CN102626588A - SNCR (Selective Non Catalytic Reduction) denitrification process and device for flue gas purification of circulating fluidized bed (CFB) - Google Patents
SNCR (Selective Non Catalytic Reduction) denitrification process and device for flue gas purification of circulating fluidized bed (CFB) Download PDFInfo
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Abstract
The invention discloses an SNCR (Selective Non Catalytic Reduction) denitrification process and device for flue gas purification of a circulating fluidized bed (CFB). The SNCR denitrification process comprises the steps of: spraying a reducing agent into air intake flues of the CFB to be mixed with air, introducing a mixture into a hearth of the CFB to undergo SNCR with NOx in flue gas, and continuously reacting unreacted reducing agent in the hearth with NOx in the flue gas in a cyclone drum of the CFB. The SNCR denitrification device takes the hearth of the CFB as a reactor and comprises the furnace hearth, the cyclone drum, an air preheater and ammonia spraying systems, wherein the air preheater is communicated with the bottom and the middle of the hearth respectively through one air intake flue, and the air intake flues are provided with the ammonia spraying systems. According to the invention, a CFB boiler system is fully utilized to increase an effect on mixing the reducing agent and coal-fired flue gas, prolong the effect contact time between the reducing agent and NOx, increase denitrification efficiency, reduce ammonia escape and reduce the production cost of the SNCR denitrification process.
Description
Technical field
The present invention relates to the smoke gas treatment technical field, be specifically related to a kind of SNCR denitrating technique and device that is used for the recirculating fluidized bed gas cleaning.
Background technology
Along with improving constantly of national requirements for environmental protection, standard limit of smog release increasingly stringent, denitrating flue gas become present one big focus.Main gas denitrifying technology has following several kinds: selective catalytic reduction (SCR), SNCR method (SNCR), SNCR and SCR combination method (SNCR-SCR), oxidation liquid absorption process, microbial method, active carbon adsorption, electronic beam method etc.Wherein, first three methods is the present industrial method of widespread usage in the world, but these three kinds of methods respectively have its weak point.
The SCR method is a method of denitration the most commonly used at present, under the effect of catalyst, changes into the natural nitrogen G&W that contains in the air to NOx through reducing agents such as ammonia, urea; This method denitration efficiency is high, and secondary pollution is little, but the equipment investment expense is big; Need use catalyst, operation and maintenance cost is high; SNCR is not having under the catalyst action, in 900～1100 ℃ of burner hearths, sprays into reducing agent, is reactor with the burner hearth, reducing agent NH
3(or be vaporized into NH
3Or pyrolysis becomes NH rapidly
3) generate nitrogen with NOx reaction in the flue gas, have a certain amount of oxygen in the burner hearth and exist, the reducing agent that sprays into optionally reacts with NOx; Very slow with the oxygen reaction reaction speed, this method does not need catalyst, and the one-time investment expense is less; But because reaction temperature is high, higher to the designing requirement of spray gun and system, if design unreasonable; Then denitration efficiency is lower, also exists the danger of the escaping of ammonia.
The SNCR denitration is a reactor with the burner hearth of recirculating fluidized bed (CFB); Bottom and middle part at burner hearth are respectively arranged with the air flue of in burner hearth, sending into air; The air flue is communicated with blower fan respectively through behind the air preheater, is communicated with the whirlwind tube on the top of burner hearth, and the bottom of whirlwind tube is communicated with burner hearth; Dust after the cyclonic separation sent in the burner hearth burn away; Flue gas after the cyclonic separation is sent into the subsequent treatment system through behind superheater, economizer and the air preheater successively through flue, also is provided with the spray ammonia system, in burner hearth or whirlwind tube, sprays into reducing agent.
Application publication number is that to disclose a kind of be the SNCR equipment for denitrifying flue gas of reducing agent with urea to the Chinese patent document of CN102274687A; Comprise that urea solid tank car, flexible pipe, articulation, solid urea control valve, solid urea storage tank, solid urea batcher, pneumatic manifold, compressed air regulating valve, agitator, urea liquid preparation jar, heater, industry water house steward, industry water control valve, urea delivery pump, urea liquid holding vessel, urea-spray pump, blender, urea return valve, pressurization industry water control valve, industrial water pump, urea dilution control valve, atomizing steam control valve, atomizing steam house steward and urea-spray unit are communicated with composition by technological requirement; This device is realized full-automatic continuous-feeding; Guarantee the concentration and the uniformity of urea liquid; Automatically regulate the urea flow according to combustion apparatus NOx discharge capacity; Make combustion apparatus NOx discharge capacity in control range, denitration effect is 60%, but the treatment facility that this device is provided with to reducing agent; Its complex structure; Technological requirement is high, so cost is high, is unfavorable for the raising of economic benefit of enterprises.
Publication number is to disclose a kind of employing ammonia decomposition catalyzer in the Chinese patent of CN101569834 to improve conventional scr and SNCR technology.This technology can be decomposed the purpose that reaches control the escaping of ammonia rate with unnecessary ammonia, but need provide higher than ammonia amount used among conventional scr or the SNCR in order to reach higher denitration efficiency through behind the ammonia restoring system, being added a kind of equipment of ammonia decomposition catalyzer.Therefore the increase of ammonia spraying amount and the decomposition of excess ammonia increased the investment and the operating cost of this technology.
Therefore develop a kind of can the reduction and have spray gun and requirement of system design now, utilize the original body construction of boiler, realize efficient denitration, can advance the practical applications process of denitrating flue gas greatly.
Summary of the invention
The invention provides a kind of SNCR denitrating technique and device that is used for the recirculating fluidized bed gas cleaning; Make full use of the CFB steam generator system; Improve the mixed effect of reducing agent and coal-fired flue-gas, increased effective time of contact of reducing agent and NOx, improved denitration efficiency; Reduce the escaping of ammonia, reduce the production cost of SNCR denitrating technique.
A kind of SNCR denitrating technique that is used for the recirculating fluidized bed gas cleaning comprises:
Reducing agent is sprayed in the air air intake flue of said recirculating fluidized bed; With in the burner hearth of sending into said recirculating fluidized bed after air mixes with flue gas in NOx carry out the SNCR reaction; In burner hearth unreacted reducing agent in the whirlwind tube of said recirculating fluidized bed, continue with flue gas in NOx reaction, the temperature in said burner hearth is higher than 1100 ℃ or said whirlwind tube outlet temperature and is lower than 800 ℃ and stops to spray into reducing agent.
Carry out air intake one time in the bottom of boiler; Secondary air is carried out at middle part at boiler, and the air of air intake and secondary air is all sent into the burning of participating in fuel in the burner hearth again after being preheating to uniform temperature, in the air flue, spray into reducing agent among the present invention; Reducing agent gets into boiler after air mixes; Participate in burning in the burner hearth air of boiler, reducing agent then with flue gas in NOx the SNCR reaction takes place, slough NOx in the flue gas; In burner hearth unreacted reducing agent continue with flue gas get in the whirlwind tube with flue gas in NOx react, reach the purpose of flue.As a kind of optimized technical scheme, said reducing agent mixes the back and sends in the burner hearth from the bottom or the middle part of burner hearth with air.Send in the burner hearth from the bottom and the middle part of burner hearth after a kind of preferred technical scheme, said reducing agent are mixed with air, the contact-making surface of reducing agent and air is wider like this, and time of contact is longer, mixes more even.
The key reaction of reducing agent in burner hearth and whirlwind tube is following:
4NH
3+4NO+O
2→4N
2+6H
2O (1)
4NH
3+5O
2→4NO+6H
2O (2)
The optimal reactive temperature of described SNCR reaction is 800～1100 ℃; When the temperature in the burner hearth is lower than 800 ℃; Reducing agent ammonia does not react, but when temperature is higher than 1100 ℃, the oxidized decomposition of reducing agent ammonia in the burner hearth; Reduce denitration efficiency, therefore the temperature in said burner hearth is higher than 1100 ℃ or said whirlwind tube outlet temperature and is lower than 800 ℃ and stops to spray into reducing agent.
The selection of reducing agent can be selected the reducing agent of conventional SNCR denitrating technique for use, and the reducing agent described in the present invention is at least a in liquefied ammonia, ammoniacal liquor and the urea.When described reducing agent was ammonia spirit, the mass percent concentration of ammonia spirit was 1%～25%; Described reducing agent is a urea liquid, and the mass percent concentration of urea liquid is 1%～55%; When described reducing agent was liquefied ammonia, liquefied ammonia was vaporized earlier and is diluted to 5% volume fraction with the dilution blower fan.
Can know that according to reaction equation (1) 1 mole of NO of SNCR reduction needs 1 mole NH in theory
3, and in the practice, because ammonia has to escape and has the oxidized decomposition of part when perhaps temperature is too high; So the mol ratio theoretical value of general reducing agent and NOx is big, the mol ratio increase of reducing agent and NOx helps the reduction of NOx in the flue gas, but when the amount of reducing agent is excessive; The effective rate of utilization of reducing agent can reduce, and is unfavorable for the control of cost, so; Among the present invention, according to the content of NO in the temperature of flue gas and the flue gas, the emitted dose of ammoniacal liquor or ammonia is preferably NH
3: NO=0.5～3 (mol ratio).Air passed through before sending into burner hearth through air preheater; Utilize the heat of flue gas that air heat is sent in the burner hearth after uniform temperature again, help the igniting of burner hearth fuel and fully burning, among the present invention; The temperature of described air air intake flue air is 150～400 ℃; Reducing agent sprays under this temperature in the air flue, and the back of being gasified fully mixes with air, sends in the burner hearth together again; Air is participated in burning, and the NOx in reducing agent and the flue gas carries out the SNCR reaction.
The present invention also provides a kind of device of realizing like described SNCR denitrating technique; Comprise burner hearth, whirlwind tube, air preheater and spray ammonia system; Be communicated with through a wind and smoke road between described air preheater and the burner hearth bottom; Be communicated with through the secondary wind flue between described air preheater and the burner hearth middle part, at least one is provided with described spray ammonia system in a described wind and smoke road and the secondary wind flue.
Wind and secondary wind are sent in the air preheater through the air flue through primary air fan and overfire air fan respectively; In air preheater, utilize fume afterheat with air heat to 150～400 ℃; On the air air intake flue between air preheater and burner hearth, in flue, spray into reducing agent such as liquefied ammonia, ammoniacal liquor etc. through the spray ammonia system; Reducing agent is sent in the burner hearth after air mixes in flue; Air is participated in burning; NOx in reducing agent and the flue gas reacts, in burner hearth unreacted reducing agent with flue gas get in the whirlwind tube continue with flue gas in the NOx reaction, flue gas is discharged through superheater, economizer and the air preheater of recirculating fluidized bed after cyclonic separation successively.
A said wind and smoke road is connected with primary air fan through first pipeline in the air preheater; Said secondary wind flue is connected with overfire air fan through second pipeline in the air preheater.
The spray gun of spray ammonia requires high temperature resistant (800～1100 ℃), wear-resistant (exhaust gas dust content is high in the burner hearth), therefore having relatively high expectations to spray gun in burner hearth; In the air intake stack, spray into reducing agent among the present invention, the temperature in the intake stack is lower, and is low to the requirement of spray ammonia system; Spray gun only need 150～400 ℃, do not have to work under the dust condition, technological requirement is much lower, can reduce the technology cost; Because burner hearth has two air air intake flues; Spray into reducing agent on any therein air air intake flue and can both reach the object of the invention, as a kind of optimized technical scheme, described spray ammonia system is arranged on wind and smoke road; As another kind of optimized technical scheme, described spray ammonia system is arranged on the secondary wind flue.
For reducing agent is better disperseed in burner hearth, need reducing agent better be dispersed in the air intake air of burner hearth in advance, so, be equipped with the spray ammonia system on a described wind and smoke road and the secondary wind flue as a kind of preferred technical scheme.
Reducing agent is mixed with air by the gasification back in the air flue; In order to make reducing agent and flue gas obtain better mixing; Need to prolong its effective incorporation time; So, as a kind of optimized technical scheme, described spray ammonia system be arranged on wind and smoke road and/or the secondary wind flue near the air preheater position.
Beneficial effect of the present invention:
1. in the flue of air intake or secondary air, spray into reducing agent, make full use of original boiler and carry out reducing agent to wind system and mix,, realize that flue gas evenly mixes through a wind air intake of CFB kiln gas blast cap; Temperature is in the good denitration reaction interval in the CFB stove hall, has prolonged effective time of contact of reducing agent and nitrogen oxide, helps fully carrying out of denitration reaction.And spray into reducing agent at the flue of burner hearth or furnace outlet back, and the distance weak point is mixed at the place of spraying into, temperature is high, is prone to cause mixing inhomogeneous, and amount of ammonia slip is excessive.
2. unreacted ammonia and NOx carry out secondary and mix and reaction in this technology in the whirlwind tube, further improve denitration efficiency and have reduced the escape of ammonia, thereby alleviated the infringement to the boiler follow-up equipment that is caused by the escaping of ammonia in the existing SNCR technology.
The spray ammonia system at air intake or secondary air flue place than the furnace outlet place or the flue of furnace outlet back; Have that temperature is low, air quantity is little, flue is narrow and dust concentration is zero characteristics basically; Therefore the technological requirement to spray gun greatly reduces, and the cost of spraying system also reduces relatively.
4. to the not infringement of boiler and water-cooling wall, and perforate is convenient, installs simple.
5. mix owing to reducing agent, so ammonia nitrogen is smaller, can reduce operating cost with respect to existing SNCR technology.
Description of drawings
Fig. 1 is a structural representation of the present invention;
Fig. 2 is the system ammonia spray ammonia system when being reducing agent with ammoniacal liquor;
Fig. 3 is the system ammonia spray ammonia system when being reducing agent with liquefied ammonia.
The specific embodiment
As shown in Figure 1, a kind of SNCR denitrification apparatus is a reactor with the burner hearth 1 of recirculating fluidized bed, in recirculating fluidized bed, sprays reducing agent through spray ammonia system 3, carries out denitrating flue gas.
Primary air fan 1, overfire air fan 2, wind and smoke road 4, secondary wind flue 5, burner hearth 6, whirlwind tube 7, superheater 8, economizer 9 and an air preheater 10 are the intrinsic part of recirculating fluidized bed; Primary air fan 1 and overfire air fan 2 are all through the corresponding pipeline connection in pipeline and the air preheater 10; Air preheater 10 is communicated with through a wind and smoke road 4 with the bottom of burner hearth 6; Be communicated with through secondary wind flue 5 with the middle part of burner hearth 6; The inlet of whirlwind tube 7 is communicated with the top of burner hearth 6; Bottom flying dust outlet is communicated with the bottom of burner hearth 6, and the top of whirlwind tube 7 is communicated with superheater 8, economizer 9 and air preheater 10 successively through flue, at last flue gas is sent into next flue gas treatment process.
On wind and smoke road 4 and secondary wind flue 5, all be communicated with spray ammonia system 3 near air preheater 10 positions; Spray ammonia system 3 is carried out difference setting according to the kind difference of reducing agent; With regard to spray ammonia system 3, can adopt spray ammonia system ripe in the prior art.
When reducing agent is ammoniacal liquor; Spray ammonia system 3 is as shown in Figure 1; Comprise ammoniacal liquor tank car 301, ammoniacal liquor dispenser pump 302, tank used for storing ammonia 303, ammoniacal liquor delivery pump 304, dilution water storage tank 306, dilution water delivery pump 307, metering mixing module 309; Through ammoniacal liquor dispenser pump 302 ammoniacal liquor in the ammoniacal liquor tank car 301 is sent in the tank used for storing ammonia 303; Ammoniacal liquor in the tank used for storing ammonia 3 is sent in the metering mixing module 308 through ammoniacal liquor delivery pump 304, and dilution water supply 305 is sent in the dilution water storage tank 306, delivers in the metering mixing module 309 through dilution water delivery pump 307 then; In metering mixing module 309, feed compressed air 8 simultaneously, the reducing agent for preparing sprays into reducing agent 11 and compressed air 11 in wind and smoke road 4 and the secondary wind flue 5 through spray gun.
When reducing agent is liquefied ammonia; Spray ammonia system 3 is as shown in Figure 2; Comprise liquefied ammonia tank car 312, pump 313, liquid ammonia storage tank 314, ammonia evaporimeter 315, ammonia buffer tank 316, blower fan 318 and blender 319; Through pump 313 liquefied ammonia in the liquefied ammonia tank car 312 is delivered in the liquid ammonia storage tank 314, the liquefied ammonia in the liquid ammonia storage tank 314 is gasificated into ammonia in ammonia evaporimeter 315, is stored in then in the ammonia buffer tank 316; Ammonia in the ammonia buffer tank 316 is sent in the blender 319; Through blower fan 318 air 317 is sent in the blender 319 simultaneously, ammonia is diluted to 5% volume fraction, through ammonia-spraying grid 320 reducing agent is sprayed in wind and smoke road 4 and the secondary wind flue 5 then.
Technological process of the present invention is following:
One time air intake is sent in the air preheater 10 through primary air fan 1; Utilize fume afterheat with air heat to 150～400 ℃; Deliver to the bottom of burner hearth 6 then through wind and smoke road 4; Secondary air is sent in the air preheater 10 through overfire air fan 2, utilizes flue gas and people with air heat to 150～400 ℃, delivers to the middle part of burner hearth 6 then through secondary wind flue 5.
In wind and smoke road 4 and secondary wind flue 5, spray into reducing agent through spray ammonia system 3, reducing agent is delivered to after air mixes in the burner hearth 6, and air is participated in burning, and the NOx generation one-level in reducing agent and the flue gas changes into N with the NOx in the flue gas
2And water; The unreacted reducing agent gets in the whirlwind tube 7 with flue gas in burner hearth 6; In whirlwind tube 7, carrying out secondary mixes and the secondary denitration; After flue is delivered to subsequent processing after lowering the temperature through superheater 8, economizer 8 and preheater 10 successively, the flying dust in the whirlwind tube 7 after the cyclonic separation is back in the burner hearth 6 and burns away flue gas in the whirlwind tube 7 after the secondary denitration through cyclonic separation.
Temperature in burner hearth 6 is higher than 1100 ℃ or whirlwind tube 7 outlet temperatures and is lower than 800 ℃ and stops to spray into reducing agent.
When described reducing agent was ammonia spirit, the mass percent concentration of ammonia spirit was 1%～25%; Described reducing agent is a urea liquid, and the mass percent concentration of urea liquid is 1%～55%; When described reducing agent was liquefied ammonia, liquefied ammonia was vaporized earlier and is diluted to 5% volume fraction with the dilution blower fan.
The smoke gas on-line monitor monitoring that The data Siemens Company such as smoke components produces in following examples.
Embodiment 1
In certain engineering test, an air intake air quantity is 220200Nm
3/ h, gas component is following: O
2Be 21%, N
2Be 79%, 300 ℃ of gas temperatures.The exhaust gas volumn that produces is 260000Nm
3/ h, flue gas composition is following: O
2Be 4.89%, SO
2Be 1531mg/m
3, NO is 202mg/m
3Adopt mass fraction be 10% ammonia spirit as reducing agent, ammonia nitrogen utilizes technology of the present invention than according to 1: 1.2 (mol ratio), carries out denitration.The one-level denitration efficiency can reach 70%, and NO is 61mg/m in the flue gas
3, after the secondary denitration, whirlwind tube exit NO is 48mg/m
3, overall denitration efficiency 76%.
In certain engineering test, an air intake air quantity is 230110Nm
3/ h, gas component is following: O
2Be 21%, N
2Be 79%, 300 ℃ of gas temperatures.The exhaust gas volumn that produces is 270150Nm
3/ h, flue gas composition is following: O
2Be 4.65%, SO
2Be 1480mg/m
3, NO is 212mg/m
3Adopt volume fraction be 5% ammonia as reducing agent, ammonia nitrogen utilizes technology of the present invention than according to 1: 1.2 (mol ratio), carries out denitration.The one-level denitration efficiency can reach 71%, and NO is 61mg/m in the flue gas
3, after the secondary denitration, whirlwind tube exit NO is 50mg/m
3, overall denitration efficiency 76.5%.
Embodiment 3
In certain engineering test, an air intake air quantity is 240350Nm
3/ h, gas component is following: O
2Be 21%, N
2Be 79%, 300 ℃ of gas temperatures.The exhaust gas volumn that produces is 278000Nm
3/ h, flue gas composition is following: O
2Be 4.98%, SO
2Be 1624mg/m
3, NO is 189mg/m
3.Adopt mass fraction be 10% urea liquid as reducing agent, ammonia nitrogen utilizes technology of the present invention than according to 1: 1.2 (mol ratio), carries out denitration.The one-level denitration efficiency can reach 65%, and NO is 66mg/m in the flue gas
3, after the secondary denitration, whirlwind tube exit NO is 55mg/m
3, overall denitration efficiency 71%.
Claims (10)
1. a SNCR denitrating technique that is used for the recirculating fluidized bed gas cleaning is characterized in that, comprising:
Reducing agent is sprayed in the air air intake flue of said recirculating fluidized bed; With in the burner hearth of sending into said recirculating fluidized bed after air mixes with flue gas in NOx carry out the SNCR reaction; In burner hearth unreacted reducing agent in the whirlwind tube of said recirculating fluidized bed, continue with flue gas in NOx reaction, the temperature in said burner hearth is higher than 1100 ℃ or said whirlwind tube outlet temperature and is lower than 800 ℃ and stops to spray into reducing agent.
2. SNCR denitrating technique according to claim 1 is characterized in that, said reducing agent mixes the back and sends in the burner hearth from the bottom or the middle part of burner hearth with air.
3. SNCR denitrating technique according to claim 1 is characterized in that, said reducing agent mixes the back and sends in the burner hearth from the bottom and the middle part of burner hearth with air.
4. the device of realization such as the described SNCR denitrating technique of the arbitrary claim of claim 1～3; Comprise burner hearth (6), whirlwind tube (7), air preheater (10) and spray ammonia system (3); Be communicated with through a wind and smoke road (4) between described air preheater (10) and burner hearth (6) bottom; Be communicated with through secondary wind flue (5) between described air preheater (10) and burner hearth (6) middle part; It is characterized in that at least one is provided with described spray ammonia system (3) in a described wind and smoke road (4) and the secondary wind flue (5).
5. device according to claim 4 is characterized in that, a said wind and smoke road (4) is connected with primary air fan (1) through first pipeline in the air preheater (10).
6. device according to claim 4 is characterized in that, said secondary wind flue (5) is connected with overfire air fan (2) through second pipeline in the air preheater (10).
7. device according to claim 4 is characterized in that, described spray ammonia system (3) is arranged on the wind and smoke road (4).
8. device according to claim 4 is characterized in that, described spray ammonia system (3) is arranged on the secondary wind flue (5).
9. device according to claim 4 is characterized in that, is equipped with spray ammonia system (3) on a described wind and smoke road (4) and the secondary wind flue (5).
10. according to the described device of the arbitrary claim of claim 7～9, it is characterized in that, described spray ammonia system (3) be arranged on a wind and smoke road (4) and/or the secondary wind flue (5) near air preheater (10) position.
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| CN103349898A (en) * | 2013-07-04 | 2013-10-16 | 张蕊 | SNCR (Selective Non-catalytic Reduction) denitration device and denitration method |
| CN103406013A (en) * | 2013-08-24 | 2013-11-27 | 中能东讯新能源科技(大连)有限公司 | Catalysis-free reduction method two-stage denitration device of circulating fluidized bed boiler |
| CN103432955A (en) * | 2013-08-19 | 2013-12-11 | 江苏新中环保股份有限公司 | Device for diluting ammonia-water solution |
| CN103752160A (en) * | 2014-01-28 | 2014-04-30 | 上海交通大学 | Method for realizing ultra-low emission of NOx of circulating fluidized bed boiler |
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| CN110756030A (en) * | 2019-11-01 | 2020-02-07 | 王惠生 | Economical and efficient in-furnace denitration method |
| CN110975581A (en) * | 2019-12-12 | 2020-04-10 | 湖南人文科技学院 | Device for improving SNCR (selective non-catalytic reduction) denitration efficiency of circulating fluidized bed boiler |
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