CN103977702B - A kind of circulating fluid bed flue-gas desulfurizing denitration demercuration integrated apparatus and method - Google Patents

A kind of circulating fluid bed flue-gas desulfurizing denitration demercuration integrated apparatus and method Download PDF

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CN103977702B
CN103977702B CN201410210209.0A CN201410210209A CN103977702B CN 103977702 B CN103977702 B CN 103977702B CN 201410210209 A CN201410210209 A CN 201410210209A CN 103977702 B CN103977702 B CN 103977702B
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flue
order reaction
reaction district
flue gas
gas
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CN103977702A (en
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卢平
黄震
李雅宁
吉苗苗
陈宇曼
钱舒琳
周娇
史俊丽
许晨萌
徐森荣
祝秀明
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Nanjing Normal Univ
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Nanjing Normal Univ
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    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02ATECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
    • Y02A50/00TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
    • Y02A50/20Air quality improvement or preservation, e.g. vehicle emission control or emission reduction by using catalytic converters

Abstract

The invention discloses a kind of circulating fluid bed flue-gas desulfurizing denitration demercuration integrated apparatus and method.Recirculating fluidized bed reaction tower in device is provided with smoke-box, Venturi tube, first order reaction district, reducing, second order reaction district and reaction tower outlet from bottom to top successively, is respectively equipped with atomizing lance in first order reaction district and second order reaction district; Recirculating fluidized bed reaction tower evenly arranges 4 ~ 6 bypass ducts outward, and bypass duct is imported and exported and is connected with bottom smoke-box and second order reaction district respectively; Absorbent activator and returning charge activator are equipped with oxidant interpolation mouth, and the absorbent after activation and returning charge lime-ash directly enter bottom first order reaction district.The present invention is improved and operation parameter optimization by the digestion of calcium-base absorbing agent scene, recirculating fluidized bed reaction tower structure, on the basis ensureing desulfuration efficiency, enhances first order reaction district inner absorbent to NO xwith gaseous elemental mercury (Hg 0) catalytic oxidation ability, and by the reasonable combination of I and II reaction zone, achieve the integration of desulfurization denitration demercuration.

Description

A kind of circulating fluid bed flue-gas desulfurizing denitration demercuration integrated apparatus and method
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 quick growth of coal utilization amount, the SO of fire coal boiler fume discharge x, NO xand the pollutant such as heavy metal Hg remains high, and has a strong impact on ecological environment and human health.It is the comparatively ripe Pollutant Control Technology adopted 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 it is high to there is investment operation and maintenance cost in wet process of FGD, blocking, corrosion and serious wear, the defects such as desulfurization wastewater is more difficult.Due to the effect of catalyst, SCR denitration significantly can increase SO 3growing amount, and with excessive NH 3generate NH 4hSO 4, thus cause back-end ductwork Corrosion blockage phenomenon, and in addition, catalyst poisoning and SO 3secondary pollution problem also can not be ignored.Active carbon sprays demercuration rule and has 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 controls different pollutants respectively in independently device, has that system complex, floor space are large, investment and a defect such as operating cost is high, 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, and this technique has investment and operating cost is low, desulfuration efficiency is high, without the need to features such as wastewater treatments, be at home and abroad widely used.This technique is repeatedly circulated in reaction tower by desulfurizing agent, the time of contact of prolong smoke and desulfurizing agent, and then the removal efficiency that improve pollutant.But the CFB-FGD technique of routine 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 integration, 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 spraying 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 controls difficulty, equipment easily blocks and the defect such as to corrode, and 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, sprays into oxygen enrichment high activity adsorbent, realize SO in flue gas particular by recirculating fluidized bed reaction tower 2, NO xremove with while mercury, but this method does not carry out corresponding optimization to fume desulfurizing tower, there is absorbent reaction condition equally and 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, is realized the SO in flue gas by spray-absorption liquid in absorption tower 2, NO xremove with heavy metal, this spraying method belongs to wet processing simultaneously, and it has the defects such as system complex, device is 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 SO be realized 2, NO xremove combining of multiple pollutant with mercury etc., but there is 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 the activated coke of filling in this technology utilization Benitration reactor and desulfurization reactor, removes the NO in flue gas respectively 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 the defect overcoming the existence of existing circulating fluid bed flue gas desulfurization technique, a kind of circulating fluid bed flue-gas desulfurizing denitration demercuration integrated apparatus and method are provided, while 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, boiler tail flue gas enters thus; Recirculating fluidized bed absorption tower, the main place of reacting as pollutant and absorbent and flue gas 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 are connected successively with chimney, are connected bottom pre-duster with returning charge activator, and the outlet of returning charge activator is connected with bottom first order reaction district; Be provided with material-returning device bottom described sack cleaner, material-returning device is connected with cinder tank pump with returning charge activator respectively.
Atomizing lance is respectively equipped with in the first order reaction district of recirculating fluidized bed reaction tower and second order reaction district.
Recirculating fluidized bed reaction tower evenly arranges 4 ~ 6 bypass ducts outward, and bypass duct is imported and exported and is connected, for regulating flue gas load with bottom smoke-box and second order reaction district respectively.
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 °.
Absorbent activator and returning charge activator are respectively equipped with oxidant interpolation mouth.
The method of circulating fluid bed flue-gas desulfurizing denitration demercuration integration involved in the present invention is:
1) boiler smoke (about 140 DEG C) enters the smoke-box bottom recirculating fluidized bed reaction tower through inlet flue duct, two-way is divided in smoke-box, wherein a road flue gas (accounting for total exhaust gas volumn about 80%) directly enters first order reaction district through Venturi tube, and another road flue gas (accounting for total exhaust gas volumn about 20%) 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) enter absorbent activator through dispenser, at this and oxidant (KMnO 4, NaClO 2, CaClO 2with the mixed solution of one or more in NaCl) carry out mixing and activation process, wherein oxidant addition is 0.5 ~ 5% of calcium-base absorbing agent.First order reaction district directly sent into by absorbent after activation process; 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 at a high speed effect of spurting, and form the high humidity reaction zone that flue-gas temperature is about 60 DEG C, relative humidity is 40% ~ 90%, and then by catalytic oxidation, by NO and Hg in flue gas 0be oxidized to the NO that solubility is high respectively 2, N 2o 3with oxidation state mercury (Hg 2+), and then by the SO in flue gas x, NO xwith 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, thus realize SO in flue gas x, NO xwith once removing of the pollutants such as Hg.
3) along with the upwards flowing of flue gas, flue gas in first order reaction district and solid particle material, second order reaction district is entered after reducing is accelerated, the boiler smoke (about 20%) entered at this and bypass duct mixes, by the adjustment of atomized water and exhaust gas volumn, flue-gas temperature in control second order reaction district between 65 ~ 75 DEG C, thus realizes SO in flue gas under suitable approach temperature and oxidizing condition xremove with the secondary of the pollutants such as mercury.
4) flue gas flowed out from the outlet of recirculating fluidized bed reaction tower enters pre-duster, under the effect of pre-duster inner 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, the clean flue gas after final dusting through air-introduced machine and chimney emptying.Meanwhile, the total solids material that pre-duster is collected and the fraction solids granule materials that sack cleaner is collected, be transmitted back in first order reaction district after the activation of returning charge activator.
When entering boiler load and changing, can control by regulating the aperture of valve on the actual use radical of bypass duct and every root pipeline the exhaust gas volumn entering I and II reaction zone, making the stable operation in 50% ~ 120% load range of recirculating fluidized bed reaction tower.
In sum, the present invention is improved and operation parameter optimization by the structure of the digestion of calcium-base absorbing agent scene, recirculating fluidized bed reaction tower, on the basis ensureing desulfuration efficiency, enhances absorbent to NO xwith gaseous elemental mercury (Hg 0) catalytic oxidation ability; Meanwhile, the method enhances the repeatedly circulation of reaction tower inner absorbent, extends the reaction time of absorbent and gaseous contaminant, thus effectively improve absorbent utilization rate and to SO in flue gas x, NO xwith the oxidation removal efficiency of the pollutants such as mercury.
Compared with prior art, the present invention has the following advantages:
1) by methods such as the digestion of absorbent scene, the improvement of reaction tower structure and operation parameter optimizations, by means of function division, absorbent is enhanced to NO xwith the catalytic oxidation ability of mercury, achieve the integration of circulating fluidized bed desulfur denitration demercuration.
2) adopt the scene of cheap calcium-base absorbing agent and returning charge lime-ash to digest, eliminate expensive absorbent and purchase and the absorbent preparation system of complexity, small investment, operating cost is low.
3) adopt simple bypass to design, recirculating fluidized bed reaction tower and system architecture thereof are simply, easy to operate, stable, can adapt to boiler load change well.
4) desulfuration efficiency of recirculating fluidized bed integrated apparatus can reach more than 90%, NO xcan more than 50% be reached 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.
Detailed description of the invention
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, atomizing lance 12 is respectively equipped with in first order reaction district 203 and second order reaction district 206, recirculating fluidized bed reaction tower evenly arranges 4 ~ 6 bypass ducts 204 outward.By reducing 205 transition between the first order reaction district 203 of recirculating fluidized bed reaction tower 2 and second order reaction district 206, reducing 205 can accelerate the velocity of flue gas entering second order reaction district 206.Several piece smoke deflector and porous plate are set in pre-duster 5.
Boiler smoke (about 140 DEG C) enters the smoke-box 201 bottom recirculating fluidized bed reaction tower 2 through inlet flue duct 1, two-way is divided in smoke-box, wherein a road flue gas (accounting for total exhaust gas volumn about 80%) directly enters first order reaction district 203 through Venturi tube 202, another road flue gas (accounting for total exhaust gas volumn about 20%) 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 bottom four bypass ducts and second order reaction district, connected mode is 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 reducing to spurt the immixture of flue gas in second order reaction district 206.
Calcium-base absorbing agent in absorbent warehouse 3 is (as Ca (OH) 2, CaO) enter absorbent activator 4 through dispenser 301, absorbent activator is provided with oxidant and adds mouth 401, adds oxidant (KMnO at this 4, NaClO 2, CaClO 2with the mixed solution of one or more in NaCl) scene mixing and activation process are carried out to absorbent, wherein oxidant addition is 0.5 ~ 5% of calcium-base absorbing agent.First order reaction district 203 directly sent into by absorbent after activation; 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 at a high speed effect of spurting, and form the high humidity reaction zone that flue-gas temperature is about 60 DEG C, relative humidity is 40% ~ 90%, and then by catalytic oxidation, by the SO in flue gas x, NO xwith 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 the upwards flowing of flue gas, flue gas in first order reaction district 203 and solid particle material, second order reaction district 206 is entered after reducing 205 is accelerated, the boiler smoke (about 20%) entered at this and bypass duct mixes, by the adjustment of atomized water and exhaust gas volumn, flue-gas temperature in control second order reaction district 206 between 65 ~ 75 DEG C, thus realizes SO in flue gas under suitable approach temperature and oxidizing condition xremove with the secondary of the pollutant such as mercury, thus ensure higher desulphurization and denitration and demercuration efficiency.
The flue gases flowed out from recirculating fluidized bed reaction tower outlet 207 enter pre-duster 5, under the effect of pre-duster 5 inner deflector 501 and porous plate 502, remove most granule materials (absorbent and lime-ash); Flue gas after pre-duster 5 one-time dedusting enters sack cleaner 6 again and carries out final dusting, the clean flue gas after final dusting through air-introduced machine 7 and chimney 8 emptying.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 then through the outer row of cinder tank pump 11; In returning charge activator 10, be provided with oxidant add mouth 1001, the total solids material that pre-duster 5 is collected and the fraction solids granule materials that sack cleaner 6 is collected are transmitted back in first order reaction district 203 after returning charge activator 10 activates.Repeatedly circulate at excessive desulfurizing agent, the time of contact of further extension of absorbent and flue gas, the reaction of strengthening 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 digestion of calcium-base absorbing agent scene, the improvement of recirculating fluidized bed reaction tower structure and operation parameter optimizations, enhance the repeatedly circulation of reaction tower inner absorbent, extend the reaction time of absorbent and gaseous contaminant, on the basis ensureing desulfuration efficiency, enhance absorbent to NO xwith gaseous elemental mercury (Hg 0) catalytic oxidation ability, thus effectively improve absorbent utilization rate and to SO in flue gas x, NO xwith the oxidation removal efficiency of the pollutants such as mercury.In addition, when boiler load changes, can control by regulating the aperture of valve on the actual use radical of bypass duct 205 and every root pipeline the exhaust gas volumn entering I and II reaction zone, making fluidized bed fume purifying device stable operation in 50% ~ 120% load range.
Although combine by embodiment the embodiment being considered to optimum at present in this article to describe the present invention, but the present invention is by the restriction of described embodiment, be intended to cover feature in the scope of the invention that claims limit and other applies the various combination or amendment carried out.

Claims (7)

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 reaction tower (2), the main place of reacting as pollutant and absorbent and flue gas 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, reaction tower outlet (207) is connected with pre-duster (5), and bypass duct (204) is arranged on recirculating fluidized bed reaction tower (2) cylindrical shell outward and be 15 ~ 75 ° with the angle α of cylindrical shell normal direction;
Absorbent warehouse (3) and dispenser (301), absorbent activator (4) are connected successively;
Described pre-duster (5), sack cleaner (6), air-introduced machine (7) are connected successively with chimney (8), 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: be respectively equipped with atomizing lance (12) in the first order reaction district (203) of recirculating fluidized bed reaction tower (2) and second order reaction district (206).
3. a kind of circulating fluid bed flue-gas desulfurizing denitration demercuration integrated apparatus according to claim 1, it is characterized in that: recirculating fluidized bed reaction tower (2) evenly arranges 4 ~ 6 bypass ducts (204) outward, bypass duct is imported and exported and is connected, for regulating flue gas load with second order reaction district (206) bottom with smoke-box (201) respectively.
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. a kind of circulating fluid bed flue-gas desulfurizing denitration demercuration integrated apparatus according to claim 1, is characterized in that: absorbent activator (4) and returning charge activator (10) are respectively equipped with oxidant interpolation mouth.
6. a circulating fluid bed flue-gas desulfurizing denitration demercuration integral method, is characterized in that, detailed process is as follows:
1) temperature is that the boiler smoke of 140 DEG C enters smoke-box bottom recirculating fluidized bed reaction tower through inlet flue duct, and in smoke-box, be divided into two-way, 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%; Another road flue gas enters second order reaction district through bypass duct, and this part flue gas accounts for total exhaust gas volumn 20%;
2) calcium-base absorbing agent in absorbent warehouse enters absorbent activator through dispenser, carries out mixing and activation process at this and oxidant, and wherein oxidant addition is 0.5 ~ 5% of calcium-base absorbing agent; First order reaction district directly sent into by absorbent after activation process; 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 at a high speed effect of spurting, and form the high humidity reaction zone that flue-gas temperature is 60 DEG C, relative humidity is 40% ~ 90%, and then by catalytic oxidation, by NO and Hg in flue gas 0be oxidized to the NO that solubility is high respectively 2, N 2o 3with oxidation state mercury, and then by the SO in flue gas x, NO xcaSO is separately converted to gaseous elemental mercury pollutant 3, CaSO 4, Ca (NO 3) 2and oxidation state mercury, and adsorbed by solid particle, thus realize SO in flue gas x, NO xwith once removing of Hg pollutant;
3) along with the upwards flowing of flue gas, flue gas in first order reaction district and solid particle material, second order reaction district is entered after reducing is accelerated, the boiler smoke entered at this and bypass duct mixes, by the adjustment of atomized water and exhaust gas volumn, flue-gas temperature in control second order reaction district between 65 ~ 75 DEG C, thus realizes SO in flue gas under suitable approach temperature and oxidizing condition x, NO xremove with the secondary of Hg pollutant;
4) flue gas flowed out from the outlet of recirculating fluidized bed reaction tower enters pre-duster, under the effect of pre-duster inner 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, the clean flue gas after final dusting through air-introduced machine and chimney emptying; Meanwhile, the total solids material that pre-duster is collected and the fraction solids granule materials that sack cleaner is collected, be transmitted back in first order reaction district after the activation of returning charge activator.
7. a kind of circulating fluid bed flue-gas desulfurizing denitration demercuration integral method according to claim 6, it is characterized in that, the oxidant in described step (2) is KMnO 4, NaClO 2and CaClO 2in the mixed solution of one or more.
CN201410210209.0A 2014-05-16 2014-05-16 A kind of circulating fluid bed flue-gas desulfurizing denitration demercuration integrated apparatus and method Expired - Fee Related CN103977702B (en)

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CN105582793A (en) * 2015-03-25 2016-05-18 孙厚杰 Resourcelized desulfurization, denitrification and demercuration integrated process
CN104826489B (en) * 2015-03-31 2017-03-15 山东鑫源环保工程技术有限公司 A kind of combined desulfurization and denitration fluidized bed plant based on activated carbon and low temperature catalyst
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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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