CN104941431A - Desulphurization and denitration device and method - Google Patents
Desulphurization and denitration device and method Download PDFInfo
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- CN104941431A CN104941431A CN201510303399.5A CN201510303399A CN104941431A CN 104941431 A CN104941431 A CN 104941431A CN 201510303399 A CN201510303399 A CN 201510303399A CN 104941431 A CN104941431 A CN 104941431A
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Abstract
The invention discloses a desulphurization and denitration device and method. The desulphurization and denitration device comprises desulphurization and denitration equipment, slurry cyclic delivery equipment and hydrogen peroxide supplement equipment. A spraying and absorption zone, a hydrogen peroxide spray oxidation reaction layer and a slurry storage zone are arranged in the desulphurization and denitration equipment. The hydrogen peroxide spray oxidation reaction layer is arranged in the spraying and absorption zone. The device and method realize combination of magnesium desulfurization and hydrogen peroxide oxidation denitration, improve an arrangement position of a hydrogen peroxide spray oxidation reaction layer in the existing device, provide the optimal hydrogen peroxide excitation conditions, improve nitrogen oxide and sulfur dioxide remove rates, reduce a H2O2 injection amount, save a cost, and prevent an explosion risk caused by superfluous H2O2 and a high temperature. Compared with the existing device and method, the device and method simplify equipment and greatly reduce desulphurization and denitration early stage construction investment, floor space and operation cost.
Description
Technical field
The present invention relates to a kind of desulfuring and denitrifying apparatus and method, especially a kind of apparatus and method of the sulfur and nitrogen oxides removed in flue gas.
Background technology
SO
2being one of Air Pollutant Discharge, is the important symbol whether measurement air is polluted.It has huge harm to the aspect such as health, environment, is the main cause forming acid rain.China is that a few take coal as one of country of main energy sources in the world.A large amount of fire coals causes China SO
2the acid deposition of polluting and cause thus is polluted very serious.The SO of China
2pollution control is started late, and present situation is still very severe.Meanwhile, the situation that NOx discharge maintenance increases, so the pollution control of NOx has also been subject to the great attention of national correlation department.The Section 3 controlling coal-burning boiler, the discharge of steel sintering pelletizing equipment NOx is classified as after flue gas ash removal, desulfurization is polluted keypoint treatment work by national environmental protection portion, and by standard by 400mg/Nm before
3(generally area), 200mg/Nm
3(key area) has brought up to 200mg/Nm
3, 100mg/Nm
3.This impels people to study, develops efficient simultaneous SO_2 and NO removal technology, more effectively, economically to complete the task of gas pollution control.
At present, the desulphurization denitration technology that China generally adopts is Wet Flue Gas Desulfurization Technology WFGD (calcium method is in the majority)+selective catalytic reduction SCR (or selective non-catalytic reduction SNCR).Although this technology to remove pollutant efficiency higher, its complex process, controlled condition is harsh, and investment, operating cost are expensive, medium-high sulfur coal bad adaptability, the accessory substance nitrogen N of especially denitration
2without value, owing to there is these shortcomings, be difficult to realize large area commercial introduction in China.
Chinese patent application CN104258701A discloses following a kind of denitrating technique: denitration flue gas and denitration oxidant first carry out oxidation reaction, adopt sodium chlorite as denitration oxidant, oxidation reaction was carried out before flue gas enters in tower, reaction temperature is within the scope of the cigarette temperature of 120 ~ 130 DEG C, and dust content is at 50 ~ 200mg/Nm
3in scope, this process exists that oxidant sodium chlorite at high temperature produces decomposition, oxidant loses activity, and causes the problem that denitration efficiency is lower.And sodium chlorite contacts with organic matter and can set off an explosion, and in use has certain limitation.Meanwhile, because denitration efficiency is lower, it is more difficult that this technology meets existing discharged nitrous oxides standard.Sodium chlorite price is per ton more than 10,000 yuan, even if reach discharge standard, its denitration cost is also very high, significantly adds the desulphurization denitration cost of enterprise.
Chinese patent application CN102327735A discloses a kind of based on H
2o
2the system and method to flue gas and desulfurizing and denitrifying of effect.Chinese patent application CN103463978A discloses a kind of based on H
2o
2the apparatus and method of catalytic oxidation flue gas and desulfurizing and denitrifying.Both utilize H
2o
2strong oxidizing property by the sulfur dioxide (SO in flue gas
2) and nitrogen oxide (NO
x) being oxidized to sulfuric acid and nitric acid, its arrangement is all inject H at gas approach place
2o
2, this injection mode has the defect of following several respects:
1, due to H
2o
2there is unstability, more than 120 DEG C, especially 140 DEG C and above time can there is decomposition (intensive decomposition becomes H
2o and O
2), lose antioxidant nitroxide (NO
x) ability, and most of flue gas in the flue-gas temperature of flue section (before not entering absorption tower) exactly within this temperature range.
2, be the sintering device flue gas of steel mill or fire coal boiler fume all containing more dust, H
2o
2the active material hydroxyl radical free radical excited runs into dust and can lose activity, and reduces oxidation efficiency.
3, H
2o
2at 50 ~ 70 DEG C, atomization moisture content, 10% ~ 13%, can inspire more hydroxyl radical free radical OH and O under the condition of environment water content 30% ~ 40%
2h, and gas approach position cigarette temperature is too high and water content is lower, does not reach such condition, causes H
2o
2inspire active material hydroxyl radical free radical OH and O of substantive oxidation meaning
2the amount of H reduces greatly.
4, tower is outer many and complicated for the equipment of denitration, and floor space is large, adds investment, operating cost.
Summary of the invention
In order to overcome the defect of prior art, the invention provides a kind of flue gas desulfurization and denitrification apparatus and method, especially a kind ofly utilizing desulphurization denitration slurries to carry out wet absorption and (being mainly SO in conjunction with the oxysulfide that catalytic oxidation of hydrogen peroxide technology removes in flue gas
2) and nitrogen oxide (NO
x) method and apparatus.Apparatus and method of the present invention are particularly useful for the process containing sulfur and nitrogen oxides flue gas such as coal-burning boiler, steel sintering machine, pelletizing, can make magnesium processes wet desulphurization and H
2o
2oxidation and denitration technology obtains working in coordination with utilization more efficiently, gives full play to the advantage of magnesium processes wet desulphurization and solves H
2o
2there is the existing H such as decomposition, oxidation efficiency is low, investment operating cost is high
2o
2oxidation and denitration technology Problems existing.
The invention provides a kind of desulfuring and denitrifying apparatus, comprising:
Desulphurization denitration equipment, its inside is provided with:
Hydrogen peroxide spraying oxidation reaction layer, in order to spray hydrogen peroxide, the nitrogen oxide in this hydrogen peroxide oxidation flue gas and part sulfur dioxide, to form intermediate reaction product;
Spray-absorption district, in order to spray desulphurization denitration slurries, the part sulfur dioxide in these desulphurization denitration slurries and above-mentioned intermediate reaction product and flue gas reacts, to form absorption product;
Slurries memory block, for storing desulphurization denitration slurries, and receives the absorption product from spray-absorption district;
Serum recycle conveying equipment, for being transported to described spray-absorption district by the desulphurization denitration serum recycle of described slurries memory block;
Hydrogen peroxide supply arrangement, for supplying hydrogen peroxide to hydrogen peroxide spraying oxidation reaction layer;
Wherein, described hydrogen peroxide spraying oxidation reaction floor is arranged in described spray-absorption district.
According to desulfuring and denitrifying apparatus of the present invention, preferably, described spray-absorption district comprises at least two-layer spray-absorption floor, and described hydrogen peroxide spraying oxidation reaction layer is arranged between ground floor spray-absorption layer and last one deck spray-absorption layer.
According to desulfuring and denitrifying apparatus of the present invention, preferably, described hydrogen peroxide spraying oxidation reaction layer is arranged between ground floor spray-absorption layer and second layer spray-absorption layer.
According to desulfuring and denitrifying apparatus of the present invention, preferably, described spray-absorption district comprises ground floor spray-absorption floor, second layer spray-absorption floor and third layer spray-absorption floor; Ground floor spray-absorption layer, second layer spray-absorption layer and third layer spray-absorption layer are arranged from the bottom up; Described hydrogen peroxide spraying oxidation reaction layer is arranged between ground floor spray-absorption layer and second layer spray-absorption layer or is arranged between second layer spray-absorption layer and third layer spray-absorption layer.
According to desulfuring and denitrifying apparatus of the present invention, preferably, interlayer arrange described hydrogen peroxide spraying oxidation reaction layer adjacent two-layer spray-absorption layer between distance be 2.5 meters ~ 3.5 meters.
According to desulfuring and denitrifying apparatus of the present invention, preferably, interlayer does not arrange that the spacing of the adjacent two-layer spray-absorption layer of described hydrogen peroxide spraying oxidation reaction layer is 1.5 meters ~ 2.2 meters.
The present invention also provides a kind of method utilizing above-mentioned desulfuring and denitrifying apparatus to carry out desulphurization denitration, comprises the steps:
Desulphurization denitration slurries supplying step: the desulphurization denitration serum recycle of slurries memory block is transported to spray-absorption district and sprays by serum recycle conveying equipment;
Hydrogen peroxide supplying step: supply hydrogen peroxide to hydrogen peroxide spraying oxidation reaction layer by hydrogen peroxide supply arrangement;
Flue gas oxidation step: hydrogen peroxide spraying oxidation reaction layer ejection hydrogen peroxide, the nitrogen oxide in oxidation flue gas and part sulfur dioxide are to form intermediate reaction product; Described intermediate reaction product comprises nitric acid, nitrous acid and sulfuric acid;
Wet absorption step: the part sulfur dioxide in the desulphurization denitration slurries utilizing spray-absorption district to spray and above-mentioned intermediate reaction product and flue gas reacts, and to form absorption product, and falls into slurries memory block;
Wherein, described desulphurization denitration slurries contain magnesia and magnesium hydroxide; Described absorption product comprises magnesium sulfate, magnesium sulfite, magnesium nitrate and magnesium nitrite.
According to method of the present invention, preferably, the process conditions of hydrogen peroxide spraying oxidation reaction layer are: temperature is 50 ~ 80 DEG C, and moisture content is 10% ~ 13%, relative temperature is 30% ~ 40%.
According to method of the present invention, preferably, described method also comprises:
Slurries memory block adds the step of hydrogen peroxide decomposition catalyst: in slurries memory block, add catalyst resolve into water and oxygen to make the hydroperoxidation of non-provocative reaction, magnesium nitrite and magnesium sulfite are oxidized into magnesium nitrate and magnesium sulfate by the oxygen of generation.
According to method of the present invention, preferably, described method also comprises the step of magnesium sulfate and magnesium nitrate being discharged process.
Apparatus and method of the present invention, combine magnesium processes desulfurization and hydrogen peroxide oxidation denitration, and improve hydrogen peroxide spraying oxidation reaction layer setting position of the prior art, improve the effect of simultaneously carrying out desulphurization denitration.Oxidation reaction of being sprayed by hydrogen oxide floor is arranged in spray-absorption district, hydrogen peroxide can being made to obtaining optimum shooting condition, producing more active material.And magnesia is the metal oxide that a kind of activity is very high, more can excitation portion H
2o
2produce active material hydroxyl radical free radical, therefore, magnesianly add the efficiency not only increasing desulfurization, and can play the synchronous effect promoted to the efficiency of denitration, this is that other wet desulphurization modes are unattainable.The present invention effectively raises the removal efficiency of nitrogen oxide and sulfur dioxide, SO
2removal efficiency can reach 100%, NO
xremoval efficiency can reach more than 80%, reduces H simultaneously
2o
2injection rate, it also avoid H while having saved cost
2o
2the danger that excessive, high temperature is explosion caused.In addition, apparatus and method of the present invention are relative to prior art, and equipment simplifies, and greatly reduce desulphurization denitration construction investment occupation of land in early stage and operating cost.
Accompanying drawing explanation
Fig. 1 is the schematic diagram of a kind of existing desulfuring and denitrifying apparatus of comparative example 1.
Fig. 2 is the schematic diagram of the desulfuring and denitrifying apparatus of comparative example 2 (improving based on Fig. 1).
In Fig. 1 and Fig. 2: 11 is H
2o
2storage tank, 12 is syringe pump, and 13 is H
2o
2shower nozzle, 14 is H
2o
2catalytic decomposition device, 15 is air blast, and 16 is active material shower nozzle, and 17 is preheating device, and 18 is heater.
Fig. 3 is the schematic diagram of the desulfuring and denitrifying apparatus of embodiments of the invention 1.
In Fig. 3: 21 is desulphurization denitration equipment, 22 is circulating pump, and 23 is ground floor spray-absorption layer, and 24 is second layer spray-absorption layer, and 25 is third layer spray-absorption layer, and 26 is desulphurization denitration slurry nozzle, and 27 is gas approach, and 28 is H
2o
2storage tank, 29 is syringe pump, and 210 is H
2o
2spraying oxidation reaction layer, 211 is H
2o
2nozzle, 212 is slurries memory block, and 213 is hydrogen peroxide decomposition catalyst.
Detailed description of the invention
Below the specific embodiment of the present invention is further described, but protection scope of the present invention is not limited to this.
" device " of the present invention is a kind of product, the i.e. system set of each component devices.Flue gas of the present invention can be the industrial smoke of various sulfur-containing oxide and nitrogen oxide, such as, be the flue gas of the sulfur-containing oxides such as coal-burning boiler, steel sintering machine, pelletizing and nitrogen oxide.In the present invention, entrance and import have identical implication, and the two can be replaced." moisture content " of the present invention is absolute drift, represents with percentage by weight.
Desulphurization denitration slurries of the present invention, containing Mg
2+and OH
-, be the alkali lye that magnesium processes wet desulphurization well known in the art is used, what preferably utilize MgO to make contains MgO and Mg (OH)
2mixed serum, for removing the acidic materials in flue gas or intermediate reaction product, especially oxysulfide, nitrogen oxide and intermediate product (below can be further specified) thereof.
Sulfur and nitrogen oxides of the present invention is the sulfur and nitrogen oxides of the various valence states usually contained in industrial smoke, and concrete main component refers to chemical reaction equation involved in this paper reaction principle described later.
< flue gas desulfurization and denitrification device >
Flue gas desulfurization and denitrification device of the present invention, comprises desulphurization denitration equipment, serum recycle conveying equipment and hydrogen peroxide supply arrangement.Described desulphurization denitration device interior is provided with: spray-absorption district, hydrogen peroxide spraying oxidation reaction floor and slurries memory block.Wherein, described hydrogen peroxide spraying oxidation reaction floor is arranged in described spray-absorption district.
Desulphurization denitration equipment of the present invention comprises spray-absorption district, and it for adopting the sulfur and nitrogen oxides in desulphurization denitration slurries wet absorption flue gas, and forms absorption product.Particularly, spray-absorption district of the present invention can spray desulphurization denitration slurries, part sulfur dioxide in these desulphurization denitration slurries and intermediate reaction product (hydrogen peroxide spray the intermediate product that oxidation reaction layer is formed) and flue gas reacts, to form absorption product.
Desulphurization denitration equipment of the present invention comprises hydrogen peroxide spraying oxidation reaction layer, it is in order to spray hydrogen peroxide, nitrogen oxide in this hydrogen peroxide oxidation flue gas and part sulfur dioxide, to form intermediate reaction product (comprising nitrous acid, nitric acid and sulfuric acid).Hydrogen peroxide spraying oxidation reaction floor of the present invention is arranged in described spray-absorption district, is different from the mode that traditional flue place arranges hydrogen peroxide spraying oxidation reaction.Through the spray-absorption of ground floor spray-absorption layer, affect hydrogen peroxide activated composition in flue gas to be absorbed in a large number, hydrogen peroxide can be made to produce more active material, effectively raise the removal efficiency (being hereafter described in detail) of nitrogen oxide.In hydrogen peroxide spraying oxidation reaction layer, go out hydrogen peroxide by hydrogen peroxide atomizing spray parts Jet with downward flow direction.The atomizing spray parts that hydrogen peroxide spraying oxidation reaction layer adopts have no particular limits, can use well known in the art those.As preferably, atomizing spray parts of the present invention are corrosion-resistant atomizing spray parts, are more preferably acid-fast alkali-proof corrosion atomizing spray parts.According to an embodiment of the invention, described atomizing spray parts preferably include stainless steel nozzle.
Spray-absorption district of the present invention preferably includes at least one for removing the spray-absorption floor of SO 2 from fume in flue gas and/or dust, and it is positioned at the below of hydrogen peroxide spraying oxidation reaction layer.More preferably, described spray-absorption district comprises at least three spray-absorption floor, and described three spray-absorption layers do not adjoin each other.
According to an embodiment of flue gas desulfurization and denitrification device of the present invention, described spray-absorption district is furnished with three floor spray-absorption floor, and described three layers of spray-absorption layer and described hydrogen peroxide spraying oxidation reaction layer distributing order are from the bottom up followed successively by: ground floor spray-absorption layer, hydrogen peroxide spraying oxidation reaction layer, second layer spray-absorption layer and third layer spray-absorption layer.Optionally, spray-absorption district of the present invention is also provided with other spray-absorption floor, and its quantity is depending on sulfureous in flue gas oxide and amount of nitrogen oxides.The spacing of ground floor spray-absorption layer and second layer spray-absorption layer is 2.5 ~ 3.5 meters, is preferably 2.8 meters ~ 3.0 meters.The spacing of second layer spray-absorption layer and third layer spray-absorption layer is 1.5 meters ~ 2.2 meters, is preferably 1.8 meters ~ 2.0 meters.1 ~ 1.8 meter, hydrogen peroxide spraying oxidation reaction layer distance ground floor spray-absorption layer, is preferably 1.2 ~ 1.6 meters.
According to another embodiment of flue gas desulfurization and denitrification device of the present invention, described spray-absorption district is furnished with three floor spray-absorption floor, and described three layers of spray-absorption layer and described hydrogen peroxide spraying oxidation reaction layer distributing order are from the bottom up followed successively by: ground floor spray-absorption layer, second layer spray-absorption layer, hydrogen peroxide spraying oxidation reaction layer and third layer spray-absorption layer.Optionally, spray-absorption district of the present invention is also provided with other spray-absorption floor, and its quantity is depending on sulfureous in flue gas oxide and amount of nitrogen oxides.The spacing of ground floor spray-absorption layer and second layer spray-absorption layer is 1.5 meters ~ 2.2 meters, is preferably 1.8 meters ~ 2.0 meters.The spacing of second layer spray-absorption layer and third layer spray-absorption layer is 2.5 ~ 3.5 meters, is preferably 2.8 meters ~ 3.0 meters.1 ~ 1.8 meter, hydrogen peroxide spraying oxidation reaction layer distance second layer spray-absorption layer, is preferably 1.2 ~ 1.6 meters.
Above two kinds of embodiments, hydrogen peroxide can be made to obtain optimum shooting condition, and (temperature is at 50 ~ 70 DEG C, saturated flue gas water content is 10% ~ 13%, relative temperature is in 30 ~ 40% scopes, flue gas is through the spray-absorption of ground floor, the material affecting hydrogen peroxide oxidation performance reduces), hydrogen peroxide can be made to produce more active material, effectively raise the removal efficiency of nitrogen oxide and oxysulfide, reduce the injection rate of hydrogen peroxide simultaneously, while having saved cost, it also avoid the danger that hydrogen peroxide is excessive, high temperature is explosion caused.
Desulphurization denitration equipment of the present invention comprises slurries memory block, and it is for storing desulphurization denitration slurries, and receives the absorption product from spray-absorption district.As preferably, slurries bank bit of the present invention, in the bottom of desulphurization denitration equipment, more preferably, is positioned at the below of gas approach.
Flue gas desulfurization and denitrification device of the present invention comprises serum recycle conveying equipment, and it is for being transported to described spray-absorption district by the desulphurization denitration serum recycle of described slurries memory block.The circulating pump that described serum recycle conveying equipment can be commonly used for this area.
According to an embodiment of the invention, desulphurization denitration slurries in slurries memory block are delivered to spray-absorption district by circulating pump through desulphurization denitration slurries transfer pipeline, after absorption product (comprising sulfate, sulphite, the NO3-N and NO2-N) condensation that wet absorption is formed, the weight against self falls into the slurries memory block of desulphurization denitration equipment.
According to an embodiment of the invention, in the desulphurization denitration slurries in slurries memory block, add hydrogen peroxide decomposition catalyst.In this embodiment, the hydrogen peroxide of non-provocative reaction falls into slurries memory block and contacts with the hydrogen peroxide decomposition catalyst of slurries, resolve into water and the oxygen of non-secondary pollution, sulphite, nitrite-oxidizing are become sulfate, nitrate by oxygen again that generate.The type of hydrogen peroxide decomposition catalyst has no particular limits, can use well known in the art those.Preferably, hydrogen peroxide decomposition catalyst comprises iron chloride, di-iron trioxide, manganese dioxide, cupric oxide etc., also can use CN101252991A, CN103272615A, CN104307520A, CN104289228A those disclosed.Preferably, hydrogen peroxide decomposition catalyst of the present invention is manganese dioxide.The consumption of hydrogen peroxide decomposition catalyst also has no particular limits, and is determined by actual conditions.If slurries oxidization condition is better, in desulphurization denitration slurries, also hydrogen peroxide decomposition catalyst can not be added.
Flue gas desulfurization and denitrification device of the present invention comprises hydrogen peroxide supply arrangement, and it is for supplying hydrogen peroxide to hydrogen peroxide spraying oxidation reaction layer.According to an embodiment of the invention, hydrogen peroxide supply arrangement comprises Hydrogen peroxide storage, wherein stores hydrogen peroxide.The type of Hydrogen peroxide storage has no particular limits, can use well known in the art those.In the present invention, hydrogen peroxide comprises pure hydrogen peroxide, hydrogenperoxide steam generator.Consider storage safe and easy-to-use, preferably there is (aliment) in the hydrogen peroxide in hydrogen peroxide supply arrangement, its concentration is preferably 3wt% ~ 35wt%, is more preferably 10wt% ~ 27.5wt% as an aqueous solution.According to an embodiment of the invention, the hydrogen peroxide in Hydrogen peroxide storage is delivered to hydrogen peroxide spraying oxidation reaction layer by syringe pump through hydrogen peroxide transfer pipeline.Quantity and the arrangement of hydrogen peroxide transfer pipeline have no particular limits, and can use circuit design well known in the art.
Optionally, flue gas desulfurization and denitrification device of the present invention also comprises dust arrester, and it is positioned at flue gas and enters optional position before desulphurization denitration equipment, for removing the dust carried secretly in flue gas.Type and the process conditions of dust arrester have no particular limits, and can use dust arrester well known in the art and technique.
Optionally, flue gas desulfurization and denitrification device of the present invention also comprises demister, and it is positioned at above spray-absorption district, for the dehydrating demisting of desulphurization denitration flue gas, avoids the steam carried secretly in desulphurization denitration flue gas and acid smog to the corrosion of emptying equipment.Type and the process conditions of demister have no particular limits, and can use demister known in the art and technique.
< desulfurization denitration method >
Utilize said apparatus of the present invention to carry out the method for desulphurization denitration, comprise the steps: desulphurization denitration slurries supplying step, wet absorption step, hydrogen peroxide supplying step, flue gas oxidation step and desulphurization denitration product condensation drop-off step.Optionally, denitration method for flue gas of the present invention also comprises dust removal step and demist step.Desulphurization denitration slurries supplying step of the present invention is supply desulphurization denitration slurries by slurries memory block to spray-absorption district.Desulphurization denitration slurries in slurries memory block are delivered to spray-absorption district by serum recycle conveying equipment (such as conventional circulating pump) through desulphurization denitration slurries transfer pipeline.According to an embodiment of the invention, in the desulphurization denitration slurries in slurries memory block, add hydrogen peroxide decomposition catalyst.Hydrogen peroxide decomposition catalyst kind as previously mentioned, repeats no more here.The consumption of hydrogen peroxide decomposition catalyst also has no particular limits, and is determined by actual conditions.If slurries oxidization condition is better, in desulphurization denitration slurries, also hydrogen peroxide decomposition catalyst can not be added.
Wet absorption step of the present invention is that the desulphurization denitration slurries absorption flue gas utilizing spray-absorption district to spray comprises sulfur and nitrogen oxides at interior absorbable materials.Particularly, wet absorption step of the present invention is that the part sulfur dioxide in the intermediate reaction product that formed of the desulphurization denitration slurries that utilize spray-absorption district to spray and flue gas oxidation step and flue gas reacts, and to form absorption product, and falls into slurries memory block.Preferably, desulphurization denitration slurries of the present invention contain magnesia and magnesium hydroxide.Be described as example, the sulfur dioxide in flue gas and desulphurization denitration slurry reaction generate the absorption product comprising magnesium sulfite.Containing nitrous acid, nitric acid and sulfuric acid in intermediate reaction product, itself and desulphurization denitration slurry reaction generate the absorption product comprising magnesium nitrite, magnesium nitrate and magnesium sulfate.Like this, absorption product of the present invention can comprise magnesium sulfate, magnesium sulfite, magnesium nitrate and magnesium nitrite.
What desulphurization denitration slurries of the present invention preferably utilized MgO to make contains MgO and Mg (OH)
2mixed serum.Compare other Wet Flue Gas Desulfurization Technique, magnesium oxide method desulfur technology is more suitable for arranging in pairs or groups with catalytic oxidation of hydrogen peroxide denitration technology forming simultaneous SO_2 and NO removal technology.Mainly due to magnesium oxide method sulfur removal technology, there is following advantage:
1) absorption efficiency is high: absorb slurries and be strongly atomized in absorption tower, in absorption tower, coverage rate reaches 200% ~ 220%, absorption efficiency ensures to reach more than 98%, even if only use one deck spraying layer to carry out flue gas desulfurization, also can reach the removal efficiency of more than 90%.
2) applied widely: countercurrent spray scrubbing tower is to the non-constant width of the scope of application of different exhaust gas volumn, flue gas concentration flue gas.Can adjust arbitrarily in the load range of 30 ~ 110%.
3) operating cost is low:
The liquid-gas ratio that a is lower: the liquid-gas ratio that magnesium oxide method desulfurization adopts is generally less than 5L/m
3, the liquid-gas ratio general control 8 ~ 10L/m on general limestone-gypsum absorption tower
3left and right, so also just greatly reduces the energy consumption needed for serum recycle.
B flue gas resistance is little: because magnesium oxide method desulfurization adopts lower liquid-gas ratio, reduce the resistance of flue gas by spraying layer, the air velocity that absorption tower and flue are selected is reasonable, therefore desulphurization system overall resistance is little, just can save the booster fan of traditional sulfur method, flue gas can rely on the overbottom pressure of coal-burning boiler air-introduced machine or agglomerates of sintered pellets main exhauster to be transported in desulfurizing tower by flue gas completely, further reduces desulphurization system investment and operating cost.
C is without line clogging phenomenon: the by-produced gypsum that traditional calcium method desulfurization generates, stable in properties, is deposited in a large number in inside, absorption tower and process pipe, greatly have impact on the normal operation of desulphurization system, serious blocking accident even occurs time serious; And the accessory substance that magnesium oxide method generates is magnesium sulfate, is water-soluble slurries, there is not clogging.
In addition, magnesia is the metal oxide that a kind of activity is very high, more can excitation portion H
2o
2produce active material hydroxyl radical free radical, therefore, magnesianly add the efficiency not only increasing desulfurization, and can play the synchronous effect promoted to the efficiency of denitration, this is that other wet desulphurization modes are unattainable.
According to an embodiment of the invention, described wet absorption step comprises makes flue gas from the bottom to top successively by ground floor spray-absorption layer, hydrogen peroxide spraying oxidation reaction layer, second layer spray-absorption layer and third layer spray-absorption layer.
According to another implementation of the invention, described wet absorption step comprises and makes flue gas from the bottom to top successively by ground floor spray-absorption layer, second layer spray-absorption layer, hydrogen peroxide spraying oxidation reaction layer and third layer spray-absorption layer.
Hydrogen peroxide supplying step of the present invention is supply hydrogen peroxide by hydrogen peroxide supply arrangement to hydrogen peroxide spraying oxidation reaction layer.According to an embodiment of the invention, hydrogen peroxide is stored in Hydrogen peroxide storage as an aqueous solution, by syringe pump, the aqueous hydrogen peroxide solution in Hydrogen peroxide storage is delivered to hydrogen peroxide spraying oxidation reaction layer through hydrogen peroxide transfer pipeline.In Hydrogen peroxide storage, the concentration of aqueous hydrogen peroxide solution is preferably 3wt% ~ 35wt%, is more preferably 10wt% ~ 27.5wt%.
Flue gas oxidation step of the present invention is, hydrogen peroxide spraying oxidation reaction layer ejection hydrogen peroxide, the nitrogen oxide in oxidation flue gas and part sulfur dioxide generate intermediate product (nitric acid, nitrous acid and sulfuric acid) respectively.These intermediate products then react with the magnesia in desulphurization denitration slurries, magnesium hydroxide and generate magnesium nitrate, magnesium nitrite and magnesium sulfate in spray-absorption district.
In hydrogen peroxide spraying oxidation reaction layer, go out hydrogen peroxide by hydrogen peroxide atomizing spray parts Jet with downward flow direction.The atomizing spray technique that described flue gas oxidation step adopts has no particular limits, can use well known in the art those.According to an embodiment of the invention, described flue gas oxidation step preferably adopts stainless steel nozzle to spray hydrogen peroxide.According to an embodiment of the invention, described flue gas oxidation step comprises makes flue gas from the bottom to top by hydrogen peroxide spraying oxidation reaction layer.
The key reaction principle of sweetening process involved in the present invention and denitrification process is as follows:
A. sweetening process:
Mg(OH)
2+H
2SO
3→MgSO
3↓+2H
2O
Mg(OH)
2+H
2SO
4→MgSO
4+2H
2O
MgSO
3+1/2O
2→MgSO
4
B. denitrification process
(1) H
2o
2be excited the generation active material that reacts, and reaction principle is as follows:
H
2O
2→2·OH
H
2O
2+·OH→HO
2·+H
2O
(2) H under normal temperature
2o
2with NO, NO
2oxidation reaction
H
2o
2(g)+NO (g) → NO
2(g)+H
2o (g) (slower)
H
2o
2(g)+NO
2(g) → HNO
3(g) (rapider)
(3) reaction of active material free radical and flue gas major pollutants
SO
2+·OH→HSO
3
HSO
3+·OH→H
2SO
4
NO+·OH→NO
2+·H
NO+HO
2·→NO
2+·OH
NO+·OH→HNO
2
NO
2+·OH→HNO
3
HNO
2+·OH→HNO
3
Mg(OH)
2+2HNO
2→Mg(NO
2)
2+2H
2O
Mg(OH)
2+HNO
3→Mg(NO
3)
2+2H
2O
Mg(NO
2)
2+O
2→Mg(NO
3)
2
(4) optionally, in desulphurization denitration slurries, hydrogen peroxide decomposition catalyst is added, as MnO
2, now, the hydrogen peroxide of non-provocative reaction generates oxygen under the effect of hydrogen peroxide decomposition catalyst:
In this case, the oxygen in desulphurization denitration equipment just derives from two parts, and a part is the oxygen contained in former flue gas, and another part is the H of non-provocative reaction
2o
2at catalyst MnO
2effect under the oxygen that generates.
Optionally, method of the present invention also comprises the step of magnesium sulfate and magnesium nitrate being discharged process.Can discharge through excavationg pump and enter magnesium sulfate and magnesium nitrate byproduct preparation system recycles.
Optionally, flue gas oxidation step of the present invention also comprises makes flue gas by other hydrogen peroxide spraying oxidation reaction layer, and its quantity has no particular limits, depending on oxidization condition.
The process conditions of hydrogen peroxide spraying oxidation reaction layer are preferably: temperature is 50 ~ 80 DEG C, is more preferably 60 ~ 70 DEG C; Moisture content is 10% ~ 13%, is more preferably 11% ~ 12%; Relative temperature is 30% ~ 40%, is more preferably 33% ~ 38%.
Optionally, wet absorption step of the present invention also comprises the spray-absorption layer making flue gas by other, and its quantity is depending on sulfureous in flue gas oxide and amount of nitrogen oxides.After magnesium sulfate, magnesium sulfite, magnesium nitrate and the magnesium nitrite condensation that wet absorption step is formed, the weight against self falls into the slurries memory block of desulphurization denitration equipment.
Below in conjunction with accompanying drawing, by comparing the apparatus and method of apparatus of the present invention and method and prior art, the present invention will be described in more detail.
First the raw material used in following comparative example and embodiment is described as follows:
The slurries containing magnesia and magnesium hydroxide that desulphurization denitration slurries are made for magnesia being added to the water (magnesia weight: water weight=3:17);
H
2o
2solution is aqueous hydrogen peroxide solution, and concentration of hydrogen peroxide is wherein 27.5wt%;
Hydrogen peroxide decomposition catalyst is manganese dioxide.
comparative example 1
Comparative example 1 is a kind of existing desulfuring and denitrifying apparatus and method.This desulfuring and denitrifying apparatus as shown in Figure 1, comprises H
2o
2storage tank 11, syringe pump 12, H
2o
2shower nozzle 13, H
2o
2catalytic decomposition device 14, air blast 15 and active material shower nozzle 16.
This technological process is: with syringe pump 12 H
2o
2h in storage tank 11
2o
2liquid transfer is to H
2o
2h above catalytic decomposition device 14
2o
2in shower nozzle 13, H
2o
2liquid is from H
2o
2shower nozzle 13 sprays, with H
2o
2catalyst reaction in catalytic decomposition device 14 produces active material, and the air-flow that active material blasts with air blast 15 enters flue by active material shower nozzle 16, oxidize sulfur dioxide and nitrogen oxide in flue.The major parameter of this technique is in table 1.
Table 1
| Sequence number | Parameter | Unit | Numerical value |
| 1 | Device portal exhaust gas volumn (operating mode) | m 3/h | 320000 |
| 2 | Device portal cigarette temperature | ℃ | 120～180 |
| 3 | Magnesium sulphur ratio | Mg/S | 1.02 |
| 4 | H 2O 2With NO XMol ratio | H 2O 2/NO X | 2 |
| 5 | Oxidization time | s | 1 |
| 6 | Most high desulfurization efficiency | ％ | 98 |
| 7 | The highest denitration efficiency | ％ | 69.4 |
comparative example 2
Comparative example 2 is desulfuring and denitrifying apparatus and the method for example 1 improvement based on the comparison.This device is on the basis of the device of the comparative example 1 shown in Fig. 1, at air blast 15 and H
2o
2preheating device 17 is added, at H between catalytic decomposition device 14
2o
2heater 18 has been wrapped up outside catalytic decomposition device 14.
The technological process of the method is: with syringe pump 12 H
2o
2h in storage tank 11
2o
2liquid transfer is to H
2o
2h above catalytic decomposition device 14
2o
2in shower nozzle 13, H
2o
2liquid is from H
2o
2shower nozzle 13 sprays, with H
2o
2catalyst reaction in catalytic decomposition device 14 produces active material, H
2o
2h given by heater 18 outside catalytic decomposition device 14
2o
2with catalyst heating, stimulate H
2o
2produce more active material, the thermal current that active material blasts with air blast 15 and preheating device 17 enters flue by active material shower nozzle 16, oxidize sulfur dioxide and nitrogen oxide in flue.The major parameter of this technique is as shown in table 2.
Table 2
| Sequence number | Parameter | Unit | Numerical value |
| 1 | Device portal exhaust gas volumn (operating mode) | m 3/h | 320000 |
| 2 | Device portal cigarette temperature | ℃ | 120～180 |
| 3 | Preheating device | ℃ | 100～140 |
| 4 | Heater | ℃ | 40～100 |
| 5 | Magnesium sulphur ratio | Mg/S | 1.02 |
| 6 | H 2O 2With NO XMol ratio | H 2O 2/NO X | 2 |
| 7 | Oxidization time | s | 1 |
| 8 | Most high desulfurization efficiency | ％ | 99.5 |
| 9 | The highest denitration efficiency | ％ | 79.3 |
embodiment 1
This embodiment relates to a kind of desulfuring and denitrifying apparatus of the present invention and method.As shown in Figure 3, described desulfuring and denitrifying apparatus comprises desulphurization denitration equipment 21 and hydrogen peroxide supply arrangement (comprises H
2o
2storage tank 28 and syringe pump 29) and as the circulating pump 22 of serum recycle conveying equipment, desulphurization denitration equipment 21 inside is provided with spray-absorption district (comprising ground floor spray-absorption floor 23, second layer spray-absorption floor 24 and third layer spray-absorption floor 25), H
2o
2spraying oxidation reaction layer 210 and slurries memory block 212.Wherein, H
2o
2spraying oxidation reaction layer 210 is arranged between ground floor spray-absorption layer 23 and second layer spray-absorption layer 24.Slurries memory block 212 is added with hydrogen peroxide decomposition catalyst 213.Ground floor spray-absorption layer 23 is 3.0 meters with the spacing of second layer spray-absorption layer 24.Second layer spray-absorption layer 24 is 2.0 meters with the spacing of third layer spray-absorption layer 25.Hydrogen peroxide spraying oxidation reaction layer 210 and apart 1.6 meters, ground floor spray-absorption layer 23.Exemplary desulphurization denitration slurry nozzle 26 and the H having marked the setting of ground floor spray-absorption layer 23 in Fig. 3
2o
2the H that spraying oxidation reaction layer 210 is arranged
2o
2nozzle 211.Described desulfuring and denitrifying apparatus also comprises gas approach 27, and gas approach 27 is communicated with desulphurization denitration equipment 21, flue gas can be made to enter in desulphurization denitration equipment 21 by gas approach 27.Circulating pump 22 is communicated with each spray-absorption layer and slurries memory block 212 as serum recycle conveying equipment, for the desulphurization denitration slurries in slurries memory block 212 are delivered to each spray-absorption layer.
The technological process utilizing described desulfuring and denitrifying apparatus to carry out desulphurization denitration is: enter desulphurization denitration equipment 21 from coal-burning boiler by gas approach 27, to react the most of SO removed in flue gas with desulphurization denitration slurries (desulphurization denitration slurries are delivered to ground floor spray-absorption layer 23, second layer spray-absorption layer 24 and third layer spray-absorption layer 25 from slurries memory block 212 by circulating pump 22, are atomized Jet with downward flow direction by desulphurization denitration slurry nozzle 26) reverse contact
2and dust, and form the absorption product containing magnesium sulfite.The flue gas of preliminary purification again with from H
2o
2the H that spraying oxidation reaction layer 210 sprays
2o
2(H
2o
2h in storage tank 28
2o
2solution syringe pump 29 is delivered to H
2o
2spraying oxidation reaction layer 210, passes through H
2o
2nozzle 211 Jet with downward flow direction) there is oxidation reaction, nitrogen oxide in oxidation flue gas and part sulfur dioxide generate nitric acid, nitrous acid and sulfuric acid respectively, and react with the magnesium hydroxide in desulphurization denitration slurries absorption product then that generate containing magnesium nitrate, magnesium nitrite and magnesium sulfate.The absorption product containing magnesium sulfite, magnesium sulfate, magnesium nitrite, magnesium nitrate of final generation falls into the slurries memory block 212 of desulphurization denitration equipment 21, (part is the oxygen contained in former flue gas, and another part is unreacted H for magnesium sulfite wherein and magnesium nitrite and oxygen
2o
2the oxygen generated is reacted with the hydrogen peroxide decomposition catalyst 213 in desulphurization denitration slurries) there is oxidation reaction and generate magnesium sulfate and magnesium nitrate.The major parameter of this technique is as shown in table 3.
Table 3
| Sequence number | Parameter | Unit | Numerical value |
| 1 | Device portal exhaust gas volumn (operating mode) | m 3/h | 320000 |
| 2 | Device portal cigarette temperature | ℃ | 120～180 |
| 3 | Magnesium sulphur ratio | Mg/S | 1.02 |
| 4 | H 2O 2With NO XMol ratio | H 2O 2/NO X | 1.2 |
| 5 | Oxidization time | s | 1 |
| 6 | Most high desulfurization efficiency | ％ | 100 |
| 7 | The highest denitration efficiency | ％ | 81.5 |
embodiment 2
This embodiment relates to the another kind of desulfuring and denitrifying apparatus of the present invention and method.The difference of the desulfuring and denitrifying apparatus of this desulfuring and denitrifying apparatus and embodiment 1 is, H
2o
2spraying oxidation reaction layer is arranged between second layer spray-absorption layer and third layer spray-absorption layer.The spacing of ground floor spray-absorption layer and second layer spray-absorption layer is 2.0 meters.The spacing of second layer spray-absorption layer and third layer spray-absorption layer is 3.0 meters.Hydrogen peroxide spraying oxidation reaction layer and second layer spray-absorption layer are at a distance of 1.6 meters.Other setting is identical with the device of the embodiment 1 that Fig. 1 represents.
Utilize the desulfurization denitration method of this desulfuring and denitrifying apparatus identical with the desulfurization denitration method of embodiment 1.The major parameter of the desulfurization denitration method of this embodiment is as shown in table 4.
Table 4
| Sequence number | Parameter | Unit | Numerical value |
| 1 | Device portal exhaust gas volumn (operating mode) | m 3/h | 320000 |
| 2 | Device portal cigarette temperature | ℃ | 120～180 |
| 3 | Magnesium sulphur ratio | Mg/S | 1.02 |
| 4 | H 2O 2With NO XMol ratio | H 2O 2/NO X | 1.2 |
| 5 | Oxidization time | s | 1 |
| 6 | Most high desulfurization efficiency | ％ | 100 |
| 7 | The highest denitration efficiency | ％ | 81.2 |
comparative example 3
The difference of the desulfuring and denitrifying apparatus of this comparative example and the desulfuring and denitrifying apparatus of embodiment 1 is, H
2o
2spraying oxidation reaction layer is arranged on flue entrance place, and other setting is identical with the device of the embodiment 1 that Fig. 1 represents.
The desulfuring and denitrifying apparatus of this comparative example is utilized to carry out the method for desulphurization denitration only based on above-mentioned H
2o
2the difference of spraying oxidation reaction layer arranges and adjusts accordingly the method described in embodiment 1.One skilled in the art will readily appreciate that how this operates, and repeats no more here.
The major parameter of the method for denitration of this comparative example is as shown in table 5.
Table 5
| Sequence number | Parameter | Unit | Numerical value |
| 1 | Device portal exhaust gas volumn (operating mode) | m 3/h | 320000 |
| 2 | Device portal cigarette temperature | ℃ | 120～180 |
| 3 | Magnesium sulphur ratio | Mg/S | 1.02 |
| 4 | H 2O 2With NO XMol ratio | H 2O 2/NO X | 1.2 |
| 5 | Oxidization time | s | 1 |
| 6 | Most high desulfurization efficiency | ％ | 98 |
| 7 | The highest denitration efficiency | ％ | 63.4 |
Relatively can find out that desulfurizing and denitrifying process method of the present invention and device have significant progress from above-described embodiment 1-2 and comparative example 1-3.Hydrogen peroxide sprayer unit is arranged in the position of flue, as comparative example 1, even if H
2o
2with NO
xmol ratio is 2.0, and denitration efficiency also can only reach 69.4%.Even if increase equipment with modifying device and technique to the device of comparative example 1 as comparative example 2, and make H
2o
2with NO
xwhen mol ratio is 2.0, denitration efficiency can not reach 80%.And the embodiment 2 hydrogen peroxide sprayer unit being arranged in the embodiment 1 between ground floor and second layer spraying layer or being arranged between the second layer and third layer spraying layer, at H
2o
2with NO
x(H when mol ratio is only 0.9
2o
2the half of the not enough comparative example 1 and 2 of relative usage), denitration effect is still more than 80%.And adopt H
2o
2spraying oxidation reaction layer is arranged on device and the technique of the comparison 3 at flue entrance place, when keeping other process conditions identical with 2 with embodiment 1, the highest denitration efficiency only has 63.4%, than the denitration efficiency respectively low 18.1% and 17.8% of embodiment 1 and 2.In addition, the most high desulfurization efficiency of embodiment 1 and 2 can reach 100%, and comparative example 1-3 can not reach.Above data show that the present invention can meet the minimum discharge of environmental requirement clearly, can reduce again investment and operating cost simultaneously.
The present invention is not limited to above-mentioned embodiment, and when not deviating from flesh and blood of the present invention, any distortion that it may occur to persons skilled in the art that, improvement, replacement all fall into scope of the present invention.
Claims (10)
1. a desulfuring and denitrifying apparatus, is characterized in that, comprising:
Desulphurization denitration equipment, its inside is provided with:
Hydrogen peroxide spraying oxidation reaction layer, in order to spray hydrogen peroxide, the nitrogen oxide in this hydrogen peroxide oxidation flue gas and part sulfur dioxide, to form intermediate reaction product;
Spray-absorption district, in order to spray desulphurization denitration slurries, the part sulfur dioxide in these desulphurization denitration slurries and above-mentioned intermediate reaction product and flue gas reacts, to form absorption product;
Slurries memory block, for storing desulphurization denitration slurries, and receives the absorption product from spray-absorption district;
Serum recycle conveying equipment, for being transported to described spray-absorption district by the desulphurization denitration serum recycle of described slurries memory block;
Hydrogen peroxide supply arrangement, for supplying hydrogen peroxide to hydrogen peroxide spraying oxidation reaction layer;
Wherein, described hydrogen peroxide spraying oxidation reaction floor is arranged in described spray-absorption district.
2. desulfuring and denitrifying apparatus according to claim 1, is characterized in that, described spray-absorption district comprises at least two-layer spray-absorption floor, and described hydrogen peroxide spraying oxidation reaction layer is arranged between ground floor spray-absorption layer and last one deck spray-absorption layer.
3. desulfuring and denitrifying apparatus according to claim 2, is characterized in that, described hydrogen peroxide spraying oxidation reaction layer is arranged between ground floor spray-absorption layer and second layer spray-absorption layer.
4. desulfuring and denitrifying apparatus according to claim 1, is characterized in that, described spray-absorption district comprises ground floor spray-absorption floor, second layer spray-absorption floor and third layer spray-absorption floor; Ground floor spray-absorption layer, second layer spray-absorption layer and third layer spray-absorption layer are arranged from the bottom up; Described hydrogen peroxide spraying oxidation reaction layer is arranged between ground floor spray-absorption layer and second layer spray-absorption layer or is arranged between second layer spray-absorption layer and third layer spray-absorption layer.
5. desulfuring and denitrifying apparatus according to claim 4, is characterized in that, the distance between the adjacent two-layer spray-absorption layer that interlayer arranges described hydrogen peroxide spraying oxidation reaction layer is 2.5 meters ~ 3.5 meters.
6. desulfuring and denitrifying apparatus according to claim 5, is characterized in that, interlayer does not arrange that the spacing of the adjacent two-layer spray-absorption layer of described hydrogen peroxide spraying oxidation reaction layer is 1.5 meters ~ 2.2 meters.
7. utilize the desulfuring and denitrifying apparatus described in any one of claim 1-6 to carry out a method for desulphurization denitration, it is characterized in that, comprise the steps:
Desulphurization denitration slurries supplying step: the desulphurization denitration serum recycle of slurries memory block is transported to spray-absorption district and sprays by serum recycle conveying equipment;
Hydrogen peroxide supplying step: supply hydrogen peroxide to hydrogen peroxide spraying oxidation reaction layer by hydrogen peroxide supply arrangement;
Flue gas oxidation step: hydrogen peroxide spraying oxidation reaction layer ejection hydrogen peroxide, the nitrogen oxide in oxidation flue gas and part sulfur dioxide are to form intermediate reaction product; Described intermediate reaction product comprises and comprises nitric acid, nitrous acid and sulfuric acid;
Wet absorption step: the part sulfur dioxide in the desulphurization denitration slurries utilizing spray-absorption district to spray and above-mentioned intermediate reaction product and flue gas reacts, and to form absorption product, and falls into slurries memory block;
Wherein, described desulphurization denitration slurries contain magnesia and magnesium hydroxide; Described absorption product comprises magnesium sulfate, magnesium sulfite, magnesium nitrate and magnesium nitrite.
8. method according to claim 7, is characterized in that, the process conditions of hydrogen peroxide spraying oxidation reaction layer are: temperature is 50 ~ 80 DEG C, and moisture content is 10% ~ 13%, relative temperature is 30% ~ 40%.
9. method according to claim 7, is characterized in that, described method also comprises:
Slurries memory block adds the step of hydrogen peroxide decomposition catalyst: in slurries memory block, add catalyst resolve into water and oxygen to make the hydroperoxidation of non-provocative reaction, magnesium nitrite and magnesium sulfite are oxidized into magnesium nitrate and magnesium sulfate by the oxygen of generation.
10. method according to claim 9, is characterized in that, described method also comprises the step of magnesium sulfate and magnesium nitrate being discharged process.
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|---|---|---|---|
| CN201510303399.5A CN104941431A (en) | 2015-06-05 | 2015-06-05 | Desulphurization and denitration device and method |
| HK16103123.6A HK1215224A1 (en) | 2015-06-05 | 2016-03-17 | Desulphurization and denitration device and method |
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|---|---|---|---|
| CN201510303399.5A CN104941431A (en) | 2015-06-05 | 2015-06-05 | Desulphurization and denitration device and method |
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| CN105903330A (en) * | 2016-06-02 | 2016-08-31 | 西安热工研究院有限公司 | System and method for efficient combined desulfurization and denitration |
| CN107042062A (en) * | 2017-01-19 | 2017-08-15 | 四川京典能源科技有限公司 | Gas sweetening method of denitration |
| CN108187474A (en) * | 2017-12-29 | 2018-06-22 | 新疆天之蓝环境工程有限公司 | The method and desulfuring and denitrifying apparatus of desulphurization denitration |
| CN108261900A (en) * | 2018-03-28 | 2018-07-10 | 南京工业大学 | Sectional type device and method for flue gas desulfurization and denitrification |
| CN109179485A (en) * | 2018-11-13 | 2019-01-11 | 常宁市华兴冶化实业有限责任公司 | A method of it emulsifying zinc oxide desulfurization and prepares zinc sulfate |
| CN111905547A (en) * | 2019-05-07 | 2020-11-10 | 山东师范大学 | Method for oxidizing low-concentration NO in gas by using hydrogen peroxide |
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| CN105903330A (en) * | 2016-06-02 | 2016-08-31 | 西安热工研究院有限公司 | System and method for efficient combined desulfurization and denitration |
| CN105903330B (en) * | 2016-06-02 | 2018-06-26 | 西安热工研究院有限公司 | A kind of system and method for efficient joint desulphurization denitration |
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| CN109179485A (en) * | 2018-11-13 | 2019-01-11 | 常宁市华兴冶化实业有限责任公司 | A method of it emulsifying zinc oxide desulfurization and prepares zinc sulfate |
| CN111905547A (en) * | 2019-05-07 | 2020-11-10 | 山东师范大学 | Method for oxidizing low-concentration NO in gas by using hydrogen peroxide |
| CN113117485A (en) * | 2019-12-30 | 2021-07-16 | 中晶环境科技股份有限公司 | Method for desulfurization and denitrification by using ammonium bisulfite |
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| CN112999844B (en) * | 2021-03-05 | 2022-07-01 | 合肥热电集团有限公司 | Coal-fired power plant flue gas desulfurization and denitrification integrated treatment system and method |
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