CN104624028A - Coal combustion boiler flue gas denitrification device capable of recycling HNO3 solution - Google Patents

Coal combustion boiler flue gas denitrification device capable of recycling HNO3 solution Download PDF

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Publication number
CN104624028A
CN104624028A CN201410819025.4A CN201410819025A CN104624028A CN 104624028 A CN104624028 A CN 104624028A CN 201410819025 A CN201410819025 A CN 201410819025A CN 104624028 A CN104624028 A CN 104624028A
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China
Prior art keywords
hno
solution
flue gas
coal boiler
spray
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Pending
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CN201410819025.4A
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Chinese (zh)
Inventor
蒋开明
梁磊
顾强
吴卫锋
冯炜
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JIANGSHU YIHUAN GROUP CO Ltd
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JIANGSHU YIHUAN GROUP CO Ltd
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Priority to CN201410819025.4A priority Critical patent/CN104624028A/en
Publication of CN104624028A publication Critical patent/CN104624028A/en
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Abstract

The invention discloses a coal combustion boiler flue gas denitrification device capable of recycling a HNO3 solution, and relates to the field of coal combustion boiler flue gas denitrification devices. The coal combustion boiler flue gas denitrification device comprises an inlet flue duct, a spraying and absorbing tower and a HNO3 solution storage tank, wherein the bottom of the spraying and absorbing tower is provided with a pipeline for connecting the HNO3 solution storage tank; the pipeline is provided with a circulation pump. The coal combustion boiler flue gas denitrification device is characterized in that the inlet flue duct is provided with a NO oxidation reactor which is internally provided with an O3 injecting device connected with an external ozone generator. The removing rate to NOX by the coal combustion boiler flue gas denitrification device can reach 90% above, and meanwhile the HNO3 solution with relatively good economic benefit is obtained, so that under the condition of NOX emission according to the standard, harm turns to benefit, and waste is turned to be wealth, and the resourceful utilization of toxic waste is realized.

Description

A kind of recovery HNO 3the fire coal boiler fume denitrification apparatus of solution
Technical field
The present invention relates to fire coal boiler fume denitration device field, particularly relate to and reclaim HNO 3the fire coal boiler fume denitrification apparatus of solution.
Background technology
At present, in world wide, fire coal boiler fume denitration generally adopts SNCR(non-selective catalytic reduction) and SCR(SCR) technique.SNCR denitration technique adopts ammoniacal liquor or urea liquid as reducing agent, sprays into the high-temperature region of in stove 850 ~ 1100 DEG C, and denitration efficiency sprays the factors such as dosage by boiler structure, reaction temperature, Burners Positions and reducing agent affect larger.At NH 3with NO xmol ratio is that under the condition of 1.4, denitration efficiency is only about 40% ~ 50%, for import flue gas NO xthe coal-burning boiler that content is higher, is difficult to qualified discharge.Improve NH 3with NO xmol ratio is to 1.8, and denitration efficiency can reach about 75%, but system escape ammonia content is higher, with the SO in flue gas 3and water reaction generates high viscosity substance NH 4hSO 4, be attached to heat exchange element cold junction wall, heat exchange element fouling, seriously corroded, heat exchange efficiency reduces, and brings secondary pollution simultaneously.The gaseous state NH that SCR denitration technique produces with liquefied ammonia, ammoniacal liquor or Urea Evaporation or cracking 3as reducing agent, denitration efficiency is higher.When Benitration reactor adopts two-layer or three layers of catalyst, NH 3with NO xmol ratio is under the condition of 1.2, and denitration efficiency can reach 60% ~ 90%.But in only about the 3 years service life of tungsten titanium vanadium catalyst of costliness, run investment cost comparatively large, bring heavy burden to enterprise.Two kinds of techniques are directly or indirectly with NH 3for reducing agent denitration, product is N 2, generate without the accessory substance with economic benefit, therefore, the absorption method flue-gas denitration process of exploitation Cheap highly effective is significant.The main cause that NOx removes difficulty accounts for 90% of NOx total amount in flue gas for water-fast NO, uses O 3nO is oxidized to the NO of solubility 2, NO 3, N 2o 5deng, then absorb with water, denitration efficiency can reach more than 90%, is easy to meet environment protection emission requirement, non-secondary pollution, and the recyclable HNO with economic benefit 3solution, offsets part operating cost, cost-saving.
Summary of the invention
The present invention is directed to the deficiencies in the prior art, provide that a kind of equipment is simple, convenient operating maintenance, denitration efficiency are high and the recyclable HNO with economic benefit 3the fire coal boiler fume denitrification apparatus of solution.
For realizing the object of the invention, provide following technical scheme: a kind of recovery HNO 3the fire coal boiler fume denitrification apparatus of solution, comprises inlet flue duct, spray absorber, HNO 3solution storage tank, spray-absorption tower bottom arranges pipeline and connects HNO 3solution storage tank, pipeline is provided with circulating pump, it is characterized in that described inlet flue duct is provided with NO oxidation reactor, is provided with O in described NO oxidation reactor 3injection apparatus, described O 3injection apparatus connects outside ozone generator.
As preferably, described spray absorber comprises the middle part gas approach, bottom stock tank, top exhanst gas outlet, top spray equipment, the demister that are connected with inlet flue duct and rinses water layer, and bottom stock tank pipeline connects circulating pump, and circulating pump connects spray equipment.
As preferably, the flue gas flow rate in NO oxidation reactor is 3.5m/s, and the time of staying of flue gas in NO oxidation reactor is 1s, and temperature is that dust remover for coal boiler exports former flue-gas temperature 120 ~ 140 DEG C.
As preferably, the O that ozone generator provides 3be 1.1:1 with NO mol ratio in former flue gas.
As preferably, in spray absorber, flue gas flow rate is 3 ~ 4m/s, and the time of staying is 2 ~ 3s.
As preferably, spray absorber is hollow-spraying-tower, and absorbing medium is water, and spray equipment is set to one or more layers according to exhaust gas volumn, and supporting circulating pump is one or more, and demister is one-level or two-stage.
As preferably, the HNO in the stock tank of bottom 3solution pH value controls between 1.5 ~ 7.
As preferably, the spray liquid-gas ratio of described spray equipment, according to coal-burning boiler mark condition flue gas flow and NOx content, is set to 1 ~ 3L/Nm3.
For better explaining the present invention, its operation principle is as follows: the fire coal boiler fume of 120 ~ 140 DEG C enters NO oxidation reactor by inlet flue duct, the O sprayed with injection apparatus 3, there is violent gas gas oxidation reaction in counter current contacting, generates the NO being very easily dissolved in water 2, NO 3, N 2o 5deng.O 3thered is provided by ozone generator, control O 3be 1.1:1 with NO mol ratio, oxidation time is 1s, and namely the flue gas time of staying is in the reactor 1s, and flue gas flow rate is 3.5m/s.Containing NO in flue gas 2, SO 2, several material with NO with competitive oxidation such as CO and Hg, but O 3with the relative response speed of the NO reaction speed much larger than itself and other several material, have well selective, O 3preferential and NO reacts, and competitive oxidation impact is very little, and therefore, NO oxidation efficiency is higher, can reach more than 90%.
Flue gas after oxidation enters spray absorber, utilizes NO 2, NO 3, N 2o 5soluble in the characteristic of water, removed and formed HNO 3solution.Absorption tower stock tank slurries PH controls 1.5 ~ 7, to NO 2, NO 3, N 2o 5deng absorption formed HNO 3solution produces damping action hardly, according to the time of staying and denitration efficiency determination plasma discharge time, can obtain the HNO of variable concentrations 3solution.Spray liquid-gas ratio is set to 1 ~ 3L/Nm3 according to mark condition flue gas flow and NOx content, and spray coverage rate is 170% ~ 250%, and denitration efficiency can reach more than 90%, is better than SCR and SNCR denitration technique.For flue gas after guaranteeing denitration takes away comparatively juicy, demister is set on top, absorption tower, and is equipped with corresponding flushing water layer.Flue gas after denitration is discharged by absorption tower top exit flue, forms finite concentration salpeter solution and pump into storage tank in stock tank.
Beneficial effect of the present invention: apparatus of the present invention utilize O 3nO is oxidized to the NO of solubility 2, NO 3, N 2o 5deng, then absorb with water, denitration efficiency can reach more than 90%, is easy to meet environment protection emission requirement, non-secondary pollution, and the recyclable HNO with economic benefit 3solution, offsets part operating cost, cost-saving.
Accompanying drawing explanation
Fig. 1 is structural representation of the present invention.
Detailed description of the invention
The fire coal boiler fume of embodiment 1:120 ~ 140 DEG C enters NO oxidation reactor 002, NO oxidation reactor 002 front end by inlet flue duct 001 and arranges O 3injection apparatus 003, O 3thered is provided by ozone generator 004, the NO in flue gas is at this and O 3there is violent oxidation reaction and generate NO 2, NO 3, N 2o 5deng.After oxidation, flue gas enters spray absorber 005, the slurries counter current contacting sprayed with spray equipment 051, the NO in flue gas 2, NO 3, N 2o 5etc. be dissolved in water formed HNO 3solution.Spray equipment 051 slurries, from stock tank bottom absorption tower 052, are carried by circulating pump 053.Demister 054 is established on spray equipment 051 top, removes the moisture in flue gas, and demister 054 arranges and rinses water layer 055, can dust, dirty layer on periodic flushing demister.HNO in stock tank 052 3solution pumps into HNO after reaching finite concentration 3solution basin 006, establishes water replanishing device bottom spray absorber 005, and regulate the stock tank water yield, liquid level, after denitration, flue gas is discharged by absorption tower top exit flue 056.Flue gas flow rate in NO oxidation reactor 002 is 3.5m/s, and the time of staying of flue gas in NO oxidation reactor 002 is 1s, and temperature is that dust remover for coal boiler exports former flue-gas temperature 120 ~ 140 DEG C.The O that ozone generator 004 provides 3be 1.1:1 with NO mol ratio in former flue gas.In spray absorber 005, flue gas flow rate is 3 ~ 4m/s, and the time of staying is 2 ~ 3s.Spray absorber 005 is hollow-spraying-tower, and absorbing medium is water, and spray equipment 051 is set to one or more layers according to exhaust gas volumn, and supporting circulating pump 053 is one or more, and demister 054 is one-level or two-stage.HNO in bottom stock tank 052 3solution pH value controls between 1.5 ~ 7.The spray liquid-gas ratio of described spray equipment 051, according to coal-burning boiler mark condition flue gas flow and NOx content, is set to 1 ~ 3L/Nm3.
75t/h CFBB, flue-gas temperature is 140 DEG C, and exhaust gas volumn is 127787Nm3/h, NO xcontent is 500mg/ Nm3.Adopt technological process as described in Example 1, the specification of NO oxidation reactor is Φ 4.4m × 3.5m, the maximum O of ozone generator 3generation is 108Kg/h.Spray absorber specification is Φ 4.4m × 12.8m, also comprises two circulating pumps, corresponding two-layer spraying layer.
The denitration efficiency of this denitration purification process requires to be not less than 90%, and the smoke NOx content after purification is less than 50 mg/ Nm3.The HNO of 20% concentration 3output is about 646Kg/h, has certain economic value, can offset part operating cost.As calculated, this technique NO xremove unit cost and be about 4.1 yuan/Kg, a little more than SNCR technique (about 3.8 yuan/Kg), lower than SCR technique (about 5.5 yuan/Kg).But for import NOx content 500mg/ Nm3,50 below mg/ Nm3 are down in outlet, ensure that denitration efficiency more than 90%, SNCR technique may reach hardly, SCR technique is also difficult to reach.Increasingly strict with environmental emission standard, this technique can replace SCR technique, has certain applicability.

Claims (8)

1. one kind is reclaimed HNO 3the fire coal boiler fume denitrification apparatus of solution, comprises inlet flue duct, spray absorber, HNO 3solution storage tank, spray-absorption tower bottom arranges pipeline and connects HNO 3solution storage tank, pipeline is provided with circulating pump, it is characterized in that described inlet flue duct is provided with NO oxidation reactor, is provided with O in described NO oxidation reactor 3injection apparatus, described O 3injection apparatus connects outside ozone generator.
2. one according to claim 1 reclaims HNO 3the fire coal boiler fume denitrification apparatus of solution, it is characterized in that described spray absorber comprises the middle part gas approach, bottom stock tank, top exhanst gas outlet, top spray equipment, the demister that are connected with inlet flue duct and rinses water layer, bottom stock tank pipeline connects circulating pump, and circulating pump connects spray equipment.
3. one according to claim 1 reclaims HNO 3the fire coal boiler fume denitrification apparatus of solution, is characterized in that: the flue gas flow rate in NO oxidation reactor is 3.5m/s, and the time of staying of flue gas in NO oxidation reactor is 1s, and temperature is that dust remover for coal boiler exports former flue-gas temperature 120 ~ 140 DEG C.
4. one according to claim 1 reclaims HNO 3the fire coal boiler fume denitrification apparatus of solution, is characterized in that the O that ozone generator provides 3be 1.1:1 with NO mol ratio in former flue gas.
5. one according to claim 1 reclaims HNO 3the fire coal boiler fume denitrification apparatus of solution, it is characterized in that in spray absorber, flue gas flow rate is 3 ~ 4m/s, the time of staying is 2 ~ 3s.
6. one according to claim 2 reclaims HNO 3the fire coal boiler fume denitrification apparatus of solution, it is characterized in that spray absorber is hollow-spraying-tower, absorbing medium is water, and spray equipment is set to one or more layers according to exhaust gas volumn, and supporting circulating pump is one or more, and demister is one-level or two-stage.
7. one according to claim 2 reclaims HNO 3the fire coal boiler fume denitrification apparatus of solution, is characterized in that the HNO in the stock tank of bottom 3solution pH value controls between 1.5 ~ 7.
8. one according to claim 2 reclaims HNO 3the fire coal boiler fume denitrification apparatus of solution, is characterized in that: the spray liquid-gas ratio of described spray equipment, according to coal-burning boiler mark condition flue gas flow and NOx content, is set to 1 ~ 3L/Nm3.
CN201410819025.4A 2014-12-25 2014-12-25 Coal combustion boiler flue gas denitrification device capable of recycling HNO3 solution Pending CN104624028A (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106139852A (en) * 2016-08-29 2016-11-23 中国恩菲工程技术有限公司 Benitration reactor
CN107215854A (en) * 2017-03-22 2017-09-29 傅国琳 A kind of devices and methods therefor for producing nitric acid

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5039275A (en) * 1973-08-10 1975-04-11
CN1768902A (en) * 2005-10-14 2006-05-10 浙江大学 Ozone oxidation and denitration method of boiler flue gas
CN101352644A (en) * 2008-08-29 2009-01-28 浙江大学 Wet flue gas denitration technique for nitrite recovery
CN103100293A (en) * 2011-11-10 2013-05-15 中国石油化工股份有限公司 Process method for flue gas denitrification through biological method
EP2659947A1 (en) * 2012-04-30 2013-11-06 Linde Aktiengesellschaft Method and apparatus for removing contaminants from exhaust gases
CN103801176A (en) * 2014-01-27 2014-05-21 浙江大学 Flue gas denitration technology and flue gas denitration device implemented by combining ozonation and spraying cooling
CN204380494U (en) * 2014-12-25 2015-06-10 江苏一环集团有限公司 A kind of recovery HNO 3the fire coal boiler fume denitrification apparatus of solution

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5039275A (en) * 1973-08-10 1975-04-11
CN1768902A (en) * 2005-10-14 2006-05-10 浙江大学 Ozone oxidation and denitration method of boiler flue gas
CN101352644A (en) * 2008-08-29 2009-01-28 浙江大学 Wet flue gas denitration technique for nitrite recovery
CN103100293A (en) * 2011-11-10 2013-05-15 中国石油化工股份有限公司 Process method for flue gas denitrification through biological method
EP2659947A1 (en) * 2012-04-30 2013-11-06 Linde Aktiengesellschaft Method and apparatus for removing contaminants from exhaust gases
CN103801176A (en) * 2014-01-27 2014-05-21 浙江大学 Flue gas denitration technology and flue gas denitration device implemented by combining ozonation and spraying cooling
CN204380494U (en) * 2014-12-25 2015-06-10 江苏一环集团有限公司 A kind of recovery HNO 3the fire coal boiler fume denitrification apparatus of solution

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106139852A (en) * 2016-08-29 2016-11-23 中国恩菲工程技术有限公司 Benitration reactor
CN107215854A (en) * 2017-03-22 2017-09-29 傅国琳 A kind of devices and methods therefor for producing nitric acid

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Application publication date: 20150520