CN110585900A - Coke oven flue gas denitration and waste heat utilization combined device and method for denitration by using same - Google Patents
Coke oven flue gas denitration and waste heat utilization combined device and method for denitration by using same Download PDFInfo
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/86—Catalytic processes
- B01D53/8621—Removing nitrogen compounds
- B01D53/8625—Nitrogen oxides
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- B01D2251/00—Reactants
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- B01D2251/2062—Ammonia
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- B01D2255/20769—Molybdenum
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Abstract
The application discloses coke oven flue gas denitration and waste heat utilization combined device and method for denitration by using the same, and belongs to the technical field of coke oven flue gas denitration, the device comprises an inlet flue, a denitration reactor and a steam drum, wherein the inlet flue is provided with a flue gas inlet, an ammonia gas inlet pipeline and three flue gas outlet pipelines, each flue gas outlet pipeline is connected with an inlet corresponding to the top of the denitration reactor, a clean flue gas outlet is formed in a lower shell of the denitration reactor, a flue gas flow equalizing component, a denitration catalyst, an evaporation heat exchanger and a preheating heat exchanger are sequentially arranged in a denitration reactor cavity above the clean flue gas outlet from top to bottom, the inlet and the outlet of the evaporation heat exchanger are respectively connected with the steam drum through pipelines, the inlet of the preheating evaporator is connected with a soft water pipeline, and the outlet of the preheating evaporator is connected with the steam drum through. By using the device, 2500 tons of NOx are reduced annually, 10 ten thousand tons of recovered steam are annually generated, and the denitration efficiency is more than 96%.
Description
Technical Field
The invention belongs to the field of coke oven flue gas denitration, and particularly relates to a coke oven flue gas denitration and waste heat utilization combined device and a denitration method by using the same.
Background
For flue gas denitration, a reduction method using ammonia as a raw material is mature and reliable, and the reaction principle is as follows: NO +0.25O2+NH3＝N2+1.5H2O, ammonia reduces NOx to nitrogen and water, eliminating pollution. 1mol of NO consumes 1mol of ammonia, converted to 1 ton of NO20.37 ton of ammonia was consumed. The project is designed according to the maximum value, and the consumed ammonia per hour is 130 kg. The methods are classified into non-catalytic selective reduction (SNCR) methods without a catalyst and Selective Catalytic Reduction (SCR) methods with a catalyst. The SNCR method requires that the reaction temperature is 850 ℃ and 950 ℃ and the denitration efficiency is 50-70%. It is clear that coke oven flue gas is not suitable for SNCR.
The coke oven flue gas has the following characteristics:
(1) the temperature is lower, the general temperature is between 200-2240 ℃, and the normal temperature is about 220 ℃. Although the temperature of the flue gas is also reduced to about 1300-1500 ℃, due to the particularity of the coke oven structure (adopting a heat storage heat exchange mode, and adopting a tubular heat exchange mode for a boiler), the catalyst layer can hardly be inserted in series in the coke oven, and the denitration can only be implemented by utilizing the temperature zone of the flue gas.
(2) The NOx content of the flue gas is higher and is 800-1200mg/Nm3In the meantime.
(3) The dust content is low, and is generally 30mg/Nm3About less than 100mg/Nm3。
Thus, conventional boiler catalysts are not well suited for denitration of coke oven flue gas.
The residual heat brought by the coke oven flue gas accounts for nearly one third of the residual heat utilization of the whole coking system. In order to save a smoke outlet induced draft fan and possible problems thereof in the past, smoke is directly discharged from an underground flue communicated chimney, and for a combustion chamber of a coke oven, the smoke directly forms creeping force to provide air for the coke oven.
In recent years, with the improvement of energy conservation, especially environmental protection standard, the utilization of the waste heat of the flue gas of the coke oven becomes an important direction. However, the existing waste heat utilization device is easy to have the problem of operation stability due to the particularity of the coke oven flue gas.
Disclosure of Invention
The invention aims to provide a coke oven flue gas denitration and waste heat utilization combined device and a denitration method by using the same.
Based on the purpose, the invention adopts the following technical scheme:
the utility model provides a coke oven flue gas denitration and waste heat utilization combined device, includes entry flue, denitration reactor and steam pocket, the entry flue is equipped with flue gas inlet, ammonia inlet pipe and three exhanst gas outlet pipe, every exhanst gas outlet pipe links to each other with the import that denitration reactor top corresponds, be equipped with clean exhanst gas outlet on the lower part casing of denitration reactor, be equipped with flue gas flow equalizing member, denitration catalyst, evaporation heat exchanger and preheating heat exchanger from last to down in proper order in the denitration reactor cavity of clean exhanst gas outlet top, the import and the export of evaporation heat exchanger link to each other through pipeline and steam pocket respectively, the import of preheating evaporator even has soft water pipeline, the export of preheating evaporator links to each other through hot water pipeline and steam pocket, the steam pocket is equipped with steam output tube.
Further, the entry flue is the S type, by last horizontal part, vertical portion of horizontal part and connection lower horizontal part constitutes, the left end import of lower horizontal part is the flue gas inlet, the right-hand member branch of going up the horizontal part is equipped with three exhanst gas outlet pipe ways, all be equipped with the gas burner on every exhanst gas outlet pipe way, gas burner and gas line intercommunication, the top of denitration reactor is equipped with three import, three exhanst gas outlet pipe ways link to each other with the three import at denitration reactor top respectively, be equipped with two division boards in the cavity of denitration reactor, the division board upwards extends to the top of denitration reactor cavity, downwardly extending to the bottom of denitration catalyst.
And further, an ammonia gas mixing component is arranged below the vertical part of the inlet flue and is connected with an ammonia gas inlet pipeline outside the inlet flue, the ammonia gas mixing component comprises an ammonia gas branch pipe, and a jet pipe is vertically arranged on the ammonia gas branch pipe.
Further, the denitration catalyst is provided with three layers at intervals from top to bottom, the filling height of each layer is 1.0-1.8 m, and the distance between adjacent layers is 1.0-1.6 m.
Further, the flue gas flow equalizing member is a pore plate, the thickness of the pore plate is 6-20 mm, the opening of the pore plate is a square hole, a round hole or a strip-shaped hole, and the flow area of the hole is one fourth to one third of the cross-sectional area of the denitration reactor.
Further, the catalyst is honeycomb-shapedThe catalyst is characterized in that honeycomb holes are round holes, square holes or hexagonal holes, the size of the honeycomb holes is 3-6 mm, and the honeycomb catalyst contains MoO3V of2O5/TiO2Catalyst and MoO3In the mass of the catalyst is between 2.5 and 5 percent of the total mass of the catalyst, V2O5The mass of (A) is 1.5 to 3.0% of the total catalyst.
Furthermore, the evaporation heat exchanger and the preheating heat exchanger are both tube type heat exchangers with finned tubes, the fins are made of aluminum sheets, the distance between the fins is 3mm to 6mm, and the height of the fins is 25mm to 45 mm.
The method for denitration by using the coke oven flue gas denitration and waste heat utilization combined device comprises the following steps:
(1) the temperature after desulfurization is 200 ℃ to 240 ℃, NOXThe content is 600-1200mg/Nm3The flue gas enters the inlet flue through the flue gas inlet, the ammonia water steam enters the ammonia gas mixing component through the ammonia gas inlet pipeline and is sprayed out to be mixed with ammonia gas to obtain mixed gas, and NH is enabled to be generated3The molar ratio of NO/is between 0.95 and 1.05,
(2) when the mixed gas passes through the gas burner, the gas burner heats the mixed gas, the heated mixed gas enters the catalyst layer through the flue gas flow equalizing component, and NH is generated under the catalytic action of the catalyst3Reacting with NO;
(3) the NOx content in the denitrified smoke is less than 50mg/Nm3Sequentially contacting with an evaporation heat exchanger and a preheating heat exchanger, wherein the temperature of flue gas after heat exchange is 150-170 ℃, and discharging the flue gas through a clean flue gas outlet.
Preferably, the ammonia water vapor is obtained by vaporizing an ammonia water solution with the concentration of 10-20wt%, the temperature of the ammonia water vapor is 140 ℃, and the volume flow is 900-3Hr, flue gas flow rate of 54 ten thousand m3The speed of the jet pipe is more than or equal to 80 m/s.
By using the device and the catalyst, the emission of NOx is reduced to 2500 tons every year, the quantity of recovered steam is 10 ten thousand tons every year, and the denitration efficiency is as follows: greater than 96%; outlet NOx: less than 50mg/Nm3The service cycle of the catalyst is more than two years, and good economy is obtainedAnd (4) benefit.
Drawings
FIG. 1 is a schematic structural diagram of a combined device for denitration and waste heat utilization of coke oven flue gas;
fig. 2 is a schematic view of the ammonia mixing component of fig. 1.
Detailed Description
The technical solutions of the present invention are further described in detail below with reference to the drawings and examples, but the present invention is not limited thereto.
Example 1
A coke oven flue gas denitration and waste heat utilization combined device is shown in figure 1 and comprises an inlet flue 200, a denitration reactor 100 and a steam drum 300, the inlet flue 200 is provided with a flue gas inlet, an ammonia gas inlet pipeline 1 and three flue gas outlet pipelines, each flue gas outlet pipeline is connected with a corresponding inlet at the top of the denitration reactor 100, the lower shell of the denitration reactor 100 is provided with a clean flue gas outlet 9, a flue gas flow equalizing member 30, a denitration catalyst 40, an evaporating heat exchanger 50 and a preheating heat exchanger 60 are sequentially arranged in a chamber of the denitration reactor above the clean flue gas outlet 9 from top to bottom, the steam drum 300 is connected with the inlet of the evaporation heat exchanger 50 through a downpipe line 5, the outlet of the evaporation heat exchanger 50 is connected with the steam drum 300 through an uppipe line 6, the inlet of the preheating evaporator 60 is connected with a soft water line 2, and the outlet of the preheating evaporator 60 is connected with the steam drum 300 through a hot water line 4. And a steam output pipe 7 is arranged on the steam pocket 300.
The inlet flue 200 is S-shaped and comprises an upper horizontal part, a lower horizontal part and a vertical part connected with the upper horizontal part and the lower horizontal part, the inlet at the left end of the lower horizontal part is a flue gas inlet, the right branch of the upper horizontal part is provided with three flue gas outlet pipelines, each flue gas outlet pipeline is provided with a gas burner 400, the gas burners 400 are communicated with a gas pipeline 3, the top of the denitration reactor 100 is provided with three inlets, the three flue gas outlet pipelines are respectively connected with the three inlets at the top of the denitration reactor 100, two partition plates 20 are arranged in the cavity of the denitration reactor 100, and the partition plates 20 extend upwards to the top of the cavity of the denitration reactor 100 and downwards extend to the bottom of the denitration catalyst 40.
An ammonia mixing component 10 is arranged below the vertical part of the inlet flue 200, the ammonia mixing component 10 is connected with an ammonia inlet pipeline 1 outside the inlet flue 100, as shown in fig. 2, the ammonia mixing component 10 comprises an ammonia branch pipe 12, jet pipes 11 are vertically arranged on the ammonia branch pipe 12, and the jet pipes 11 are distributed in a matrix shape.
The denitration catalyst 40 is provided with three layers at intervals from top to bottom, the filling height of each layer is 1.0-1.8 m, and the distance between adjacent layers is 1.0-1.6 m.
The flue gas flow equalizing member 30 is a pore plate, the thickness of the pore plate is 6-20 mm, the opening of the pore plate is a square hole, a round hole or a strip-shaped hole, and the flow area of the hole is one fourth to one third of the cross-sectional area of the denitration reactor 100.
The denitration catalyst 40 is a honeycomb catalyst, the honeycomb holes are round holes, square holes or hexagonal holes, the size of the honeycomb holes is 3-6 mm, and the honeycomb catalyst contains MoO3V of2O5/TiO2Catalyst and MoO3In the mass of the catalyst is between 2.5 and 5 percent of the total mass of the catalyst, V2O5The mass of (A) is 1.5 to 3.0% of the total catalyst.
The catalyst adopts a low and medium temperature denitration catalyst suitable for coke oven smoke, and the chemical component of the catalyst is vanadium V2O5Molybdenum MoO3And titanium TiO2I.e. V2O5-MoO3/TiO2Wherein vanadium is the active component, molybdenum is the electron and structural assistant, and titanium is the carrier. Referred to as vanadium-molybdenum-titanium catalysts, referred to as molybdenum-based catalysts.
The catalyst has the following characteristics:
the initial activity temperature is low, generally the tungsten is 200 ℃, and the molybdenum is 150 ℃;
② high sulfur tolerance, because of MoO3Is the main active component of sulfur-resistant shift catalyst, and sulfur has promoting effect on molybdenum catalyst. Therefore, the molybdenum catalyst is very suitable for the condition of coke oven smoke (the coke oven has leakage from a carbonization chamber to a combustion chamber, especially the old coke oven has trace organic sulfur and hydrogen sulfide in the smoke);
③ the molybdenum catalyst has better SO inhibition2Oxidation ability, reduction of SO in flue gas3The content of the catalyst is increased, and the service life of the catalyst is prolonged;
and the molybdenum catalyst has higher water resistance. This is particularly true for coke oven flue gas, which typically has a moisture content of around 20% compared to 5-8% for conventional boiler flue gas.
Further, the evaporation heat exchanger 50 and the preheating heat exchanger 60 are both tube type heat exchangers with finned tubes, the fins are made of aluminum sheets, the distance between the fins is 3mm to 6mm, and the height of the fins is 25mm to 45 mm.
The method for denitration by using the coke oven flue gas denitration and waste heat utilization combined device comprises the following steps:
(1) the temperature after desulfurization is 200 ℃ to 240 ℃, NOXThe content is 600-1200mg/Nm3The flue gas enters the inlet flue 100 through the flue gas inlet, the ammonia water steam enters the ammonia gas mixing component 10 through the ammonia gas inlet pipeline 1 and is sprayed out to be mixed with ammonia gas to obtain mixed gas, and NH is enabled to be generated3The molar ratio of NO/is between 0.95 and 1.05;
(2) when the mixed gas passes through the gas burner 400, the gas burner 400 heats the mixed gas, the heated mixed gas enters the catalyst layer through the flue gas flow equalizing member 30, and NH is generated under the catalytic action of the catalyst3Reacting with NO;
(3) the NOx content in the denitrified smoke is less than 50mg/Nm3Sequentially contacting with the evaporation heat exchanger 50 and the preheating heat exchanger 60, wherein the temperature of the flue gas after heat exchange is 150-170 ℃, and discharging the flue gas through a clean flue gas outlet 9.
The denitrated flue gas is still a high-temperature gas mixture, soft water enters the preheating heat exchanger 60 and then exchanges heat with the flue gas primarily, the heated soft water enters the steam drum 300, water in the steam drum 300 exchanges heat with hot flue gas through the evaporation heat exchanger 50, so that the water is vaporized into steam, the steam and the water in the steam drum 300 are separated to generate 0.6MPa saturated steam, and the saturated steam is output outwards through the steam output pipe 7.
Preferably, the ammonia water vapor is 10-20wt% in concentrationThe ammonia water solution is obtained by vaporization, the temperature of the ammonia water vapor is 140 ℃, the volume flow is 900-3Hr, flue gas flow rate of 54 ten thousand m3The speed of the jet pipe 11 is more than or equal to 80 m/s.
27 ten thousand Nm (meters per second) of full-load smoke gas of coke oven3Measured in/hr, the NOx content in the flue gas is 1000mg/Nm3And a temperature of 260 ℃. The denitration efficiency is 96 percent, and the steam yield is 14T/hr. The total amount of annual denitration is 2270.6 tons, and the annual steam production amount is 12.264 ten thousand tons.
And (3) carrying out 168-hour detection data on the integrated project of denitration of the coke oven flue gas and utilization of residual heat. All technical indexes of the project reach the ultra-low emission standard. In the following table, sulfur dioxide: mg/Nm3Nitrogen oxides: mg/Nm3And the smoke amount: nm3/hr。
12.12.12.2018
12 and 13 months in 2018
12 months and 14 days in 2018
12 month and 15 days 2018
12 and 16 months in 2018
12 month and 17 days 2018
18 days 12 and 2018
From the above monitoring data, the device of the present invention has good operation condition. By implementing the coke oven flue gas denitration and waste heat utilization combined device, nitrogen oxide discharged by the flue gas is less than 50mg/Nm3The exhaust heat byproduct steam is 8t/h, and the emission index is superior to the ultralow emission (SO) of Henan province2<35mg/Nm3Dust and dirt<10mg/Nm3、NOX<50mg/Nm3) Standard, economic and environmental protection benefits are obvious. From the viewpoints of environmental protection and energy conservation, the research and implementation of the technology have long-term social significance and wide popularization and application prospects.
Claims (9)
1. The utility model provides a coke oven flue gas denitration and waste heat utilization combined device, includes entry flue, denitration reactor and steam pocket, its characterized in that, the entry flue is equipped with flue gas inlet, ammonia inlet pipe and three flue gas outlet pipe, every flue gas outlet pipe links to each other with the import that denitration reactor top corresponds, be equipped with clean flue gas export on the lower part casing of denitration reactor, be equipped with flue gas flow equalizing member, denitration catalyst, evaporation heat exchanger and preheating heat exchanger from last to having in proper order down in the denitration reactor cavity of clean flue gas export top, the import and the export of evaporation heat exchanger link to each other through pipeline and steam pocket respectively, the import of preheating evaporator even has soft water pipeline, the export of preheating evaporator links to each other through hot water pipeline and steam pocket, the steam pocket is equipped with steam output tube.
2. The coke oven flue gas denitration and waste heat utilization combined device as claimed in claim 1, wherein the inlet flue is S-shaped and is composed of an upper horizontal portion, a lower horizontal portion and a vertical portion connecting the upper horizontal portion and the lower horizontal portion, the left end inlet of the lower horizontal portion is a flue gas inlet, the right end branch of the upper horizontal portion is provided with three flue gas outlet pipelines, each flue gas outlet pipeline is provided with a gas burner, the gas burners are communicated with a gas pipeline, the top of the denitration reactor is provided with three inlets, the three flue gas outlet pipelines are respectively connected with the three inlets at the top of the denitration reactor, two partition plates are arranged in the cavity of the denitration reactor, and the partition plates extend upwards to the top of the cavity of the denitration reactor and downwards to the bottom of the denitration catalyst.
3. The coke oven flue gas denitration and waste heat utilization combined device as claimed in claim 2, wherein an ammonia gas mixing member is arranged below the vertical part of the inlet flue, the ammonia gas mixing member is connected with an ammonia gas inlet pipeline outside the inlet flue, the ammonia gas mixing member comprises an ammonia gas branch pipe, and a jet pipe is vertically arranged on the ammonia gas branch pipe.
4. The coke oven flue gas denitration and waste heat utilization combined device as claimed in claim 1, wherein the denitration catalyst is provided with three layers at intervals from top to bottom, the filling height of each layer is 1.0-1.8 m, and the distance between adjacent layers is 1.0-1.6 m.
5. The coke oven flue gas denitration and waste heat utilization combined device as claimed in claim 1, wherein the flue gas flow equalizing member is a perforated plate, the thickness of the perforated plate is 6mm to 20mm, the opening of the perforated plate is a square hole, a circular hole or a strip-shaped hole, and the flow area of the hole is one fourth to one third of the cross-sectional area of the denitration reactor.
6. The coke oven flue gas denitration and waste heat utilization combined device as claimed in claim 1, wherein the catalyst is a honeycomb catalyst, honeycomb holes are circular holes, square holes or hexagonal holes, the size of the honeycomb hole is 3-6 mm, and the honeycomb catalyst is a catalyst containing MoO3V of2O5/TiO2Catalyst and MoO3In the mass of the catalyst is between 2.5 and 5 percent of the total mass of the catalyst, V2O5The mass of (A) is 1.5 to 3.0% of the total catalyst.
7. The coke oven flue gas denitration and waste heat utilization combined device as claimed in claim 1, wherein the evaporation heat exchanger and the preheating heat exchanger are both tube type heat exchangers with finned tubes, the fins are made of aluminum sheets, the spacing between the fins is 3mm to 6mm, and the height of the fins is 25mm to 45 mm.
8. The method for denitration by using the coke oven flue gas denitration and waste heat utilization combined device as claimed in any one of claims 1 to 7, is characterized by comprising the following steps:
(1) the temperature after desulfurization is 200 ℃ to 240 ℃, NOXThe content is 600-1200mg/Nm3The flue gas enters the inlet flue through the flue gas inlet, the ammonia water steam enters the ammonia gas mixing component through the ammonia gas inlet pipeline and is sprayed out to be mixed with ammonia gas to obtain mixed gas, and NH is enabled to be generated3The molar ratio of NO/is between 0.95 and 1.05,
(2) when the mixed gas passes through the gas burner, the gas burner heats the mixed gas, the heated mixed gas enters the catalyst layer through the flue gas flow equalizing component, and NH is generated under the catalytic action of the catalyst3Reacting with NO;
(3) the NOx content in the denitrified smoke is less than 50mg/Nm3Sequentially contacting with an evaporation heat exchanger and a preheating heat exchanger, and after heat exchangeHas a temperature of 150 ~ 170 ℃ and is discharged through a clean flue gas outlet.
9. The method as claimed in claim 8, wherein the ammonia water vapor is obtained by vaporizing an ammonia water solution with a concentration of 10-20wt%, and the ammonia water vapor has a temperature of 140 ℃ and a volume flow of 900-1350m3Hr, flue gas flow rate of 54 ten thousand m3The speed of the jet pipe is more than or equal to 80 m/s.
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Cited By (3)
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| CN111482071A (en) * | 2020-04-14 | 2020-08-04 | 中钢集团天澄环保科技股份有限公司 | Sintering flue gas multi-pollutant cooperative purification and waste heat utilization system and process |
| CN111636951A (en) * | 2020-04-28 | 2020-09-08 | 江苏峰业科技环保集团股份有限公司 | Marine diesel engine tail gas SCR deNOx systems |
| CN117969217A (en) * | 2024-04-01 | 2024-05-03 | 上海轩鼎冶金科技集团有限公司 | Flue gas treatment system for detection and medicament life detection method |
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| CN117969217B (en) * | 2024-04-01 | 2024-06-07 | 上海轩鼎冶金科技集团有限公司 | Flue gas treatment system for detection and medicament life detection method |
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Application publication date: 20191220 |