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CN1268415C - 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 PDF

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Publication number
CN1268415C
CN1268415C CNB031363865A CN03136386A CN1268415C CN 1268415 C CN1268415 C CN 1268415C CN B031363865 A CNB031363865 A CN B031363865A CN 03136386 A CN03136386 A CN 03136386A CN 1268415 C CN1268415 C CN 1268415C
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flue gas
desulfurization
nitrogen
denitrification
water vapor
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CN1565707A (en
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朱彤
丁杰
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Peking University
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Peking University
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Abstract

本发明公开了一种烟气脱硝(氮)脱硫方法及其专用设备。本发明提供的烟气脱硝(氮)脱硫方法，是将固体干式脱硝脱硫剂与烟气混合，在波长为200-400nm的紫外光线辐照下，所述脱硝脱硫剂与烟气中的NO和NO2或/和SO2发生多相反应，使烟气中的NO和NO2或/和SO2生成稳定的硫酸盐或/和硝酸盐，去除烟气中的NO和NO2或/和SO2。本发明还提供了烟气脱硝(氮)脱硫的专用设备。本发明的方法和设备适用于新建大型锅炉的烟气脱硝脱硫，特别适合于已建燃烧设备的改造应用。The invention discloses a flue gas denitrification (nitrogen) desulfurization method and special equipment thereof. The flue gas denitrification (nitrogen) desulfurization method provided by the present invention is to mix the solid dry denitrification and desulfurization agent with the flue gas, and under the irradiation of ultraviolet light with a wavelength of 200-400nm, the NO Heterogeneous reaction with NO2 or/and SO2 , making NO and NO2 or/and SO2 in the flue gas generate stable sulfate or/and nitrate, and remove NO and NO2 or/and in the flue gas SO 2 . The invention also provides special equipment for flue gas denitrification (nitrogen) desulfurization. The method and equipment of the present invention are suitable for flue gas denitrification and desulfurization of newly built large-scale boilers, and are particularly suitable for the transformation and application of existing combustion equipment.

Description

A kind of denitrating flue gas (nitrogen) sulfur method and special equipment thereof
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: limestone-gypsum method, simple and easy limestone-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 that solid dry type denitration desulfurizing agent is mixed with flue gas, is under the ultraviolet light irradiation of 200-400nm at wavelength, NO and NO in described denitration desulfurizing agent and the flue gas 2Or/and SO 2Heterogeneous reaction takes place, and makes NO and NO in the flue gas 2Or/and SO 2Generate stable sulfate or/and nitrate is removed NO and NO in the flue gas 2Or/and 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.
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
Calcium oxide 10
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, the denitrating flue gas desulphurization plant body that comprises reaction unit, quantitative dust feeder, it comprises that also emission wavelength is the ultraviolet emission device of 200-400nm ultraviolet light, and the ultraviolet ray that described ultraviolet emission device is launched can be radiated in the described reaction unit.
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
Embodiment 1, static NO, NO 2And SO 2Remove
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%.
Embodiment 2, dynamic N O, NO 2And SO 2Remove
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 (7)

1、一种烟气脱硝脱硫方法，是将固体干式脱硝脱硫剂与烟气混合，在波长为200-400nm的紫外光线辐照下，所述脱硝脱硫剂与烟气中的NO和NO2或/和SO2发生多相反应，使烟气中的NO和NO2或/和SO2生成稳定的硫酸盐或/和硝酸盐，去除烟气中的NO和NO2或/和SO2。1. A flue gas denitrification and desulfurization method, which is to mix a solid dry denitrification and desulfurization agent with flue gas, and under the irradiation of ultraviolet light with a wavelength of 200-400nm, the denitrification and desulfurization agent is mixed with NO and NO in the flue gas . Or/and SO 2 undergo multiphase reaction, make NO and NO 2 or/and SO 2 in the flue gas generate stable sulfate or/and nitrate, and remove NO and NO 2 or/and SO 2 in the flue gas. 2、根据权利要求1所述的方法，其特征在于：所述脱硝脱硫剂直接喷入烟气中后，与烟气混合。2. The method according to claim 1, characterized in that the denitration and desulfurization agent is directly sprayed into the flue gas and then mixed with the flue gas. 3、根据权利要求1或2所述的方法，其特征在于：所述脱硝脱硫在除尘之前进行。3. The method according to claim 1 or 2, characterized in that the denitrification and desulfurization are performed before dust removal. 4、根据权利要求1或2所述的方法，其特征在于：所述烟气中喷入水蒸汽后再进行紫外光线辐照。4. The method according to claim 1 or 2, characterized in that: the flue gas is sprayed with water vapor and then irradiated with ultraviolet rays. 5、一种实现权利要求1所述的烟气脱硝脱硫方法的设备，包括反应装置、定量送粉装置在内的烟气脱硝脱硫设备本体，其特征在于：它还包括发射波长为200-400nm紫外光的紫外发射装置，所述紫外发射装置发射出的紫外线能够辐射到所述反应装置中。5. A device for realizing the flue gas denitrification and desulfurization method according to claim 1, comprising a flue gas denitrification and desulfurization device body including a reaction device and a quantitative powder feeding device, characterized in that it also includes an emission wavelength of 200-400nm An ultraviolet emitting device for ultraviolet light, the ultraviolet emitted by the ultraviolet emitting device can be irradiated into the reaction device. 6、根据权利要求5所述的设备，其特征在于：所述设备还包括水蒸气发生装置。6. The device according to claim 5, characterized in that said device further comprises a water vapor generating device. 7、根据权利要求6所述的设备，其特征在于：所述设备还包括水蒸气缓冲装置和烟气水蒸气混合装置，所述水蒸气缓冲装置的输入端与所述水蒸气发生装置的输出端相接，水蒸气缓冲装置的输出端与所述烟气水蒸气混合装置的输入端相连。7. The equipment according to claim 6, characterized in that: the equipment also includes a water vapor buffer device and a flue gas water vapor mixing device, the input end of the water vapor buffer device is connected to the output of the water vapor generating device The ends are connected, and the output end of the water vapor buffering device is connected with the input end of the flue gas water vapor mixing device.
CNB031363865A 2003-06-12 2003-06-12 Denitrifying and desulfurizing method of flue gas and its specialized equipment Expired - Fee Related CN1268415C (en)

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