CN100340325C - Flue gas simultaneous desulfurization and denitrogenation by utilizing triethylenediamine cobalt (III) and carbamide - Google Patents
Flue gas simultaneous desulfurization and denitrogenation by utilizing triethylenediamine cobalt (III) and carbamide Download PDFInfo
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- CN100340325C CN100340325C CNB2005101000194A CN200510100019A CN100340325C CN 100340325 C CN100340325 C CN 100340325C CN B2005101000194 A CNB2005101000194 A CN B2005101000194A CN 200510100019 A CN200510100019 A CN 200510100019A CN 100340325 C CN100340325 C CN 100340325C
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Abstract
本发明涉及一种使用乙二胺合钴和尿素湿法烟气同时脱硫脱氮的方法，该方法通过吸收液吸收烟气中的SO2和NO，吸收液由水溶性无机钴盐、乙二胺、尿素和氢氧化钠水溶液配制而成，其中水溶性无机钴盐与乙二胺反应生成的乙二胺合钴。该方法以乙二胺合钴为NO吸收和催化氧化剂，同时为避免Co2(SO3)3沉淀降低NO脱除率，引入尿素，以O2为氧化剂下，将SO3 2-完全转化为SO4 2-，实现同时高效脱硫脱氮。该方法可使出口SO2和NO的浓度最低达0%，SO3 2-氧化率可达100%，乙二胺合钴易再生，只需一次性投料，同时尿素用量低，所以整个操作的化学剂量低，无二次污染，投资运行费用低，适合工业化应用。The invention relates to a method for simultaneous desulfurization and denitrification of flue gas using ethylenediamine cobalt and urea wet process. The method absorbs SO2 and NO in the flue gas through an absorption liquid, and the absorption liquid is composed of water-soluble inorganic cobalt salt, ethylene diamine It is prepared from amine, urea and sodium hydroxide aqueous solution, in which water-soluble inorganic cobalt salt is reacted with ethylenediamine to form ethylenediamine cobalt. In this method, ethylenediamine cobalt is used as the NO absorption and catalytic oxidant, and at the same time, in order to avoid the precipitation of Co 2 (SO 3 ) 3 and reduce the NO removal rate, urea is introduced to completely convert SO 3 2- into SO 4 2- , to achieve simultaneous and efficient desulfurization and denitrification. This method can make the concentration of SO 2 and NO at the outlet reach 0%, the SO 3 2- oxidation rate can reach 100%, ethylenediamine cobalt is easy to regenerate, only one-time feeding is required, and the urea consumption is low, so the whole operation Low chemical dosage, no secondary pollution, low investment and operation costs, suitable for industrial applications.
Description
Technical field
The present invention relates to gas cleaning and administer technical field, specifically is the desulfurization removing nitric of flue gas, particularly uses triethylenediamine cobalt and urea wet process of FGD denitride technology simultaneously.
Background technology
Contain SO
2And NO
XA large amount of dischargings of waste gas caused the serious environmental pollution problem, as destruction of acid rain, ozone layer etc.The simultanously desulfurizing and denitrification technology is just begin one's study over past ten years hot of research and development technology, wherein NO
XIn the removing of NO that account for 95% or more of concentration be still its difficult point, prior art mainly contains plasma method and minority catalysis method both at home and abroad at present because equipment investment and operating cost be than higher, product reclaims difficulty, large-scale promotion application also need be perfect.Recent years, the research of wet chemical just became simultanously desulfurizing and denitrification technology important development direction, and the advantage of this method is that equipment investment is little, and technological process is simple.Many-sides such as synthesis desulfurating denitrification effect, environmental protection, cost, present wet chemical method preferably has following three classes: the one, the urea seeding agent is desulfurization removing nitric simultaneously; The 2nd, ferrous complex is desulfurization removing nitric simultaneously; The 3rd, cobalt complex is desulfurization removing nitric simultaneously.Application number is the method that 03003768.7 and 01130154.6 Chinese patent application discloses two kinds of wet urea additive desulfurization removing nitrics, the mass percentage content of used absorbent urea is all 5～30% in two kinds of methods, chemical dose is very big, and though the cost height is its SO
2Removal efficiency can reach more than 95% but its NO
XRemoval efficiency only reaches 80%; The ferrous complex system shortcoming of desulfurization removing nitric simultaneously is ferrous complex regeneration difficulty, cost height; Application number is the method that 01105004.7,01105698.3,02110646.0 and 200310108514.0 Chinese patent application discloses nitrogen oxide in cobalt ammonia solution and the triethylenediamine cobalt solution efficient absorption flue gas, the concentration of NO is minimum in working off one's feeling vent one's spleen reaches 0%, wherein triethylenediamine cobalt is easily regenerated, and tool advantage.Wherein application number is that 02110646.0 patented technology adopts triethylenediamine cobalt co-oxidation calcium to carry out simultanously desulfurizing and denitrification, reduces SO with calcium oxide
3 2-Concentration to be avoiding reducing the NO removal efficiency, but generates the low accessory substance calcium sulfite of economic benefit, and causing to have the recovery efficiency of sulfur resource, causes equipment to stop up and the solid waste secondary pollution simultaneously, does not meet environmental requirement.Generally speaking, there is following shortcoming in prior art: urea additive is desulfurization removing nitric simultaneously, and chemical dose is big, the cost height, and take off NO and lead not high; Triethylenediamine cobalt co-oxidation calcium is desulfurization removing nitric simultaneously, though NO removal efficiency height, the easy occluding device of accessory substance calcium sulfite, and cause secondary pollution.
Summary of the invention
Purpose of the present invention is exactly in order to solve the deficiencies in the prior art part, provide a kind of triethylenediamine cobalt and urea are used the method for carrying out desulfurization removing nitric of efficient while of flue gas simultaneously, to obtain high desulfurization removing nitric rate, reduce the urea chemical dose again, and triethylenediamine cobalt is easily regenerated, only need disposable feeding intake, the raw material consumption is few, effectively fully utilizes sulphur and nitrogen resource.
Basic principle of the present invention is as follows:
The triethylenediamine cobalt that inorganic cobalt salt and reacting ethylenediamine generate.
Triethylenediamine cobalt complexing and catalytic oxidation NO and regeneration thereof:
Co(en)
3 3++OH
-+NO→Co(en)
2(NO)OH
2++en
2Co(en)
2(NO)OH
2++O
2→2Co(en)
2(NO
2)OH
2+
2Co(en)
2(NO
2)OH
2++4OH
-→2Co(en)
2(OH)
2 2++NO
2 -+NO
3 -+H
2O
Co(en)
2(OH)
2 2++en→Co(en)
3 3++2OH
-
In the above-mentioned chemical reaction, absorption and optimal reaction temperature during catalytic oxidation about 40～70 ℃ of NO in absorption liquid, because general flue gas has higher temperature, so said temperature more easily satisfies.
SO
2Easily absorbed: 2OH by alkaline solution
-+ SO
2→ SO
3 2-+ H
2O
Part SO
3 2-Under the effect of oxygen, can transfer to and be SO
4 2-Yet, still have most of SO
3 2-Exist in solution.Because SO
3 2-Amount increase gradually, easily form Co
2(SO
3)
3Precipitation reduces active component Co (en)
3 3+Content and reduce and take off NO and lead.For keeping the high NO that takes off to lead, need to reduce SO
3 2-Concentration is because Co
2(SO
4)
3Soluble in water, therefore in joining solution, introduce urea, with O in the flue gas
2Be oxidant, with SO
3 2-Complete oxidation is SO
4 2-, this reaction is quick irreversible reaction.
SO
2+(NH
2)
2CO+2H
2O+0.5O
2→(NH
4)
2SO
4+CO
2
In the above-mentioned chemical reaction, SO in solution
3 2-The reaction temperature of complete oxidation is preferably 50～80 ℃.
Purpose of the present invention is achieved through the following technical solutions:
A kind of method of using triethylenediamine cobalt and urea wet flue gas while desulfurization removing nitric: this method is for absorbing the SO in the flue gas by absorption liquid
2And NO, described absorption liquid is formulated by water-soluble inorganic cobalt salt, ethylenediamine, urea and sodium hydrate aqueous solution, and the concentration of volume percent of oxygen is 5～15% in the described flue gas.
This method water-soluble inorganic cobalt salt is a water-soluble inorganic cobalt salt general in this type of technology, as selecting cobalt chloride, cobalt acetate and cobalt nitrate etc., the preferred cobalt chloride of the present invention for use.
For better realization purpose of the present invention, during described configuration absorption liquid, the mass percentage content of urea preferred 0.1～5%, preferred 0.005～the 0.040mol/L of the molar concentration of inorganic cobalt salt, ethylenediamine concentration of volume percent preferred 0.1～2%, the molar concentration of second two cobaltammines that inorganic cobalt salt and ethylenediamine complexing form is preferably 0.005～0.040mol/L, and the absorption liquid pH value is preferably 8.0～13.0.NO concentration is preferably and is not higher than 1100ppm, SO in the described flue gas
2Concentration range be preferably and be not higher than 5000ppm; The operation temperature can be carried out at normal temperatures, and with the variation of temperature of flue gas self, preferred temperature is 50～70 ℃.The molar concentration of the triethylenediamine cobalt that absorption liquid is generated by water-soluble inorganic cobalt salt and reacting ethylenediamine in absorbing the flue gas process is controlled at the scope of 0.005～0.04mol/L; The mass percentage content of urea is controlled at 0.1～5% scope in the absorption liquid; The pH value of absorption liquid is controlled at 8.0～13.0 scope.
For further realization purpose of the present invention, in absorption liquid configuration and the use, the mass percentage content of urea preferred 0.5～2%; The absorption liquid pH value is preferably 9.0～12.0; Preferred 0.01～the 0.03mol/L of the molar concentration of triethylenediamine cobalt.
The present invention compared with prior art has following advantage and beneficial effect:
(1) in the urea additive while desulfurization removing nitric, the urea quality percent concentration is 5～30%, and chemical dose is very big, and denitrification percent can only reach 80% simultaneously; When triethylenediamine cobalt of the present invention and urea used simultaneously, the mass percent of urea was between 0.1～5%, and consumption is few, and cost reduces greatly, and the concentration that exports NO simultaneously is minimum to reach 0%, and denitrification percent improves greatly;
(2) triethylenediamine cobalt co-oxidation calcium flue gas desulfuration and denitrification technology is for avoiding Co
2(SO
3)
3The generation of precipitation reduces the NO removal efficiency, adopts calcium oxide to form CaSO
3The indissoluble thing reduces SO
3 2-Concentration easily causes equipment to stop up and CaSO
3The solid waste secondary pollution; The present invention adopts triethylenediamine cobalt and urea to use simultaneously, introduces urea in absorption liquid, is oxidant with oxygen, with SO
3 2-All be oxidized to SO
4 2-, when keeping high desulfurization removing nitric rate, recovery efficiency of sulfur nitrogen resource is arranged, no equipment clogging, also non-secondary pollution;
(3) triethylenediamine cobalt is easily regenerated, and only needs disposable feeding intake, and amount of urea is low simultaneously, so the chemical dose of whole operation is low;
(4) technological process of the present invention is simple, desulfurization removing nitric rate height, and the chemical raw material consumption is few, small investment, operating cost is low, is suitable for industrial applications.
Specific implementation method
Below in conjunction with embodiment the present invention is described in further detail, but embodiments of the present invention are not limited thereto.
Embodiment one
Simulated flue gas: gas flow is 700ml/min; SO during gas feed is formed
2Content is 600ppm, and NO is 200ppm, O
2Concentration of volume percent is 5%, and all the other are nitrogen; Temperature is 50 ℃.
Absorption liquid: volume is 150ml; Cobalt chloride concentration was 0.005M during liquid was formed, and ethylenediamine concentration is 0.1% (volume), and triethylenediamine cobalt concentration is 0.005M, and the urea quality percent concentration is 0.1%; The pH value of solution value is 8.0.
Method and detection: in 500ml GAS ABSORPTION bottle, contain SO
2Enter absorption liquid in the absorption bottle with the simulated flue gas of NO, continue 3 hours, carry out the simultanously desulfurizing and denitrification experiment, the operation temperature is 50 ℃.Gas vent concentration detects SO with formaldehyde absorption-hydrochloric acid Pararosaniline colorimetric method
2Concentration detects NO concentration, sulfate by ion chromatography SO with the Saltzman method
3 2-The oxidation situation, in 3 hours, SO
2Removal efficiency be 100%, the NO removal efficiency is 94%, SO
3 2-Oxygenation efficiency reach 92%.At this moment, the concentration of urea descends, and the pH value descends simultaneously, adds 0.1g urea, makes its concentration increase to 0.1%, and NaOH is regulated pH value to 8.0, and this absorption liquid still can keep high desulfurization removing nitric rate in next 3 hours like this, can repeat to implement.
The contrast experiment: absorbent is to add ethylenediamine in the urea liquid, and wherein the urea quality percent concentration is 10%, and the ethylenediamine mass percent concentration is 0.05%, and the operation temperature is 70 ℃ contrast experiment.Simulated flue gas, reactor and the same present embodiment of other operating condition.Gas vent concentration detects SO with formaldehyde absorption-hydrochloric acid Pararosaniline colorimetric method
2Concentration detects NO concentration with the Saltzman method, in 3 hours, and SO
2Removal efficiency be 98%, the NO removal efficiency is 75%.As seen this example improves a lot than adding the prior art of ethylenediamine as absorbent in the urea liquid aspect NO removes.
Embodiment two
Simulated flue gas: gas flow is 700ml/min; SO during gas feed is formed
21800ppm, NO 450ppm, O
28%, all the other are nitrogen; Temperature is 60 ℃.
Absorption liquid: volume is 150ml; Cobalt chloride concentration is 0.01M in the absorption liquid, and ethylenediamine concentration is 1% (volume), and triethylenediamine cobalt concentration is 0.01M, and the urea quality percent concentration is 0.5%; The absorption liquid pH value is 12.0.
Method and detection: in 500ml GAS ABSORPTION bottle, contain SO
2With the simulated flue gas of NO and the absorption liquid in the absorption bottle, continue 5.5 hours, carry out the simultanously desulfurizing and denitrification experiment, the operation temperature is 60 ℃.Gas vent concentration detects SO with formaldehyde absorption-hydrochloric acid Pararosaniline colorimetric method
2Concentration detects NO concentration, sulfate by ion chromatography SO with the Saltzman method
3 2-The oxidation situation, in 5.5 hours, SO
2Removal efficiency is 100%, and the NO removal efficiency is 97%, SO
3 2-Oxygenation efficiency reach 100%.At this moment, the concentration of urea descends and makes an appointment with half, and the pH value descends simultaneously, add 0.375g urea, its concentration is increased to about 0.5%, NaOH is regulated pH value to 12.0, this absorption liquid still can keep high desulfurization removing nitric rate in next 5.5 hours like this, can repeat to implement.
The contrast experiment: absorbent is Fe-EDTA, and concentration is 0.01M.Simulated flue gas, reactor and operating condition are the same.Gas vent concentration detects SO with formaldehyde absorption-hydrochloric acid Pararosaniline colorimetric method
2Concentration detects NO concentration with the Saltzman method, in 5.5 hours, and SO
2Removal efficiency be 92%, the NO removal efficiency is 58%.As seen this example is that the prior art of Fe-EDTA improve a lot than absorbent at NO aspect removing, at SO
2The aspect that removes also improve a lot.
Embodiment three
Simulated flue gas: gas flow is 700ml/min; SO during gas feed is formed
25000ppm, NO 1100ppm, O
215%, all the other are nitrogen; Temperature is 70 ℃.
Absorption liquid: volume is 150ml; Cobalt chloride concentration is 0.04M in the absorption liquid, and ethylenediamine concentration is 2% (volume), and triethylenediamine cobalt concentration is 0.04M, and the urea quality percent concentration is 5%; The absorption liquid pH value is 13.0.
Method and detection: in 500ml GAS ABSORPTION bottle, contain SO
2With the simulated flue gas of NO and the absorption liquid in the absorption bottle, continue 7 hours, carry out the simultanously desulfurizing and denitrification experiment, the operation temperature is 70 ℃.Gas vent concentration detects SO with formaldehyde absorption-hydrochloric acid Pararosaniline colorimetric method
2Concentration detects NO concentration, sulfate by ion chromatography SO with the Saltzman method
3 2-The oxidation situation, in 7 hours, SO
2Removal efficiency is 98%, and the NO removal efficiency is 92%, SO
3 2-Oxygenation efficiency reach 95%.At this moment, the concentration drop by half of urea, the pH value descends simultaneously, adds 3.75g urea, and its concentration is increased to about 5%, and NaOH is regulated pH value to 13.0, and this absorption liquid still can keep high desulfurization removing nitric rate in next 7 hours like this, can repeat to implement.
Embodiment four
Simulated flue gas: gas flow is 500ml/min; SO during gas feed is formed
21800ppm, NO 450ppm, O
28%, all the other are nitrogen; Temperature is 60 ℃.
Absorption liquid: volume is 80ml; Cobalt chloride concentration is 0.02M in the absorption liquid, and ethylenediamine concentration is 2% (volume), and triethylenediamine cobalt concentration is 0.02M, and the urea quality percent concentration is 2%; The absorption liquid pH value is 12.0.
Method and detection: in 500ml GAS ABSORPTION bottle, contain SO
2With the simulated flue gas of NO and the absorption liquid in the absorption bottle, continue 7 hours, carry out the simultanously desulfurizing and denitrification experiment, the operation temperature is 60 ℃.Gas vent concentration detects SO with formaldehyde absorption-hydrochloric acid Pararosaniline colorimetric method
2Concentration detects NO concentration, sulfate by ion chromatography SO with the Saltzman method
3 2-The oxidation situation, in 7 hours, SO
2Removal efficiency is 100%, and the NO removal efficiency is 95%, SO
3 2-Oxygenation efficiency reach 100%.At this moment, the concentration drop by half of urea, the pH value descends simultaneously, adds 0.8g urea, and its concentration is increased to about 2%, regulates pH value to 12.0 with NaOH, and this absorption liquid still can keep high desulfurization removing nitric rate in next 7 hours like this, can repeat to implement.
Embodiment five
Simulated flue gas: gas flow is 1600ml/min; SO during gas feed is formed
2Content is 600ppm, and NO is 200ppm, O
2Concentration of volume percent is 5%, and all the other are nitrogen; Temperature is 50 ℃.
Absorption liquid: volume is 500ml; Spray rate is 40ml/min; Cobalt chloride concentration was 0.01M during liquid was formed, and ethylenediamine concentration is 1% (volume), and triethylenediamine cobalt concentration is 0.01M, and the urea quality percent concentration is 0.5%; The pH value of solution value is 9.0.
Method and detection: at diameter 5cm, in the packed tower of high 100cm, what enter at the bottom of the tower contains SO
2With the simulated flue gas and the absorption liquid that sprays into from cat head of NO, the gas-liquid two-phase adverse current fully contacts, and continues 11 hours, carries out the simultanously desulfurizing and denitrification experiment, and the operation temperature is 50 ℃, and absorption liquid recycles.Gas vent concentration detects SO with formaldehyde absorption-hydrochloric acid Pararosaniline colorimetric method
2Concentration detects NO concentration, sulfate by ion chromatography SO with the Saltzman method
3 2-The oxidation situation, in 11 hours, SO
2Removal efficiency be 98.5%, the NO removal efficiency is 96%, SO
3 2-Oxygenation efficiency reach 96%.At this moment, the concentration drop by half of urea, the pH value descends simultaneously, add 1.25g urea, its concentration is increased to about 0.5%, regulate pH value to 9.0 with NaOH, this absorption liquid still can keep high desulfurization removing nitric rate in next 11 hours like this, can repeat to implement.
Embodiment six
Simulated flue gas: gas flow is 1000ml/min; SO during gas feed is formed
21800ppm, NO 450ppm, O
28%, all the other are nitrogen; Temperature is 50 ℃.
Absorption liquid: volume is 500ml; Spray rate is 50ml/min; In the absorption liquid, cobalt chloride concentration is 0.02M, and ethylenediamine concentration is 2% (volume), and triethylenediamine cobalt concentration is 0.02M, and the urea quality percent concentration is 1%; The pH value of solution value is 12.0.
Method and detection: at diameter 5cm, in the packed tower of high 100cm, what enter at the bottom of the tower contains SO
2With the simulated flue gas and the absorption liquid that sprays into from cat head of NO, the gas-liquid two-phase adverse current fully contacts, and continues 11 hours, carries out the simultanously desulfurizing and denitrification experiment, and the operation temperature is 50 ℃, and absorption liquid recycles.Gas vent concentration detects SO with formaldehyde absorption-hydrochloric acid Pararosaniline colorimetric method
2Concentration detects NO concentration, sulfate by ion chromatography SO with the Saltzman method
3 2-The oxidation situation, in 11 hours, SO
2Removal efficiency be 98%, the NO removal efficiency is 95%, SO
3 2-Oxygenation efficiency reach 95%.At this moment, the concentration drop by half of urea, the pH value descends simultaneously, adds 2.5g urea, and its concentration is increased to about 1%, and NaOH is regulated pH value to 12.0, and this absorption liquid still can keep high desulfurization removing nitric rate in next 11 hours like this, can repeat to implement.
Embodiment seven
Simulated flue gas: gas flow is 800ml/min; SO during gas feed is formed
23400ppm, NO 800ppm, O
210%, all the other are nitrogen; Temperature is 60 ℃.
Absorption liquid: volume is 500ml; Spray rate is 60ml/min; In the absorption liquid, cobalt chloride concentration is 0.03M, and ethylenediamine concentration is 2% (volume), and triethylenediamine cobalt concentration is 0.03M, and the urea quality percent concentration is 2%; The pH value of solution value is 12.0.
Method and detection: at diameter 5cm, in the packed tower of high 100cm, what enter at the bottom of the tower contains SO
2With the simulated flue gas and the absorption liquid that sprays into from cat head of NO, the gas-liquid two-phase adverse current fully contacts, and continues 14 hours, carries out simultanously desulfurizing and denitrification, and the operation temperature is 60 ℃, and absorption liquid recycles.Gas vent concentration detects SO with formaldehyde absorption-hydrochloric acid Pararosaniline colorimetric method
2Concentration detects NO concentration, sulfate by ion chromatography SO with the Saltzman method
3 2-The oxidation situation, in 14 hours, SO
2Removal efficiency is 97%, and the NO removal efficiency is 94%, SO
3 2-Oxygenation efficiency reaches 94%.At this moment, the concentration drop by half of urea, the pH value descends simultaneously, adds 5g urea, and its concentration is increased to about 2%, and NaOH is regulated pH value to 12.0, and this absorption liquid still can keep high desulfurization removing nitric rate in next 14 hours like this, can repeat to implement.
Claims (7)
1, a kind of method of using triethylenediamine cobalt and urea wet flue gas while desulfurization removing nitric is characterized in that described method is for absorbing the SO in the flue gas by absorption liquid
2And NO, described absorption liquid is formulated by water-soluble inorganic cobalt salt, ethylenediamine, urea and sodium hydrate aqueous solution, the concentration of volume percent of oxygen is 5～15% in the described flue gas, described absorption liquid is 0.1～5% urea by mass percentage content, molar concentration is the water-soluble inorganic cobalt salt of 0.005～0.04mol/L, and the ethylenediamine of concentration of volume percent 0.1～2% and sodium hydrate aqueous solution mixed configuration form; The addition of sodium hydrate aqueous solution is 8.0～13.0 for making the absorption liquid pH value.
2, the method for application triethylenediamine cobalt according to claim 1 and urea wet flue gas while desulfurization removing nitric is characterized in that the mass percentage content of urea is 0.5～2% in the described absorption liquid.
3, the method for application triethylenediamine cobalt according to claim 1 and urea wet flue gas while desulfurization removing nitric is characterized in that described water-soluble inorganic cobalt salt is a cobalt chloride.
4, the method for application triethylenediamine cobalt according to claim 1 and urea wet flue gas while desulfurization removing nitric is characterized in that NO concentration is not higher than 1100ppm, SO in the described flue gas
2Concentration be not higher than 5000ppm.
5, the method for application triethylenediamine cobalt according to claim 1 and urea wet flue gas while desulfurization removing nitric is characterized in that, the SO of described absorption liquid in absorbing flue gas
2In the NO process, the molar concentration of the triethylenediamine cobalt that is generated by water-soluble inorganic cobalt salt and reacting ethylenediamine is controlled in the scope of 0.005～0.04mol/L; The mass percentage content of urea is controlled in 0.1～5% the scope in the described absorption liquid; The pH value of absorption liquid is controlled in 8.0～13.0 the scope.
6, the method for application triethylenediamine cobalt according to claim 5 and urea wet flue gas while desulfurization removing nitric is characterized in that the molar concentration of described triethylenediamine cobalt is controlled in 0.01～0.03mol/L scope.
7, use triethylenediamine cobalt and the urea wet flue gas method of desulfurization removing nitric simultaneously according to claim 1 or 5, it is characterized in that described absorption liquid pH value is controlled in 9.0～12.0 scopes.
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| CN101810996B (en) * | 2010-04-30 | 2013-04-17 | 成都信息工程学院 | Method for producing ammonium sulfate and ammonium nitrate by simultaneously desulfurizing and denitrating ammonia water and cobaltic ethylenediamine (II) |
| CN104043322A (en) * | 2014-06-24 | 2014-09-17 | 浙江工商大学 | Method for denitrifying coal-fired flue gas through synergy of plasma and complex catalysis |
| CN105126564B (en) * | 2015-08-26 | 2018-07-24 | 北京国能中电节能环保技术有限责任公司 | The method and apparatus of flue gas and desulfurizing and denitrifying |
| CN106975346A (en) * | 2017-03-31 | 2017-07-25 | 盐城工学院 | Absorbent solution and preparation method thereof |
| CN109289494A (en) * | 2018-12-04 | 2019-02-01 | 紫金铜业有限公司 | A kind of two-stage method low-temperature denitration method of low cost |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4081509A (en) * | 1975-03-31 | 1978-03-28 | Hitachi, Ltd. | Method for removing nitrogen oxides from flue gas by absorption |
| CN1377722A (en) * | 2001-12-30 | 2002-11-06 | 国家环境保护总局华南环境科学研究所 | Urea additive wet flue gas simultaneous desulfurization and denitrification method |
| CN1433834A (en) * | 2003-02-20 | 2003-08-06 | 国家环境保护总局华南环境科学研究所 | Method for urea catalyst simultaneously processing flue gas and desulfurizing denitrification |
| US6875409B1 (en) * | 1999-01-04 | 2005-04-05 | Hydrocarbon Technologies, Inc. | Catalyst and process for oxidation and removal of nitrogen oxides (NOx) from combustion gases |
-
2005
- 2005-09-29 CN CNB2005101000194A patent/CN100340325C/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4081509A (en) * | 1975-03-31 | 1978-03-28 | Hitachi, Ltd. | Method for removing nitrogen oxides from flue gas by absorption |
| US6875409B1 (en) * | 1999-01-04 | 2005-04-05 | Hydrocarbon Technologies, Inc. | Catalyst and process for oxidation and removal of nitrogen oxides (NOx) from combustion gases |
| CN1377722A (en) * | 2001-12-30 | 2002-11-06 | 国家环境保护总局华南环境科学研究所 | Urea additive wet flue gas simultaneous desulfurization and denitrification method |
| CN1433834A (en) * | 2003-02-20 | 2003-08-06 | 国家环境保护总局华南环境科学研究所 | Method for urea catalyst simultaneously processing flue gas and desulfurizing denitrification |
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