CN1565707A - Denitrifying and desulfurizing method of flue gas and its specialized equipment - Google Patents
Denitrifying and desulfurizing method of flue gas and its specialized equipment Download PDFInfo
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- CN1565707A CN1565707A CNA031363865A CN03136386A CN1565707A CN 1565707 A CN1565707 A CN 1565707A CN A031363865 A CNA031363865 A CN A031363865A CN 03136386 A CN03136386 A CN 03136386A CN 1565707 A CN1565707 A CN 1565707A
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- flue gas
- nitrogen
- denitration
- ultraviolet
- desulfurizing agent
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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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- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
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Abstract
The invention discloses a method for denitration (denitrogenation) and desulfurization of flue gas and its special device. The method provided by the invention includes the following steps: mixing denitration (denitrogenation) and desulfurization agent with flue gas, undergoing a heterogeneous reaction between denitration (denitrogenation) and desulfurization agent and SO#-[2], NO and NO#-[2] in flue gas by ultraviolet radiation to obtain stable solid salts, and removing SO#-[2], NO and NO#-[2] in flue gas.
Description
Technical field
The present invention relates to a kind of denitration (nitrogen) sulfur method and special equipment thereof, particularly a kind of denitrating flue gas (nitrogen) sulfur method and special equipment thereof.
Background technology
Flue gas desulfurization, its method can be divided into wet method, semidry method and dry method.The flue gas desulfurization technique of countries in the world employing at present mainly contains: lime stone-gypsum method, simple and easy lime stone-gypsum method, sea water desulfuration method, ammonium phosphate compound fertilizer method, spray drying process, sorbent gunite, electron beam doctor treatment or the like.Spray drying process be with after the pulp in advance of desulfurizing agent lime stone with being pumped to atomizer, lime stone slurry is atomized in atomizer and carefully drips and enter in the flue gas of spray-drying absorber, while evaporating and SO
2Gas reaction, the reactant of generation dry state, this kind method also is called semi-dry process flue gas desulphurization.Electron beam flue gas desulfurization is to the flue gas irradiating electron beam by the electron beam exhaust smoke processing device, the energy major part of electron beam is absorbed by nitrogen, oxygen, water vapour, generates hydrogen-oxygen (hydroxyl) free radical (OH), oxygen atom, the hydroperoxyl free radical (HO that are rich in chemical reactivity
2) etc., with SO
2Reaction generates H
2SO
4, with the NH of pre-irradiation adding
3Carry out neutralization reaction, generate (NH
4)
2SO
4, reach the effect of solid sulphur, desulfurization.The electronic beam method desulfuration efficiency is higher, but electron beam generation equipment is comparatively huge, expensive, is difficult for applying.
NO, NO in the flue gas
2Remove and mainly contain dual mode, a kind of is with NO, NO
2Reduction, as utilize ammonia (NH
3) as reducing agent, it is reduced to nitrogen (N
2), for example adopt electronic beam method, action of low-voltage pulse discharge corona plasma method or use catalyst to reduce; Another kind is with its oxidation, is converted into nitrate, removes NO and NO thereby reach
2Purpose.
Still effectively do not remove simultaneously NO in the flue gas, NO at present
2And SO
2Method.
The innovation and creation content
The purpose of this invention is to provide a kind of denitrating flue gas sulfur method that can realize denitration (nitrogen) desulfurization at the same time or separately.
Denitrating flue gas provided by the present invention (nitrogen) sulfur method is denitration (nitrogen) desulfurizing agent to be mixed the SO in (nitrogen) desulfurizing agent of denitration under ultraviolet light irradiation and the flue gas with flue gas
2With NO, NO
2Heterogeneous reaction taking place, generate stable solid-state salts substances, removes NO, NO in the flue gas
2And SO
2
After described denitration (nitrogen) desulfurizing agent can directly spray in the flue gas, mix with flue gas again.
Described denitration (nitrogen) desulfurization should be carried out before dedusting.The ultraviolet wavelength of described ultraviolet irradiation is preferably 200-400nm.
For increasing NO, NO
2And SO
2Be converted into the efficient of nitrate and sulfate, can spray into a certain amount of steam simultaneously in the described flue gas.
Wherein, described denitration (nitrogen) desulfurizing agent comprises following each components by weight portion:
Calcium carbonate 40-100
Calcium oxide 0-20
Magnesium carbonate 0-20
Titanium dioxide 0-10
Ferriferous oxide 0-10
Rare earth 0-5
Wherein, ferriferous oxide is a di-iron trioxide, ferrous oxide, one or more in the tri-iron tetroxide.
For reaching denitration preferably (nitrogen) desulfurized effect, the ratio of weight and number of each component of described taking off (nitrogen) nitre desulfurizing agent is as follows:
Calcium carbonate 40-80
Calcium oxide 5-20
Magnesium carbonate 2.5-10
Titanium dioxide 2.5-10
Ferriferous oxide 2.5-10
Rare earth 0-5
The ratio of weight and number of each component of described denitration (nitrogen) desulfurizing agent is preferably:
Calcium carbonate 70
Magnesium carbonate 7.5
Titanium dioxide 5
Di-iron trioxide 5
Rare earth 2.5
Described denitration (nitrogen) desulfurizing agent can be specifically designed to denitration (nitrogen) or desulfurization according to the difference of each constituent content.When being specifically designed to denitration (nitrogen), described denitration (nitrogen) desulfurizing agent comprises following each components by weight portion:
Calcium carbonate 40-60
Calcium oxide 10-20
Magnesium carbonate 5-10
Titanium dioxide 5-10
Ferriferous oxide 5-10
Rare earth 0-5
When described denitration (nitrogen) when desulfurizing agent is specifically designed to desulfurization, the ratio of weight and number of each component is as follows:
Calcium carbonate 50-70
Calcium oxide 10-20
Magnesium carbonate 2-5
Titanium dioxide 5-10
Ferriferous oxide 5-10
Rare earth 0-5
The granularity of described denitration (nitrogen) desulfurizing agent is generally between the 140-280 order.
Second purpose of the present invention provides the equipment of a kind of denitrating flue gas (nitrogen) desulfurization.
Denitrating flue gas provided by the present invention (nitrogen) desulphurization plant comprises denitrating flue gas (nitrogen) the desulphurization plant body and the ultraviolet emission device of reaction unit, and the ultraviolet ray that described ultraviolet emission device is launched can be radiated in the described reaction unit.
According to operating position, described equipment can further comprise quantitative dust feeder.For increasing NO, NO
2And SO
2Be converted into the efficient of nitrate and sulfate, described equipment also comprises water vapor generation device, steam buffer unit and flue gas steam mixing arrangement.The input of described steam buffer unit and the output of described water vapor generation device join, and the output of steam buffer unit links to each other with the input of described flue gas steam mixing arrangement.
Denitrating flue gas of the present invention (nitrogen) sulfur method adopts the ultraviolet ray of 200-400nm that flue gas is carried out irradiation, in conjunction with denitration (nitrogen) desulfurizing agent that is suitable for the use of denitrating flue gas of the present invention (nitrogen) desulfurizer flue gas is carried out while denitration (nitrogen) desulfurization and handles.Denitrating flue gas of the present invention (nitrogen) sulfur method belongs to dry method denitrating flue gas (nitrogen) desulfur technology.Utilize quantitative dust feeder directly to spray into special-purpose denitration (nitrogen) desulfurizing agent in the flue gas, make it fully to mix with flue gas, utilize ultraviolet ray that mixed flue gas is carried out irradiation simultaneously, can produce hydrogen-oxygen (hydroxyl) free radical (OH), oxygen atom, the hydroperoxyl free radical (HO that is rich in chemical reactivity in a large number in this process
2), O
3Deng, not only can make NO, NO
2And SO
2Oxidized in gas phase, make it on graininess denitration (nitrogen) desulfurizing agent, to be converted into stable solid-state salts substances, can the photochemistry heterogeneous chemical reaction take place on graininess denitration (nitrogen) desulfurizing agent surface simultaneously, can make NO in the flue gas, NO
2And SO
2React in a short period of time, transform, generate stable solid-state nitrate and sulfate species, thereby reach the purpose of flue gas denitration (nitrogen) simultaneously desulfurization.
Control the power of denitrating flue gas of the present invention (nitrogen) desulfurizer and the powder-feeding amount of denitration (nitrogen) desulfurizing agent and can control NO, NO in the reduction flue gas
2And SO
2What of content.Studies show that, under suitable power and denitration (nitrogen) desulfurizing agent addition, SO in the flue gas
2Removal efficiency can reach more than 95%, NO, NO
2Removal efficiency can reach more than 80%.
Denitrating flue gas of the present invention (nitrogen) sulfur method and equipment can be realized NO in the flue gas, NO
2And SO
2In time, remove; Denitration (nitrogen) and desulfuration efficiency height, operating cost is cheap, the gross investment of denitration (nitrogen) desulphurization plant is few, floor space is little, do not produce secondary pollution, system architecture is simple, operation is easy etc.; Be applicable to newly-built large-sized boiler denitrating flue gas (nitrogen) desulfurization, be particularly suitable for building the transformation application of combustion apparatus.
Description of drawings
Fig. 1 is ultraviolet irradiation flue gas denitration (nitrogen) desulfurization (nitrogen) simultaneously system.
Among the figure, 1 is drying tube, and 2 is valve, and 3 is mass flow controller, and 4 is the saturated steam generator, 5 is surge flask, and 6 is blender, and 7 is ultraviolet source, and 8 is ultraviolet source, 9 is quartz reactor, and 10 is microreactor, and 11 is flue gas analyser, and 12 is nitrogen-oxide analyzer.
The specific embodiment
As shown in Figure 1, denitration (nitrogen) desulfurizing agent (is comprised following each components by weight portion: calcium carbonate, 70; Calcium oxide, 10; Magnesium carbonate, 7.5; Titanium dioxide, 5; Di-iron trioxide, 5; Rare earth, 2.5) 200mg puts into the sample cell 10 of small-sized diffuses flow reflex response device, utilizes the variation of fourier transform infrared spectrometry monitoring graininess denitration (nitrogen) desulfurizing agent surface component.Use N
2, O
2, NO, NO
2, SO
2Gas and H
2O synthesizes simulated flue gas, NO, NO
2, SO
2Concentration is respectively 20ppm, relative humidity 40%, and the flow reactor outlet connects NOx (NO+NO
2) analyzer 12, SO
2NO, NO in the synthetic flue gas of analyzer 11 monitorings
2, SO
2The variation of content.Mixture with 8 pairs of flue gases of ultraviolet source and denitration (nitrogen) desulfurizing agent shines, and ultraviolet wavelength is 250-300nm.Under the condition of ultraviolet irradiation, graininess denitration (nitrogen) desulfurizing agent surface nitrate, sulfate growing amount are remarkable.Result of the test shows, NO, NO in the synthetic flue gas
2, SO
2Stable nitrate, sulfate can be produced on graininess CTR denitration (nitrogen) desulfurizing agent surface, NO, NO in the synthetic flue gas can be removed effectively
2And SO
2, SO in the flue gas
2Removal efficiency can reach 98%, NO, NO
2Removal efficiency can reach 85%.
As shown in Figure 1, SO in the He Cheng simulated flue gas
2Content is 500ppm, NOx (NO+NO
2) content is 500ppm.Steam that saturated steam generator 4 sends sprays in the flue gas through surge flask 5, as carrier gas denitration (nitrogen) desulfurizing agent (is comprised following each components by weight portion: calcium carbonate, 70 with synthesis of air; Calcium oxide, 10; Magnesium carbonate, 7.5; Titanium dioxide, 5; Di-iron trioxide, 5; Rare earth, 2.5) bring in the quartz reactor 9, fully mix, contact with simulated flue gas.With NOx (NO+NO
2) analyzer 12, SO
2NO, NO in the analyzer 11 monitoring outlet flue gases
2, SO
2The variation of content.Mixture with 7 pairs of flue gases of ultraviolet source and denitration (nitrogen) desulfurizing agent shines, and ultraviolet wavelength is 350nm.Under the condition of ultraviolet irradiation, SO
2Clearance reaches 95%, NOx (NO+NO
2) clearance reaches 80%.Utilize isokinetic sampling's device collecting reaction product, measure its scattered reflection Fourier transform spectrum, show NO in the flue gas, NO
2And SO
2Conversion has generated nitrate and sulfate, reaches the purpose of flue gas denitration (nitrogen) simultaneously desulfurization.
Embodiment 3, NO, NO
2Remove
As carrier gas denitration (nitrogen) desulfurizing agent (is comprised following each components by weight portion: calcium carbonate, 60 with synthesis of air; Calcium oxide, 15; Magnesium carbonate, 7.5; Titanium dioxide, 7.5; Di-iron trioxide, 7.5; Rare earth, 2.5) bring in the quartz reactor (among Fig. 1 9), fully mix, contact with simulated flue gas.NOx (NO+NO in the synthetic simulated flue gas
2) content is 500ppm.With NOx (NO+NO
2) NO, NO in the analyzer monitoring outlet flue gas
2The variation of content.Under the condition of ultraviolet irradiation, NOx (NO+NO
2) clearance reaches 80%.Utilize isokinetic sampling's device collecting reaction product, measure its scattered reflection Fourier transform spectrum, show NO in the flue gas, NO
2Conversion has generated nitrate, reaches the purpose of denitrating flue gas.
Embodiment 4, SO
2Remove
As shown in Figure 1, as carrier gas denitration (nitrogen) desulfurizing agent (is comprised following each components by weight portion: calcium carbonate, 60 with synthesis of air; Calcium oxide, 15; Magnesium carbonate, 5.5; Titanium dioxide, 7.5; Di-iron trioxide, 7.5; Rare earth, 4.5) bring in the quartz reactor 9, fully mix, contact with simulated flue gas.SO in the synthetic simulated flue gas
2Content is 500ppm.Use SO
2SO in the analyzer monitoring outlet flue gas
2The variation of content.Under the condition of ultraviolet irradiation, SO
2Clearance reaches 95%.Utilize isokinetic sampling's device collecting reaction product, measure its scattered reflection Fourier transform spectrum, show SO in the flue gas
2Conversion has generated sulfate, reaches the purpose of flue gas desulfurization.
Embodiment 5, to denitration of boiler smoke (nitrogen) desulfurization
Denitrating flue gas (nitrogen) desulphurization plant is installed in the flue before the cleaner, comprises the denitrating flue gas desulphurization plant body of reaction unit, comprises the ultraviolet emission device, and the ultraviolet ray that described ultraviolet emission device is launched can be radiated in the described reaction unit.Denitrating flue gas (nitrogen) desulphurization plant comprises quantitative dust feeder, and denitration (nitrogen) desulfurizing agent is positioned in the quantitative dust feeder, and quantitatively dust feeder mixes its quantitative ejection with flue gas.
In order to make the better effects if of denitration (nitrogen) desulfurization, denitrating flue gas (nitrogen) desulphurization plant can also comprise water vapor generation device, steam buffer unit and flue gas steam mixing arrangement, the input of steam buffer unit and the output of water vapor generation device join, and the output of steam buffer unit links to each other with the input of flue gas steam mixing arrangement.
Claims (9)
1, a kind of denitrating flue gas (nitrogen) sulfur method is denitration (nitrogen) desulfurizing agent to be mixed the SO in (nitrogen) desulfurizing agent of denitration under ultraviolet light irradiation and the flue gas with flue gas
2With NO, NO
2Heterogeneous reaction taking place, generate stable solid-state salts substances, removes NO, NO in the flue gas
2And SO
2
2, method according to claim 1 is characterized in that: after described denitration (nitrogen) desulfurizing agent directly sprays in the flue gas, mix with flue gas.
3, method according to claim 1 and 2 is characterized in that: described denitration (nitrogen) desulfurization was carried out before dedusting.
4, method according to claim 1 and 2 is characterized in that: the ultraviolet wavelength of described ultraviolet irradiation is 200-400nm.
5, method according to claim 1 and 2 is characterized in that: carry out ultraviolet light irradiation again after spraying into water vapour in the described flue gas.
6, a kind of denitrating flue gas desulphurization plant comprises denitrating flue gas (nitrogen) the desulphurization plant body of reaction unit, and it is characterized in that: it also comprises the ultraviolet emission device, and the ultraviolet ray that described ultraviolet emission device is launched can be radiated in the described reaction unit.
7, denitrating flue gas according to claim 6 (nitrogen) desulphurization plant, it is characterized in that: described equipment also comprises quantitative dust feeder.
8, according to claim 6 or 7 described denitrating flue gas (nitrogen) desulphurization plants, it is characterized in that: described equipment also comprises water vapor generation device.
9, denitrating flue gas according to claim 8 (nitrogen) desulphurization plant, it is characterized in that: described equipment also comprises steam buffer unit and flue gas steam mixing arrangement, the input of described steam buffer unit and the output of described water vapor generation device join, and the output of steam buffer unit links to each other with the input of described flue gas steam mixing arrangement.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB031363865A CN1268415C (en) | 2003-06-12 | 2003-06-12 | Denitrifying and desulfurizing method of flue gas and its specialized equipment |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB031363865A CN1268415C (en) | 2003-06-12 | 2003-06-12 | Denitrifying and desulfurizing method of flue gas and its specialized equipment |
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| CN1565707A true CN1565707A (en) | 2005-01-19 |
| CN1268415C CN1268415C (en) | 2006-08-09 |
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101940871A (en) * | 2010-09-29 | 2011-01-12 | 东南大学 | Photochemical advanced oxygenation-based simultaneous desulfuration and denitration system |
| CN101421018B (en) * | 2006-04-11 | 2012-02-15 | 卡尔斯鲁厄研究中心股份有限公司 | Process and apparatus for reducing nitrogen oxides and halogenated organic compounds in incineration plants |
| CN102734823A (en) * | 2011-04-16 | 2012-10-17 | 赵文志 | Novel power generation system |
| CN102908883A (en) * | 2012-09-27 | 2013-02-06 | 北京大学 | Method for simultaneously desulfurizing and denitrating flue gas |
| CN103285677A (en) * | 2013-06-18 | 2013-09-11 | 浙江吉天环保科技有限公司 | C-waveband desulfurizing/denitrifying bag type dust collector and dust collecting/desulfurizing/denitrifying method thereof |
| CN104474859A (en) * | 2014-12-08 | 2015-04-01 | 厦门大学 | Flue gas desulfurization and denitrification method and device and application of flue gas desulfurization and denitrification device |
| CN104492249A (en) * | 2014-12-29 | 2015-04-08 | 中国科学院广州能源研究所 | Plasma dry-type flue gas desulfurization method |
| CN105268292A (en) * | 2014-07-16 | 2016-01-27 | 鞍钢股份有限公司 | Sintering flue gas rotary spray desulfurization and denitrification system and method |
| CN110947287A (en) * | 2019-12-13 | 2020-04-03 | 西安润川环保科技有限公司 | Flue gas desulfurization and denitrification method |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101421018B (en) * | 2006-04-11 | 2012-02-15 | 卡尔斯鲁厄研究中心股份有限公司 | Process and apparatus for reducing nitrogen oxides and halogenated organic compounds in incineration plants |
| US8765089B2 (en) | 2006-04-11 | 2014-07-01 | Forschungszentrum Karlsruhe Gmbh | Process and apparatus for reducing nitrogen oxides and halogenated organic compounds in incineration plants |
| CN101940871A (en) * | 2010-09-29 | 2011-01-12 | 东南大学 | Photochemical advanced oxygenation-based simultaneous desulfuration and denitration system |
| CN102734823A (en) * | 2011-04-16 | 2012-10-17 | 赵文志 | Novel power generation system |
| CN102908883B (en) * | 2012-09-27 | 2015-07-29 | 北京大学 | A kind of flue gas and desulfurizing and denitrifying method |
| CN102908883A (en) * | 2012-09-27 | 2013-02-06 | 北京大学 | Method for simultaneously desulfurizing and denitrating flue gas |
| CN103285677A (en) * | 2013-06-18 | 2013-09-11 | 浙江吉天环保科技有限公司 | C-waveband desulfurizing/denitrifying bag type dust collector and dust collecting/desulfurizing/denitrifying method thereof |
| CN105268292A (en) * | 2014-07-16 | 2016-01-27 | 鞍钢股份有限公司 | Sintering flue gas rotary spray desulfurization and denitrification system and method |
| CN104474859A (en) * | 2014-12-08 | 2015-04-01 | 厦门大学 | Flue gas desulfurization and denitrification method and device and application of flue gas desulfurization and denitrification device |
| CN104474859B (en) * | 2014-12-08 | 2016-08-17 | 厦门大学 | A kind of method of flue gas desulfurization and denitrification, device and application thereof |
| CN104492249A (en) * | 2014-12-29 | 2015-04-08 | 中国科学院广州能源研究所 | Plasma dry-type flue gas desulfurization method |
| CN104492249B (en) * | 2014-12-29 | 2016-04-20 | 中国科学院广州能源研究所 | A kind of plasma dry fume desulphurization method |
| CN110947287A (en) * | 2019-12-13 | 2020-04-03 | 西安润川环保科技有限公司 | Flue gas desulfurization and denitrification method |
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| CN1268415C (en) | 2006-08-09 |
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