization mode, and violently and turbulently mixing sodium-based and calcium-based material particles, the newly added calcium-based absorbent and the flue gas to obtain desulfurized flue gas; the reaction in the step 2) is carried out under the condition of humidification and temperature reduction, and the humidification and temperature reduction is controlled to be that the temperature of the exhaust gas at the inlet of a chimney is not lower than 130 ℃; the solid sodium-based absorbent is NaHCO 3 (ii) a The solid calcium-based absorbent is Ca (OH) 2 ;
3) And removing dust from the desulfurized flue gas to obtain clean flue gas.
7. The method as claimed in claim 6, wherein the step 3) is carried out by cloth bag filtration to obtain clean flue gas and unreacted solid materials;
introducing a portion of said clean flue gas back to step 1) to adjust the flue gas load; returning the unreacted solid material to the step 1) and/or the step 2).
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CN111773915B (en) * | 2020-06-10 | 2022-07-15 | 上海交通大学 | Flue gas dry desulfurization process |
CN112933911B (en) * | 2021-03-08 | 2022-10-25 | 上海交通大学 | Moving bed desulfurization system based on flue gas semidry desulfurization and application thereof |
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