CN103977702A - Flue gas desulfurization, denitration and demercuration integrated device with circulating fluidized bed and method - Google Patents
Flue gas desulfurization, denitration and demercuration integrated device with circulating fluidized bed and method Download PDFInfo
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- CN103977702A CN103977702A CN201410210209.0A CN201410210209A CN103977702A CN 103977702 A CN103977702 A CN 103977702A CN 201410210209 A CN201410210209 A CN 201410210209A CN 103977702 A CN103977702 A CN 103977702A
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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Abstract
The invention discloses a flue gas desulfurization, denitration and demercuration integrated device with a circulating fluidized bed and a method. A circulating fluidized bed reaction tower in the device is sequentially provided with a smoke chamber, a venturi tube, a first-order reaction zone, a shrinking opening, a second-order reaction zone and a reaction tower outlet from bottom to top, and atomizing spray guns are respectively arranged in the first-order reaction zone and the second-order reaction zone; 4-6 bypass pipelines are uniformly arranged outside the circulating fluidized bed reaction tower, and an inlet and an outlet of each bypass pipeline are respectively connected with the smoke chamber and the bottom of the second-order reaction zone; oxidizing agent adding openings are formed in an absorbent activator and a returning material activator, and activated absorbents and returning material ash directly enter the bottom of the first-order reaction zone. Through site digestion of calcium-based absorbents, structural improvement of the circulating fluidized bed reaction tower and optimization of operating parameters, on the basis of ensuring the desulfurization efficiency, the device strengthens the catalytic oxidation ability of the absorbents in the first-order reaction zone to NOx and gaseous elemental mercury (Hg0). The device realizes integration of desulfurization, denitration and demercuration through the reasonable combination of the first-order reaction zone and the second-order reaction zone.
Description
Technical field
The present invention relates to a kind of circulating fluid bed flue-gas desulfurizing denitration demercuration integrated apparatus and method, belong to environmental protection equipment and flue gases purification field.
Background technology
Along with the rapid growth of coal utilization amount, the SO of fire coal boiler fume discharge
x, NO
xand the pollutant such as heavy metal Hg is high, has a strong impact on ecological environment and human health.It is the comparatively ripe Pollutant Control Technology adopting at present that wet process of FGD (Wet-FGD), SCR (SCR) denitration and active carbon spray (ACI) demercuration, can obtain higher pollutant removing efficiency.But wet process of FGD exists investment operation and maintenance cost high, obstruction, corrosion and serious wear, the defect such as desulfurization wastewater is more difficult.Due to the effect of catalyst, SCR denitration meeting significantly increases SO
3growing amount, and with excessive NH
3generate NH
4hSO
4thereby, cause back-end ductwork Corrosion blockage phenomenon, in addition, catalyst poisoning and SO
3secondary pollution problem also can not be ignored.Active carbon sprays that demercuration rule exists that operating cost is high, active carbon utilization rate is low and the defect such as flying dust comprehensive utilization difficulty.Meanwhile, above-mentioned Pollutant Control Technology is independently being controlled different pollutants in device respectively, has that system complex, floor space are large, a defect such as investment and operating cost height, and therefore, the desulfurization denitration demercuration integrated apparatus of development of new is imperative.
Circulating fluid bed flue gas desulfurization technique (CFB-FGD) is one of coal-burning boiler main flume desulfur technology, this technique have investment and operating cost is low, desulfuration efficiency is high, without features such as wastewater treatments, be at home and abroad widely used.This technique is by desulfurizing agent repeatedly circulation in reaction tower, the time of contact of prolong smoke and desulfurizing agent, and then improved the removal efficiency of pollutant.But conventional CFB-FGD technique is mainly used in controlling the SO in flue gas
2, to NO in flue gas
xvery low with the removal efficiency of mercury, and load adjustment ability is poor.At present, improving load adjustment ability and realize desulfurization denitration demercuration integrated, is the important directions of CFB-FGD technology exhibition.Patent CN1498673A discloses method and the device thereof of integrated of a kind of stack gas desulfurization and dust removal of circulating fluid bed, by spray into desulfurizer slurry and the water of atomization in circulating fluidized bed desulfurization tower, and realize desulphurizing and dust-removing integral in conjunction with sack cleaner, but this method exists flue gas optimal reaction temperature to control difficulty, equipment is the defect such as obstruction and corrosion easily, can not realize SO simultaneously
2, NO
xremove with combining of Hg.Patent CN1962034A discloses a kind of method and device thereof of removing sulfur, nitrate and mercury simultaneously from boiler flue gas, specifically, by spray into oxygen enrichment high activity adsorbent in recirculating fluidized bed reaction tower, realizes SO in flue gas
2, NO
xin the time of with mercury, remove, but this method is not carried out corresponding optimization to fume desulfurizing tower, exist equally absorbent reaction condition to control the defects such as difficult, load adjustment ability is poor.Patent CN102188883A discloses a kind of flue gas desulfurization and denitrification removing heavy-metal integrated purifying device, by spray-absorption liquid in absorption tower, realizes the SO in flue gas
2, NO
xremove with heavy metal, this spraying method belongs to wet processing simultaneously, and it has system complex, installs the defects such as perishable, maintenance workload is large.CN203447967U discloses a kind of Industrial Boiler flue gas combined desulfurization and denitration mercury removal device, and this method is with ozone (O
3) and calcium-base absorbing agent be depleting agents, although can realize SO
2, NO
xremove combining of multiple pollutant with mercury etc., but have the defects such as energy consumption is high, ozone utilization rate is low.Patent CN102019135A discloses a kind of flue gas combined desulfurization and denitration method and device thereof, and in this technology utilization Benitration reactor and desulfurization reactor, the activated coke of filling, removes respectively the NO in flue gas
xand SO
2, but this method not only needs to use expensive active carbon, and have that system complex, floor space are large, the defect such as initial cost and operating cost height.
Summary of the invention
The object of the invention is to overcome the defect that existing circulating fluid bed flue gas desulfurization technique exists, a kind of circulating fluid bed flue-gas desulfurizing denitration demercuration integrated apparatus and method are provided, when improving recirculating fluidized bed reaction tower load adjustment ability, realize SO
x, NO
xremove with combining of mercury.
A kind of circulating fluid bed flue-gas desulfurizing denitration demercuration integrated apparatus involved in the present invention, comprising: inlet flue duct, and boiler tail flue gas enters thus; Recirculating fluidized bed absorption tower, the main place of reacting with absorbent as pollutant and smoke gas flow circulation passage; Absorption tower is provided with smoke-box, Venturi tube, first order reaction district, bypass duct, reducing, second order reaction district and reaction tower outlet from bottom to top successively, and reaction tower outlet is connected with pre-duster; Absorbent warehouse and dispenser, absorbent activator are connected successively; Described pre-duster, sack cleaner, air-introduced machine and chimney are connected successively, and pre-duster bottom is connected with returning charge activator, and the outlet of returning charge activator is connected with bottom, first order reaction district; Described sack cleaner bottom is provided with material-returning device, and material-returning device is connected with cinder tank pump with returning charge activator respectively.
In the first order reaction district of recirculating fluidized bed reaction tower and second order reaction district, be respectively equipped with atomizing lance.
Recirculating fluidized bed reaction tower evenly arranges 4～6 bypass ducts outward, and bypass duct is imported and exported respectively and is connected with bottom, second order reaction district with smoke-box, for regulating flue gas load.
Further, the caliber Φ of bypass duct is 300～600mm.The angle α of bypass duct and recirculating fluidized bed reaction tower cylindrical shell normal direction is 15～75 °.
On absorbent activator and returning charge activator, be respectively equipped with oxidant and add mouth.
The integrated method of circulating fluid bed flue-gas desulfurizing denitration demercuration involved in the present invention is:
1) boiler smoke (140 ℃ of left and right) enters the smoke-box of recirculating fluidized bed reaction tower bottom through inlet flue duct, in smoke-box, be divided into two-way, wherein a road flue gas (accounting for total exhaust gas volumn 80% left and right) directly enters first order reaction district through Venturi tube, and another road flue gas (accounting for total exhaust gas volumn 20% left and right) enters second order reaction district through the bypass duct of 4～6 Φ 300～600mm.
2) calcium-base absorbing agent in absorbent warehouse is (as Ca (OH)
2, CaO) through dispenser, enter absorbent activator, at this and oxidant (KMnO
4, NaClO
2, CaClO
2with one or more the mixed solution in NaCl) mix and activation processing, wherein oxidant addition is calcium-base absorbing agent 0.5～5%.Absorbent after activation processing is directly sent into first order reaction district; Meanwhile, a certain amount of atomized water and returning charge lime-ash are also admitted to first order reaction district, fully contact under the venturi effect of spurting at a high speed, and forming flue-gas temperature is the high humidity reaction zone that 60 ℃ of left and right, relative humidity are 40%～90%, and then by catalytic oxidation, by the NO in flue gas and Hg
0be oxidized to respectively the NO that solubility is high
2, N
2o
3with oxidation state mercury (Hg
2+), and then by the SO in flue gas
x, NO
xand gaseous elemental mercury (Hg
0) etc. pollutant be separately converted to CaSO
3, CaSO
4, Ca (NO
3)
2and oxidation state mercury is (as HgO, HgCl
2) etc., and adsorbed by solid particle, thereby realize SO in flue gas
x, NO
xwith once removing of the pollutants such as Hg.
3) upwards flowing along with flue gas, flue gas in first order reaction district and solid particle material, after accelerating, reducing enters second order reaction district, the boiler smoke entering with bypass duct at this (20% left and right) mixes, by the adjustment of atomized water and exhaust gas volumn, flue-gas temperature in control second order reaction district is between 65～75 ℃, thus SO realize flue gas under suitable approach temperature and oxidizing condition in
xremove with the secondary of the pollutants such as mercury.
4) flue gas flowing out from the outlet of recirculating fluidized bed reaction tower enters pre-duster, in pre-duster, under the effect of deflector and porous plate, removes most granule materials (absorbent and lime-ash); Flue gas after pre-duster one-time dedusting enters sack cleaner again and carries out final dusting, and the clean flue gas after final dusting is emptying through air-introduced machine and chimney.Meanwhile, the part solid particle material that the total solids material that pre-duster is collected and sack cleaner are collected is transmitted back in first order reaction district after the activation of returning charge activator.
When entering boiler load and change, can, by regulating the actual aperture with valve on radical and every pipeline of bypass duct to control the exhaust gas volumn that enters I and II reaction zone, make the stable operation in 50%～120% load range of recirculating fluidized bed reaction tower.
In sum, the present invention, by architecture advances and the operation parameter optimization of the on-the-spot digestion of calcium-base absorbing agent, recirculating fluidized bed reaction tower, is guaranteeing, on the basis of desulfuration efficiency, to have strengthened absorbent to NO
xand gaseous elemental mercury (Hg
0) catalytic oxidation ability; Meanwhile, the method has been strengthened the repeatedly circulation of reaction tower inner absorbent, has extended the reaction time of absorbent and gaseous contaminant, thereby has effectively improved the utilization rate of absorbent and to SO in flue gas
x, NO
xoxidation removal efficiency with pollutants such as mercury.
Compared with prior art, the present invention has the following advantages:
1) by methods such as the on-the-spot digestion of absorbent, reaction tower architecture advances and operation parameter optimizations, by means of function division, strengthened absorbent to NO
xcatalytic oxidation ability with mercury, has realized circulating fluidized bed desulfur denitration demercuration integrated.
2) adopt the scene digestion of cheap calcium-base absorbing agent and returning charge lime-ash, saved that expensive absorbent is purchased and complicated absorbent preparation system, small investment, operating cost is low.
3) adopt simple bypass design, recirculating fluidized bed reaction tower and system architecture thereof are simple, easy to operate, stable, can adapt to well boiler load and change.
4) desulfuration efficiency of recirculating fluidized bed integrated apparatus can reach more than 90%, NO
xcan reach more than 50% with the oxidation removal efficiency of mercury.
Accompanying drawing explanation
Fig. 1 is a kind of circulating fluid bed flue-gas desulfurizing denitration demercuration of the present invention integrated apparatus process chart;
Fig. 2 is that bypass duct is connected (A-A) schematic diagram with second order reaction district.
The specific embodiment
Below in conjunction with the drawings and specific embodiments, the present invention is described in further detail.
As shown in Figure 1, a kind of circulating fluid bed flue-gas desulfurizing denitration demercuration integrated apparatus involved in the present invention, comprise inlet flue duct 1, recirculating fluidized bed absorption tower 2, absorbent warehouse 3, dispenser 301, absorbent activator 4, atomizing lance 12, pre-duster 5, sack cleaner 6, material-returning device 9, returning charge activator 10, cinder tank pump 11, air-introduced machine 7 and chimney 8, wherein recirculating fluidized bed reaction tower 2 is provided with smoke-box 201 from bottom to top successively, Venturi tube 202, first order reaction district 203, reducing 205, second order reaction district 206 and reaction tower outlet 207, in first order reaction district 203He second order reaction district 206, be respectively equipped with atomizing lance 12, recirculating fluidized bed reaction tower evenly arranges 4～6 bypass ducts 204 outward.Between the first order reaction district 203He second order reaction district 206 of recirculating fluidized bed reaction tower 2, by reducing 205 transition, reducing 205 can accelerate to enter the velocity of flue gas in second order reaction district 206.Interior several piece smoke deflector and the porous plate of arranging of pre-duster 5.
Boiler smoke (140 ℃ of left and right) enters the smoke-box 201 of recirculating fluidized bed reaction tower 2 bottoms through inlet flue duct 1, in smoke-box, be divided into two-way, wherein a road flue gas (accounting for total exhaust gas volumn 80% left and right) directly enters first order reaction district 203 through Venturi tube 202, another road flue gas (accounting for total exhaust gas volumn 20% left and right) enters second order reaction district 206 through the bypass duct 204 of 4～6 caliber Φ 300～600mm, bypass duct is along reaction tower circumference uniform distribution, wherein four bypass ducts and bottom, second order reaction district connected mode are as shown in Figure 2, by changing the angle α (15～75 °) of bypass gas approach and recirculating fluidized bed reaction tower cylindrical shell normal direction, strengthen bypass flue gas and the reducing immixture of flue gas in second order reaction district 206 of spurting.
Calcium-base absorbing agent in absorbent warehouse 3 is (as Ca (OH)
2, CaO) through dispenser 301, enter absorbent activator 4, absorbent activator is provided with oxidant and adds mouthfuls 401, at this, adds oxidant (KMnO
4, NaClO
2, CaClO
2with one or more the mixed solution in NaCl) absorbent is carried out to scene mix and activation processing, wherein oxidant addition is calcium-base absorbing agent 0.5～5%.Absorbent after activation is directly sent into first order reaction district 203; Meanwhile, a certain amount of atomized water and returning charge lime-ash are also admitted to first order reaction district 203, fully contact under the venturi effect of spurting at a high speed, and forming flue-gas temperature is the high humidity reaction zone that 60 ℃ of left and right, relative humidity are 40%～90%, and then by catalytic oxidation, by the SO in flue gas
x, NO
xand gaseous elemental mercury (Hg
0) etc. pollutant be separately converted to CaSO
3, CaSO
4, Ca (NO
3)
2and oxidation state mercury is (as HgO, HgCl
2) etc., and adsorbed by solid particle, realize SO in flue gas
x, NO
xwith once removing of the pollutants such as Hg.
Along with upwards flowing of flue gas, flue gas in first order reaction district 203 and solid particle material, after accelerating, reducing 205 enters second order reaction district 206, the boiler smoke entering with bypass duct at this (20% left and right) mixes, by the adjustment of atomized water and exhaust gas volumn, flue-gas temperature in control second order reaction district 206 is between 65～75 ℃, thus SO realize flue gas under suitable approach temperature and oxidizing condition in
xremove with the secondary of the pollutant such as mercury, thereby guarantee higher desulphurization and denitration and demercuration efficiency.
The flue gas flowing out from recirculating fluidized bed reaction tower outlet 207 enters pre-duster 5, under the effect of the interior deflector 501 of pre-duster 5 and porous plate 502, removes most granule materials (absorbent and lime-ash); Flue gas after pre-duster 5 one-time dedustings enters sack cleaner 6 again and carries out final dusting, and the clean flue gas after final dusting is emptying through air-introduced machine 7 and chimney 8.Meanwhile, a part of solid particle material that sack cleaner 6 is collected enters returning charge activator 10 through material-returning device 9, and another part solid particle material is through the outer row of cinder tank pump 11; In returning charge activator 10, be provided with oxidant and add mouth 1001, the part solid particle material that the total solids material that pre-duster 5 is collected and sack cleaner 6 are collected is transmitted back in first order reaction district 203 after 10 activation of returning charge activator.At excessive desulfurizing agent, repeatedly circulate, further the time of contact of extension of absorbent and flue gas, strengthen the reaction of calcium-base absorbing agent and flue gas pollutant, and then realize the object of combined desulfurization and denitration demercuration.
The present invention is by methods such as the on-the-spot digestion of calcium-base absorbing agent, recirculating fluidized bed reaction tower architecture advances and operation parameter optimizations, strengthened the repeatedly circulation of reaction tower inner absorbent, extended the reaction time of absorbent and gaseous contaminant, guaranteeing, on the basis of desulfuration efficiency, to have strengthened absorbent to NO
xand gaseous elemental mercury (Hg
0) catalytic oxidation ability, thereby effectively improved the utilization rate of absorbent and to SO in flue gas
x, NO
xoxidation removal efficiency with pollutants such as mercury.In addition, when boiler load changes, can, by regulating the actual aperture with valve on radical and every pipeline of bypass duct 205 to control the exhaust gas volumn that enters I and II reaction zone, make fluidized bed fume purifying device stable operation in 50%～120% load range.
Although described the present invention by embodiment in conjunction with being considered to optimum embodiment at present in this article, but the present invention is not subject to the restriction of described embodiment, be intended to cover various combinations or modification that feature in the scope of the invention that claims limit and other application are carried out.
Claims (8)
1. a circulating fluid bed flue-gas desulfurizing denitration demercuration integrated apparatus, is characterized in that: comprise
Inlet flue duct (1), boiler tail flue gas enters thus;
Recirculating fluidized bed absorption tower (2), the main place of reacting with absorbent as pollutant and smoke gas flow circulation passage; Absorption tower is provided with smoke-box (201), Venturi tube (202), first order reaction district (203), bypass duct (204), reducing (205), second order reaction district (206) and reaction tower outlet (207) from bottom to top successively, and reaction tower outlet (207) is connected with pre-duster (5);
Absorbent warehouse (3) is connected successively with dispenser (301), absorbent activator (4);
Described pre-duster (5), sack cleaner (6), air-introduced machine (7) and chimney (8) are connected successively, pre-duster (5) bottom is connected with returning charge activator (10), and returning charge activator (10) outlet is connected with first order reaction district (203) bottom; Described sack cleaner (6) bottom is provided with material-returning device (9), and material-returning device (9) is connected with cinder tank pump (11) with returning charge activator (10) respectively.
2. a kind of circulating fluid bed flue-gas desulfurizing denitration demercuration integrated apparatus according to claim 1, is characterized in that: in the first order reaction district (203) of recirculating fluidized bed reaction tower (2) and second order reaction district (206), be respectively equipped with atomizing lance (12).
3. a kind of circulating fluid bed flue-gas desulfurizing denitration demercuration integrated apparatus according to claim 1, it is characterized in that: outer 4～6 bypass ducts (204) that evenly arrange of recirculating fluidized bed reaction tower (2), bypass duct is imported and exported respectively and is connected with second order reaction district (206) bottom with smoke-box (201), for regulating flue gas load.
4. a kind of circulating fluid bed flue-gas desulfurizing denitration demercuration integrated apparatus according to claim 3, is characterized in that: the caliber Φ of bypass duct (204) is 300～600mm.
5. according to a kind of circulating fluid bed flue-gas desulfurizing denitration demercuration integrated apparatus described in claim 3 or 4, it is characterized in that: bypass duct (204) is 15～75 ° with the angle α of recirculating fluidized bed reaction tower (2) cylindrical shell normal direction.
6. a kind of circulating fluid bed flue-gas desulfurizing denitration demercuration integrated apparatus according to claim 1, is characterized in that: on absorbent activator (4) and returning charge activator (10), be respectively equipped with oxidant and add mouth.
7. a circulating fluid bed flue-gas desulfurizing denitration demercuration integral method, is characterized in that, detailed process is as follows:
1) temperature is about the boiler smoke of 140 ℃ and through inlet flue duct, enters the smoke-box of recirculating fluidized bed reaction tower bottom, is divided into two-way in smoke-box, and wherein a road flue gas directly enters first order reaction district through Venturi tube, and this part flue gas accounts for total exhaust gas volumn 80% left and right; Another road flue gas enters second order reaction district through bypass duct, and this part flue gas accounts for total exhaust gas volumn 20% left and right;
2) calcium-base absorbing agent in absorbent warehouse enters absorbent activator through dispenser, at this, mixes and activation processing with oxidant, and wherein oxidant addition is calcium-base absorbing agent 0.5～5%; Absorbent after activation processing is directly sent into first order reaction district; Meanwhile, a certain amount of atomized water and returning charge lime-ash are also admitted to first order reaction district, fully contact under the venturi effect of spurting at a high speed, and forming flue-gas temperature is the high humidity reaction zone that 60 ℃ of left and right, relative humidity are 40%～90%, and then by catalytic oxidation, by the NO in flue gas and Hg
0be oxidized to respectively the NO that solubility is high
2, N
2o
3with oxidation state mercury, and then by the SO in flue gas
x, NO
xbe separately converted to CaSO with pollutants such as gaseous elemental mercuries
3, CaSO
4, Ca (NO
3)
2and oxidation state mercury etc., and adsorbed by solid particle, thereby realize SO in flue gas
x, NO
xwith once removing of Hg pollutant;
3) upwards flowing along with flue gas, flue gas in first order reaction district and solid particle material, after accelerating, reducing enters second order reaction district, the boiler smoke entering with bypass duct at this mixes, by the adjustment of atomized water and exhaust gas volumn, flue-gas temperature in control second order reaction district is between 65～75 ℃, thus SO realize flue gas under suitable approach temperature and oxidizing condition in
x, NO
xremove with the secondary of Hg pollutant;
4) flue gas flowing out from the outlet of recirculating fluidized bed reaction tower enters pre-duster, in pre-duster, under the effect of deflector and porous plate, removes most granule materials; Flue gas after pre-duster one-time dedusting enters sack cleaner again and carries out final dusting, and the clean flue gas after final dusting is emptying through air-introduced machine and chimney; Meanwhile, the part solid particle material that the total solids material that pre-duster is collected and sack cleaner are collected is transmitted back in first order reaction district after the activation of returning charge activator.
8. a kind of circulating fluid bed flue-gas desulfurizing denitration demercuration integral method according to claim 7, is characterized in that, the oxidant in described step (2) is KMnO
4, NaClO
2, CaClO
2with one or more the mixed solution in NaCl.
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| CN105582793A (en) * | 2015-03-25 | 2016-05-18 | 孙厚杰 | Resourcelized desulfurization, denitrification and demercuration integrated process |
| CN104826489A (en) * | 2015-03-31 | 2015-08-12 | 山东鑫源环保工程技术有限公司 | Activated carbon and low temperature catalyst-based combined desulfurization denitration fluidized bed device |
| CN104984656A (en) * | 2015-06-23 | 2015-10-21 | 哈尔滨工业大学 | Multistage internal circulation semi-dry method desulfurization, denitrification and demercuration integrated device |
| CN108744960A (en) * | 2018-06-14 | 2018-11-06 | 华北电力大学（保定） | A kind of flue gas and desulfurizing and denitrifying demercuration and recycling unit and method |
| CN108744960B (en) * | 2018-06-14 | 2021-06-18 | 华北电力大学（保定） | Device and method for simultaneously desulfurizing, denitrifying, removing mercury and recycling flue gas |
| CN110538558A (en) * | 2019-09-17 | 2019-12-06 | 哈尔滨理工大学 | Novel desulfurization integration device for circulating fluidized bed |
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| CN103977702B (en) | 2016-01-27 |
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