CN104941412A - Flue gas desulphurization-denitration integrated device and method - Google Patents
Flue gas desulphurization-denitration integrated device and method Download PDFInfo
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- CN104941412A CN104941412A CN201510303096.3A CN201510303096A CN104941412A CN 104941412 A CN104941412 A CN 104941412A CN 201510303096 A CN201510303096 A CN 201510303096A CN 104941412 A CN104941412 A CN 104941412A
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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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Abstract
The invention discloses a flue gas desulphurization-denitration integrated device and method. The flue gas desulphurization-denitration integrated device comprises a flue gas desulphurization-denitration device, an ozone supplement device and a hydrogen peroxide supplement device. The flue gas desulphurization-denitration device comprises an ozone spray oxidation reaction layer, a hydrogen peroxide spray oxidation reaction layer, an absorption spray zone and a slurry storage zone. The ozone spray oxidation reaction layer and the hydrogen peroxide spray oxidation reaction layer are arranged in the absorption spray zone. The flue gas desulphurization-denitration integrated device and method are suitable for desulphurization-denitration integrated treatment on SO2- and NOX-containing flue gas produced by a coal-fired boiler, a steel sintering machine, pelletizing and an industrial kiln, and solve the problem that the existing flue gas desulphurization-denitration integrated method has a high operation cost, utilizes complex equipment and has low denitration efficiency.
Description
Technical field
The present invention relates to a kind of flue gas desulfurization and denitrification integrated apparatus and method, especially a kind of integrated apparatus and method simultaneously removing sulfur dioxide in flue gas and nitrogen oxide.
Background technology
In view of sulfur dioxide (SO
2) and nitrogen oxide (NO
x) to the adverse effect of atmospheric environment and to the healthy infringement brought of people, national environmental protection portion will control coal-burning boiler, Industrial Stoves, steel sintering pelletizing equipment SO
2and NO
xdischarge be classified as and pollute keypoint treatment work, and relevant environmental protection standard increasingly stringent.If to SO
2and NO
xcarry out respectively removing process, need to introduce many complete equipments, invest high, take up an area large, so various flue gas multiple pollutant new control technology continues to bring out in recent years.At SO
2and NO
xremove, NO
xremove than SO
2difficulty is many, therefore main from removing NO
xangle set out, research the integrated of flue gas multiple pollutant remove purified treatment.
At present, main flow denitration technology is selective catalytic reduction (SCR) or selective non-catalytic reduction (SNCR).SCR method denitration efficiency is high, and secondary pollution is little, but equipment investment expense is large, and need to use catalyst, operation and maintenance cost is high; And SNCR method is invested and operating cost is less, but denitration efficiency is lower.The removal efficiency of above-mentioned two kinds of denitration technologies can reach the discharge standard of current country formulation, but its complex process, and controlled condition is harsh, and investment, operating cost costliness, floor space is large, is unwell to transformation project.When discharge standard improves constantly, the disbursement of enterprise in denitration strengthens day by day, and denitration work faces awkward situation: alternatives is few; The denitration technology operating cost on Practical Project can be applied to, construction cost is all higher.Therefore, major tasks and the developing direction that efficiency denitrating technique that is high, good economy performance becomes environmental protection industry (epi) is researched and developed.
Studying new and effective, Low investment, low cost desulfurization and denitrification integral method is the main direction of studying of current environmental protection industry (epi).Utilizing oxidant to carry out flue gas and desulfurizing and denitrifying in conjunction with wet desulphurization device is a kind of novel denitration technology, and the method utilizes the principle of forced oxidation that NO less for solubility in flue gas is oxidized to NO
2or N
2o
5etc. the nitrogen oxide (NO of high-valence state
x), and then absorb with water or alkaline matter.Oxidant carries out flue gas and desulfurizing and denitrifying technology in conjunction with wet desulphurization device can make full use of original desulphurization system, has the advantages such as improvement cost is low, the cycle is short, it is little to take up an area, technique simple, strong adaptability.
CN103977682A, CN104056538A, CN203916431U disclose one and utilize O separately
3as the flue gas and desulfurizing and denitrifying method of oxidant, adopt O
3be injected in flue as oxidant, the NO in boiler smoke is oxidized to NO soluble in water
2or N
2o
5, then same SO
2become sulfate, nitrate by water or alkali liquor absorption together, reach and remove SO in flue gas
2and NO
xobject.But, in the technique disclosed in these several sections of patents, be all add O at flue place
3, and O
3at the cigarette temperature environment more than 130 DEG C and dustiness at 50 ~ 200mg/Nm
3time in scope, very easily produce decomposition, adsorb dirt material and lose activity; And adopt O separately
3during oxidation and denitration, although oxidation efficiency is higher, O
3consumption is large, produces O
3spent electricity is surprising especially, often produces 1kg O
3need consumes power 12kwh.If the ozone generator under use prior art carries out O
3denitration, operating cost is too high.
CN102327735A discloses one and utilizes H
2o
2as the flue gas and desulfurizing and denitrifying method of oxidant.The method is by cheap H
2o
2in injection flue, oxidation NO, then washs flue gas and reaches and remove SO in absorption tower
2and NO
xobject.Although this method is invested and operating cost is lower, H
2o
2instability, more than 120 DEG C, especially at 140 DEG C and decomposition can occur (intensive decomposition becomes H above
2o and O
2, lose oxidation NO
xability), and dust can make H
2o
2itself and excite active material hydroxyl radical free radical OH and O of formation under certain condition
2h momentary aggregate loses activity, and flue gas in flue temperature is just in this temperature range, and dustiness is higher, significantly reduces H
2o
2oxidation susceptibility, cause that denitration efficiency is the highest is no more than 70%.CN103463978A adds H on the basis of CN102327735A
2o
2catalytic decomposition device, makes H
2o
2decompose and produce OH, but this kind of method tower outer use equipment is many and complicated, floor space is large, adds investment, operating cost.
Therefore, develop one and can have O concurrently
3high oxygenation efficiencies and H
2o
2the oxidation sweetening denitrification integral process of cheap two kinds of advantages and device, greatly can advance the commercial Application process of oxidative absorption desulfurization and denitrification integral technology.
CN102343212A discloses a kind of H
2o
2and O
3synergistic oxidation is in conjunction with the desulfurization and denitrification integral process of wet desulphurization device: first spray into H
2o
2solution as oxidant, then sprays into O
3as activator, oxidation NO becomes easy absorbed high-valence state nitrogen oxide, then utilizes desulfurization slurry to absorb, reaches the effect of desulfurization and denitrification integral.But this technique is equally by primary oxidant H
2o
2be expelled in flue, flue place is difficult to provide H
2o
2the optimum of oxidation, and this kind of method is by O
3as activator, underuse O
3the advantage of strong oxidizing property, simultaneously same by O
3be expelled to flue, O
3what be subject to dust and temperature affects generation decomposition, causes that total denitration efficiency is the highest can only reach about 60%.
Summary of the invention
In order to overcome the deficiency of existing desulphurization denitration technology, the invention provides a kind of by wet absorption desulphurization plant, combined with ozone and hydrogen peroxide synergistic oxidation carry out the apparatus and method of flue gas and desulfurizing and denitrifying.Apparatus and method of the present invention are particularly useful for coal-burning boiler, steel sintering machine, pelletizing, Industrial Stoves etc. containing SO
2and NO
xthe desulphurization denitration process of flue gas.
The invention provides a kind of ozone and hydrogen peroxide synergistic oxidation in conjunction with the flue gas desulfurization and denitrification integrated apparatus of wet absorption, comprising:
Flue gas desulfurization and denitrification equipment, its inside is provided with:
Ozone steam oxidation reaction layer and hydrogen peroxide spraying oxidation reaction layer, for the lower nitrogen oxides in synergistic oxidation flue gas, and form higher nitrogen oxides;
Absorbing spray district, for adopting sulfur dioxide in alkaline slurry wet absorption flue gas and nitrogen oxide, and forming absorption product; With
Slurries memory block, for supplying alkaline slurry to absorption spray district, and receives the absorption product in self-absorption spray district;
Ozone supply apparatus, for ozone steam oxidation reaction layer ozone supply; With
Hydrogen peroxide supply arrangement, for supplying hydrogen peroxide to hydrogen peroxide spraying oxidation reaction layer;
Wherein, described ozone steam oxidation reaction floor and hydrogen peroxide spraying oxidation reaction floor are all arranged in described absorption spray district.
According to flue gas desulfurization and denitrification integrated apparatus of the present invention, preferably, described absorption spray district comprises at least three and absorbs spraying layer, and described at least three absorption spraying layers do not adjoin each other, and is separated by described ozone steam oxidation reaction layer and hydrogen peroxide spraying oxidation reaction interlayer.
It is according to flue gas desulfurization and denitrification integrated apparatus of the present invention, preferably, described that absorption spray district comprises the first absorption spraying layer from the bottom to top successively, the second absorption spraying layer and the 3rd absorbs spraying layer; Ozone steam oxidation reaction layer is arranged on the first absorption spraying layer and second and absorbs between spraying layer; Hydrogen peroxide spraying oxidation reaction layer is arranged on the second absorption spraying layer and the 3rd and absorbs between spraying layer.
According to flue gas desulfurization and denitrification integrated apparatus of the present invention, preferably, described ozone steam oxidation reaction layer distance first absorbs spraying layer 0.5 ~ 1.5m; Described hydrogen peroxide spraying oxidation reaction floor distance second absorbs spray district 0.8 ~ 1.8m, and distance the 3rd absorbs spraying layer 1 ~ 2.2m.
It is according to flue gas desulfurization and denitrification integrated apparatus of the present invention, preferably, described that absorption spray district comprises the first absorption spraying layer from the bottom to top successively, the second absorption spraying layer and the 3rd absorbs spraying layer; Hydrogen peroxide spraying oxidation reaction layer is arranged on the first absorption spraying layer and second and absorbs between spraying layer; Ozone steam oxidation reaction layer is arranged on the second absorption spraying layer and the 3rd and absorbs between spraying layer.
According to flue gas desulfurization and denitrification integrated apparatus of the present invention, preferably, described hydrogen peroxide spraying oxidation reaction layer distance first absorbs spraying layer 0.5 ~ 1.5m; Described ozone steam oxidation reaction floor distance second absorbs spray district 0.8 ~ 1.8m, and distance the 3rd absorbs spraying layer 1 ~ 2.2m.
The present invention also provides a kind of and utilizes above-mentioned flue gas desulfurization and denitrification integrated apparatus to carry out the method for flue gas and desulfurizing and denitrifying, comprises the steps:
Flue gas oxidation step, in ozone steam oxidation reaction layer and hydrogen peroxide spraying oxidation reaction layer, utilizes the lower nitrogen oxides in ozone and hydrogen peroxide synergistic oxidation flue gas, and forms higher nitrogen oxides;
Wet absorption step, adopts the sulfur dioxide in alkaline slurry wet absorption flue gas and nitrogen oxide, and forms absorption product;
Alkaline slurry supplying step, supplies alkaline slurry by slurries memory block to absorption spray district;
Ozone supply step, by ozone supply device to ozone steam oxidation reaction layer ozone supply; With
Hydrogen peroxide supplying step, supplies hydrogen peroxide by hydrogen peroxide supply arrangement to hydrogen peroxide spraying oxidation reaction layer.
According to method of the present invention, preferably, in described flue gas oxidation step, the process conditions of ozone steam oxidation reaction layer are: flue-gas temperature is 50 ~ 80 DEG C, and dust content is 30 ~ 50mg/Nm
3, relative humidity is greater than 30%, and humidity of flue gas is 10% ~ 15%; The process conditions of hydrogen peroxide spraying oxidation reaction layer are: flue-gas temperature is 40 ~ 70 DEG C, and moisture content is 10% ~ 13%, and relative humidity is 30% ~ 40%.
According to method of the present invention, preferably, in described flue gas oxidation step, the ozone concentration in the aliment that described ozone supply step provides is 2 ~ 12wt%; Concentration of hydrogen peroxide in the aliment that described hydrogen peroxide supplying step provides is 3wt% ~ 35wt%.
According to method of the present invention, preferably, described alkaline slurry supplying step is also included in described alkaline slurry and adds hydrogen peroxide decomposition catalyst.
Apparatus and method of the present invention are by wet absorption desulphurization plant, and combined with ozone and hydrogen peroxide synergistic oxidation, thus can realize carrying out flue gas and desulfurizing and denitrifying process.According to the preferred technical scheme of the present invention, apparatus and method of the present invention are compared to traditional ozone oxidation desulfurization and denitrification integral process, and can save the ozone usage of more than 50%, operating cost is low, have higher economy.According to the present invention's preferred technical scheme further, apparatus and method of the present invention are compared to the existing flue gas desulfurization and denitrification integral process adding ozone, hydrogen peroxide at flue place, the generation of active material hydroxyl radical free radical improves 100% ~ 150% more than, effectively improves the removal efficiency of nitrogen oxide.Further, because apparatus and method of the present invention are without the need to carrying out large-scale redevelopment to existing desulphurization plant, improvement cost is low, the cycle is short, it is little to take up an area, and technique is simple, strong adaptability.
Accompanying drawing explanation
Fig. 1 is the device schematic diagram of comparative example 1.
In Fig. 1: 11 is air inlet flue, and 12 is ozone generator, and 13 is desulphurization denitration tower, and 14 for giving vent to anger flue, and 15 is desulphurization denitration circulating pump.
Fig. 2 is the device schematic diagram of comparative example 2.
In Fig. 2: 21 is Hydrogen peroxide storage, 22 is syringe pump, and 23 is hydrogen peroxide shower nozzle, and 24 is Catalytic Decomposition of Hydrogen Peroxide device, and 25 is air blast, and 26 is active material shower nozzle.
Fig. 3 is the device schematic diagram of comparative example 3.
In Fig. 3: 31 is smoke inlet, 32 is venturi aditus laryngis, and 33 is hydrogen peroxide atomizer, and 34 is ozone injection pipe network, and 35 is static mixer, and 36 is exhanst gas outlet.
Fig. 4-1 is the device schematic diagram of the embodiment of the present invention 1.
Fig. 4-2 is device schematic diagrames of the embodiment of the present invention 2.
In Fig. 4-1 and Fig. 4-2: 41 is flue gas desulfurization and denitrification equipment, 42 for absorbing spray district, 43 is defogging equipment, 44 is ozone steam oxidation reaction layer, 45 is ozone supply apparatus, 46 is ozone transfer pipeline, and 47 is hydrogen peroxide spraying oxidation reaction layer, and 48 is hydrogen peroxide supply arrangement, 49 is syringe pump, 410 is slurries memory block, and 411 is gas approach, and 412 is hydrogen peroxide decomposition catalyst, 413 is the first absorption spraying layer, 414 is the second absorption spraying layer, and 415 is the 3rd absorption spraying layer, and 416 is desulphurization denitration circulating pump.
Detailed description of the invention
Below in conjunction with accompanying drawing and specific embodiment, the present invention is further illustrated, 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 device.In the present invention, entrance and import have identical implication, and the two can be replaced." relative humidity " of the present invention adopts percentage to represent." flue gas moisture content " of the present invention is absolute drift, represents with percentage by weight.
In the present invention, lower nitrogen oxides represents that nitrogen is the nitrogen oxide of below trivalent (containing trivalent), comprises the nitrogen oxide (NO of the lower valencies such as NO
x); Higher nitrogen oxides represents that nitrogen is the nitrogen oxide of more than tetravalence (containing tetravalence), comprises NO
2, N
2o
5etc. the nitrogen oxide (NO of high-valence state
x).
" wet absorption " of the present invention, refers to using alkaline slurry as main desulphurization denitration and absorbs composition, but be not limited to the flue gas desulfurization and denitration technique adding other arbitrary compositions.In flue gas desulfurization and denitrification integral process of the present invention, the composition playing the alkaline slurry of desulphurization denitration effect may change to some extent, and its formula or change are known to those skilled in the art.
< flue gas desulfurization and denitrification integrated apparatus >
Ozone of the present invention and hydrogen peroxide synergistic oxidation comprise following equipment in conjunction with the flue gas desulfurization and denitrification integrated apparatus of wet absorption: flue gas desulfurization and denitrification equipment, ozone supply apparatus and hydrogen peroxide supply arrangement.According to flue gas desulfurization and denitrification integrated apparatus of the present invention, described flue gas desulfurization and denitrification device interior is provided with: ozone steam oxidation reaction floor and hydrogen peroxide spraying oxidation reaction floor, absorption spray district and slurries memory block, wherein, described ozone steam oxidation reaction floor and hydrogen peroxide spraying oxidation reaction floor are all located in described absorption spray district.Optionally, flue gas desulfurization and denitrification integrated apparatus of the present invention also comprises dust arrester and demister.
Flue gas desulfurization and denitrification equipment of the present invention comprises ozone steam oxidation reaction layer and hydrogen peroxide spraying oxidation reaction layer, it is all arranged on and absorbs (instead of being arranged in flue) in spray district, for the lower nitrogen oxides (such as NO) in synergistic oxidation flue gas, and formed easily by the higher nitrogen oxides that alkaline slurry absorbs, as NO
2, N
2o
5deng.In ozone steam oxidation reaction layer, go out ozone by ozone atomization sprinkler part Jet with downward flow direction.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 ozone steam oxidation reaction layer and hydrogen peroxide spraying oxidation reaction layer adopt 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.The ozone that ozone steam oxidation reaction layer ejects and the hydrogen peroxide that hydrogen peroxide spraying oxidation reaction layer ejects and the lower nitrogen oxides generation oxidation reaction in flue gas, formation higher nitrogen oxides, its cardinal principle is as follows.
A, ozone oxidation reaction step:
1) ozone is as oxidant, starts oxidation:
O
3+NO→NO
2+O
2
NO
2+O
3→NO
3+O
2
NO
2+NO
3→2N
2O
5
2) ozone is in suitable humidity with containing under the environment of hydroxide ion, causes chain reaction:
O
3+OH
-→HO
2·+O
2·
HO
2·→O
2 -·+H
+
O
3+O
2 -·→O
3 -·+O
2
O
3 -·+H
+→HO
3·
HO
3·→HO·+O
2·
3) active material hydroxyl radical free radical and nitrogen oxides in effluent react:
HO·+NO→HONO
HO·+HONO→NO
2+H
2O
HO·+NO
2→HNO
3
HO·+HONO→HNO
3+H·
HNO
3+OH
-→NO
3 -+HO
2
B, hydrogen peroxide oxidation reactions steps:
1) hydrogen peroxide is excited, and react generation active material:
H
2O
2→2·OH
H
2O
2+·OH→HO
2·+H
2O
2) hydrogen peroxide and nitric oxide, nitrogen dioxide generation oxidation reaction under normal temperature:
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) ozone activates hydrogen peroxide:
4) active material hydroxyl radical free radical and nitrogen oxides in effluent react:
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
Alkaline slurry+2HNO
2→ nitrite+2H
2o
Alkaline slurry+HNO
3→ nitrate+2H
2o
Nitrite+O
2→ nitrate
5) optionally, in alkaline slurry, 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:
Wherein, hydrogen peroxide oxidation reactions steps 4) in oxygen sources in three parts: a part is the oxygen contained in former flue gas, a part is the oxygen that the hydrogen peroxide of non-provocative reaction generates under hydrogen peroxide decomposition catalyst effect, and a part is the oxygen being together delivered to the residue unreacted source of the gas of flue gas desulfurization and denitrification equipment in ozone supply apparatus with the ozone generated in addition.
In flue gas desulfurization and denitrification integrated apparatus of the present invention, in ozone steam oxidation reaction layer, flue-gas temperature can be 50 ~ 80 DEG C, is preferably 60 ~ 70 DEG C; Dust content can be 30 ~ 50mg/Nm
3, be preferably 35 ~ 45mg/Nm
3; Relative humidity can more than 30%, preferably greater than 40%; Flue gas moisture content can be 10% ~ 15%, is preferably 12% ~ 13%.Under the described conditions, ozone decomposed is slow, in addition spraying layer slurries are that alkalescence provides hydroxide ion, humidity, temperature and hydroxide ion content are suitable all especially decomposites more hydroxyl radical free radical, and hydroxyl radical free radical is the material stronger than ozone oxidation performance, faster oxidation of nitric oxide can be become nitrogen dioxide, thus save ozone usage.Further, the reaction of nitrogen oxides in hydroxyl radical free radical and flue gas generates nitric acid and nitrous acid.
In flue gas desulfurization and denitrification integrated apparatus of the present invention, in hydrogen peroxide spraying oxidation reaction layer, flue-gas temperature can be 40 ~ 70 DEG C, is preferably 50 ~ 60 DEG C; Flue gas moisture content can be 10% ~ 13%, is preferably 11% ~ 12%; Relative humidity can be 30% ~ 40%, is preferably 35% ~ 38%.Under the described conditions, hydrogen peroxide can be inspired more active material hydroxyl radical free radical (OH and O
2h).Active material hydroxyl radical free radical and nitric oxide production reaction speed are 300% of hydrogen peroxide and nitric oxide reaction speed, can accelerate nitric oxide production oxidation, improve oxidation and denitration efficiency.Optionally, flue gas desulfurization and denitrification equipment of the present invention is also provided with other ozone steam oxidation reaction layer and hydrogen peroxide spraying oxidation reaction layer, and its quantity has no particular limits, depending on oxidization condition.
Flue gas desulfurization and denitrification equipment of the present invention also comprises and absorbs spray district, and it for adopting sulfur dioxide in alkaline slurry wet absorption flue gas and nitrogen oxide, and forms absorption product.Wherein, the key reaction principle of nitrogen oxide wet absorption has described above in hydrogen peroxide oxidation reactions steps to be mentioned, the key reaction principle of sulfur dioxide wet absorption is as follows.
C, sulfur dioxide wet absorption step:
Alkaline slurry+SO
2→ sulphite+H
2o
Sulphite+H
2o+SO
2→ bisulfites
Sulphite+1/2O
2→ sulfate
Wherein, above-mentioned oxygen sources and step 4 in aforementioned hydrogen peroxide oxidation step) oxygen sources identical.
In the absorption spray district of flue gas desulfurization and denitrification equipment of the present invention, calcium method, magnesium processes, ammonia process, sodium-hydroxide method or Dual alkali are preferably adopted to the wet absorption of sulfur dioxide in flue gas and nitrogen oxide, more preferably adopts wet-type magnesium method or wet-type calcium.Correspondingly, the alkaline slurry that absorption spray district of the present invention uses comprises basic component, and it is selected from: oxide, as magnesia, calcium oxide etc.; Hydroxide, as NaOH, magnesium hydroxide, calcium hydroxide etc.; Ammonia, and any combination of described material, be preferably any combination of magnesia, calcium oxide, magnesium hydroxide, calcium hydroxide or described material.The spray district that absorbs of the present invention preferably includes at least one and is positioned at absorption spraying layer below ozone steam oxidation reaction floor and hydrogen peroxide spraying oxidation reaction floor, its except can wet absorption major part sulfur dioxide except, the part dust in flue gas can also be removed, avoid dust directly to enter ozone steam oxidation reaction layer and hydrogen peroxide spraying oxidation reaction layer, affect the oxidation activity of active material hydroxyl radical free radical.More preferably, described absorption spray district comprises at least three and absorbs spraying layer, and described three absorption spraying layers do not adjoin each other, and is separated by described ozone steam oxidation reaction layer and hydrogen peroxide spraying oxidation reaction interlayer.Wherein, at least one being simultaneously positioned at below ozone steam oxidation reaction layer and hydrogen peroxide spraying oxidation reaction layer absorbs spraying layer, and it is except except wet absorption major part sulfur dioxide, can removing the part dust in flue gas.
According to an embodiment of the invention, described absorption spray district comprises the first absorption spraying layer, second from the bottom to top successively and absorbs spraying layer and the 3rd absorption spraying layer; Ozone steam oxidation reaction layer is arranged on the first absorption spraying layer and second and absorbs between spraying layer; Hydrogen peroxide spraying oxidation reaction layer is arranged on the second absorption spraying layer and the 3rd and absorbs between spraying layer.In this embodiment, ozone in ozone steam oxidation reaction layer can enter hydrogen peroxide spraying oxidation reaction layer with desulphurization denitration flue gas adverse current, this part ozone also can as the activator of hydrogen peroxide, thus excite hydrogen peroxide to produce more active material hydroxyl radical free radical.Preferably, ozone steam oxidation reaction layer is located at the first absorption spraying layer and second in flue gas desulfurization and denitrification equipment and absorbs between spraying layer, and distance first absorbs spraying layer 0.5 ~ 1.5m, is preferably the position of 0.7 ~ 1.0m; Oxidation reaction of being sprayed by hydrogen peroxide layer is located at the second absorption spraying layer and the 3rd in flue gas desulfurization and denitrification equipment and absorbs between spraying layer, and distance the 3rd absorbs spraying layer 1.0 ~ 2.2m, is preferably 1.5 ~ 2.0m, distance second absorbs spraying layer 0.8 ~ 1.8m, is preferably the position of 1.0 ~ 1.5m.According to a specific embodiment of the present invention, in flue gas denitrification equipment, ground floor spraying layer and the second spacing absorbed between spraying layer are 1.5 ~ 3.5m, are preferably 1.8 ~ 2.5m; In flue gas denitrification equipment, second layer spraying layer and the 3rd spacing absorbed between spraying layer are increased to 2.8m ~ 3.5m by 1.8 original ~ 2.5m, are preferably 2.8 ~ 3.0m.
According to another embodiment of the present invention, described absorption spray district comprises the first absorption spraying layer, second from the bottom to top successively and absorbs spraying layer and the 3rd absorption spraying layer; Hydrogen peroxide spraying oxidation reaction layer is arranged on the first absorption spraying layer and second and absorbs between spraying layer; Ozone steam oxidation reaction layer is arranged on the second absorption spraying layer and the 3rd and absorbs between spraying layer.In this embodiment, the ozone in ozone steam oxidation reaction layer sprays into hydrogen peroxide spraying oxidation reaction layer downwards, and this part ozone can as the activator of hydrogen peroxide, thus excite hydrogen peroxide to produce more active material hydroxyl radical free radical equally.Optionally, of the present invention absorption sprays the absorption spraying layer that district is also provided with other, and its quantity is depending on sulfur dioxide in flue gas and amount of nitrogen oxides.Preferably, oxidation reaction of being sprayed by hydrogen peroxide layer is located at the first absorption spraying layer and second in flue gas desulfurization and denitrification equipment and absorbs between spraying layer, and distance first absorbs spraying layer 0.5 ~ 1.5m, is preferably the position of 0.7 ~ 1.0m; Ozone steam oxidation reaction layer being located at the second absorption spraying layer and the 3rd in flue gas desulfurization and denitrification equipment absorbs between spraying layer, and distance the 3rd absorbs spraying layer 1.0 ~ 2.2m, is preferably 1.5 ~ 2.0m, distance second absorbs spraying layer 0.8 ~ 1.8m, is preferably the position of 1.0 ~ 1.5m.According to a specific embodiment of the present invention, in flue gas denitrification equipment, ground floor spraying layer and the second spacing absorbed between spraying layer are 1.5 ~ 3.5m, are preferably 1.8 ~ 2.5m; In flue gas denitrification equipment, second layer spraying layer and the 3rd spacing absorbed between spraying layer are 2.5m ~ 3.5m, are preferably 2.8 ~ 3.2m.
Flue gas desulfurization and denitrification equipment of the present invention also comprises slurries memory block, for supplying alkaline slurry to absorption spray district, and receives the absorption product in self-absorption spray district.According to an embodiment of the invention, alkaline slurry in slurries memory block is delivered to absorption spray district by circulating pump through alkaline slurry transfer pipeline, after sulphite, sulfate, nitrite and the nitrate condensation that wet absorption is formed, the weight against self falls into the slurries memory block of flue gas desulfurization and denitrification equipment.According to an embodiment of the invention, in the alkaline slurry 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 alkaline slurry, also hydrogen peroxide decomposition catalyst can not be added.
Ozone supply apparatus of the present invention, it is for ozone steam oxidation reaction layer ozone supply.Be difficult to store, usual formed in-situ onsite application because ozone is easy to decompose.According to an embodiment of the invention, ozone supply apparatus comprises ozone generator.The type of ozone generator has no particular limits, can use well known in the art those.In ozone generator, the oxygen molecule in source of the gas is converted into ozone molecule through physics and/or chemical reaction.The source of the gas of ozone generator can be selected from liquid oxygen, gaseous state oxygen or air-source, is preferably liquid oxygen.As the liquid oxygen of ozone generator source of the gas, its purity is preferably more than 90%, is more preferably 99.5%.Ozone concentration in the product (also can be called aliment) of ozone generator is preferably 2wt% ~ 12wt%, is more preferably 5wt% ~ 10wt%.According to an embodiment of the invention, the ozone in ozone supply apparatus is delivered to ozone steam oxidation reaction layer by ozone transfer pipeline.Quantity and the arrangement of ozone transfer pipeline have no particular limits, and can use circuit design well known in the art.
Hydrogen peroxide supply arrangement of the present invention, 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.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 integrated apparatus of the present invention also comprises dust arrester, and it is positioned at flue gas and enters optional position before flue gas desulfurization and denitrification 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 integrated apparatus of the present invention also comprises demister, and it is positioned at and absorbs above spray 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.
< flue gas desulfurization and denitrification integral method >
Utilize said apparatus of the present invention to carry out the method for flue gas and desulfurizing and denitrifying, comprise the steps: flue gas oxidation step, wet absorption step, alkaline slurry supplying step, ozone supply step and hydrogen peroxide supplying step.Optionally, method of the present invention also comprises dust removal step and demist step.
Flue gas oxidation step of the present invention is in ozone steam oxidation reaction layer and hydrogen peroxide spraying oxidation reaction layer, utilizes the lower nitrogen oxides in ozone and hydrogen peroxide synergistic oxidation flue gas, and forms higher nitrogen oxides.Preferably, flue gas oxidation step of the present invention comprises: in ozone steam oxidation reaction layer, goes out ozone by ozone atomization sprinkler part Jet with downward flow direction; 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 ozone and hydrogen peroxide.Ozone and hydrogen peroxide synergistic oxidation principle described above.According to an embodiment of the invention, described flue gas oxidation step comprises makes flue gas from the bottom to top successively by ozone steam oxidation reaction layer and hydrogen peroxide spraying oxidation reaction layer.In this embodiment, the unreacted ozone that ozone steam oxidation reaction layer ejects rises with flue gas and enters hydrogen peroxide spraying oxidation reaction layer, activates hydrogen peroxide further.According to another embodiment of the present invention, described flue gas oxidation step comprises makes flue gas from the bottom to top successively by hydrogen peroxide spraying oxidation reaction layer and ozone steam oxidation reaction layer.In this embodiment, the unreacted ozone that ozone steam oxidation reaction layer ejects enters hydrogen peroxide spraying oxidation reaction layer downwards, activates hydrogen peroxide further.Optionally, flue gas oxidation step of the present invention also comprises makes flue gas by other ozone steam oxidation reaction layer and hydrogen peroxide spraying oxidation reaction layer, and its quantity has no particular limits, depending on oxidization condition.The process conditions of ozone steam oxidation reaction layer, the process conditions of hydrogen peroxide spraying oxidation reaction layer as previously mentioned, repeat no more here.
Wet absorption step of the present invention is adopt sulfur dioxide in alkaline slurry wet absorption flue gas and nitrogen oxide, and forms absorption product.Described wet absorption step preferably adopts calcium method, magnesium processes, ammonia process, sodium-hydroxide method or Dual alkali, more preferably adopts wet-type magnesium method or wet-type calcium.Correspondingly, the alkaline slurry that wet absorption step of the present invention uses comprises basic component, and it is selected from: oxide, as magnesia, calcium oxide etc.; Hydroxide, as NaOH, magnesium hydroxide, calcium hydroxide etc.; Ammonia, and any combination of described material, be preferably any combination of magnesia, calcium oxide, magnesium hydroxide, calcium hydroxide or described material.
According to an embodiment of the invention, described wet absorption step comprises makes flue gas absorb spraying layer, ozone steam oxidation reaction layer, the second absorption spraying layer, hydrogen peroxide spraying oxidation reaction layer and the 3rd absorption spraying layer by first successively from the bottom to top.
According to another embodiment of the present invention, described wet absorption step comprises makes flue gas absorb spraying layer, hydrogen peroxide spraying oxidation reaction layer, the second absorption spraying layer, ozone steam oxidation reaction layer and the 3rd absorption spraying layer by first successively from the bottom to top.
Optionally, wet absorption step of the present invention also comprises the absorption spraying layer making flue gas by other, and its quantity is depending on sulfur dioxide in flue gas and amount of nitrogen oxides.After sulphite, sulfate, nitrite and the nitrate condensation that wet absorption step is formed, the weight against self falls into the slurries memory block of flue gas desulfurization and denitrification equipment.
Alkaline slurry supplying step of the present invention is supply alkaline slurry by slurries memory block to absorption spray district.According to an embodiment of the invention, the alkaline slurry in slurries memory block is delivered to absorption spray district by circulating pump through alkaline slurry transfer pipeline.According to an embodiment of the invention, in the alkaline slurry 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 alkaline slurry, also hydrogen peroxide decomposition catalyst can not be added.
Ozone supply step of the present invention is to ozone steam oxidation reaction layer ozone supply by ozone supply apparatus.According to an embodiment of the invention, in ozone generator, generate ozone by source of the gas, and by ozone transfer pipeline, generated ozone is delivered to ozone steam oxidation reaction layer.The source of the gas of ozone generator is selected from liquid oxygen, gaseous state oxygen or air-source, is preferably liquid oxygen.As the liquid oxygen of ozone generator source of the gas, its purity is preferably 99.5%.The ozone concentration that ozone generator generates, for being preferably 2wt% ~ 12wt%, is more preferably 5wt% ~ 10wt%.
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%.
Optionally, method of the present invention also comprises dust removal step, before entering flue gas desulfurization and denitrification equipment at flue gas, remove the dust carried secretly in flue gas.The process conditions of dust removal step have no particular limits, and can use dust collecting process known in the art.
Optionally, method of the present invention also comprises demist step, 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.The process conditions of demist step have no particular limits, and can use demist technique known in the art.
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.The desulfurizing agent adopted due to comparative example and the embodiment of the present invention is different, thus only carries out cost accounting to denitrfying agent.
comparative example 1
Comparative example 1 is a kind of existing ozone oxidation and simultaneous desulfurization denitrating technique, and its device schematic diagram as shown in Figure 1.This technological process is:
A, flue gas in deduster (not shown) after dedusting in air inlet flue 11 with the O that generates in ozone generator 12
3mixing, obtains mist through pre-oxidation;
B, the mist obtained through pre-oxidation enter desulphurization denitration tower 13 from the bottom of desulphurization denitration tower 13, absorbing liquid industrial ammonia is sprayed into and mist counter current contacting from desulphurization denitration tower 13 top by desulphurization denitration circulating pump 15, realize flue gas desulfurization and denitrification, the flue gas after denitration is discharged from flue 14 of giving vent to anger.
Main technologic parameters refers to table 1.According to O
3with NO
xmol ratio is 1.2, and reaching efficiency described in table needs to remove NO
x110.4kg/h, the operating cost 1635.02 yuan/h of the power consumption aspect of increase.
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 | Average inlet sulfur dioxide concentration | mg/m 3 | 1500 |
| 4 | Average inlet nitrous oxides concentration | mg/m 3 | 450 |
| 5 | O 3With NO XMol ratio | O 3/NO X | 1.2 |
| 6 | Oxidization time | s | 0.5 |
| 7 | Average outlet sulfur dioxide concentration | mg/m 3 | 102 |
| 8 | Average outlet nitrous oxides concentration | mg/m 3 | 105 |
| 9 | Most high desulfurization efficiency | ％ | 93.2 |
| 10 | The highest denitration efficiency | ％ | 76.6 |
comparative example 2
Comparative example 2 is a kind of existing hydrogen peroxide oxidation simultaneous SO_2 and NO removal technique, and its device schematic diagram as shown in Figure 2.This technological process is:
H in a, Hydrogen peroxide storage 21
2o
2liquid adds in Catalytic Decomposition of Hydrogen Peroxide device 24 the hydrogen peroxide shower nozzle 23, H be arranged in above catalyst by syringe pump 22
2o
2liquid sprays and the catalyst reaction Catalytic Decomposition of Hydrogen Peroxide device 24 from hydrogen peroxide shower nozzle 23, produces active material;
The air-flow that b, the active material produced in Catalytic Decomposition of Hydrogen Peroxide device 24 blast with air blast 25 enters flue by active material shower nozzle 26, antioxidant nitroxide in flue, last and SO
2in desulfurizing tower, ammonia absorption forms nitrate and sulfate.
Main technologic parameters refers to table 2.According to H
2o
2with NO
xmol ratio is 2.2, and reaching efficiency described in table needs to remove NO
x103.04kg/h, expends operating cost 934.23 yuan/h.
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 | Average inlet sulfur dioxide concentration | mg/m 3 | 1500 |
| 4 | Average inlet nitrous oxides concentration | mg/m 3 | 450 |
| 5 | H 2O 2With NO XMol ratio | H 2O 2/NO X | 2.2 |
| 6 | Oxidization time | s | 0.5 |
| 7 | Average outlet sulfur dioxide concentration | mg/m 3 | 95 |
| 8 | Average outlet nitrous oxides concentration | mg/m 3 | 128 |
| 9 | Most high desulfurization efficiency | ％ | 93.7 |
| 10 | The highest denitration efficiency | ％ | 71.5 |
comparative example 3
Comparative example 3 is a kind of existing ozone and hydrogen peroxide synergistic oxidation simultaneous SO_2 and NO removal technique, and its device schematic diagram as shown in Figure 3.This technological process is:
A, flue gas enter from the smoke inlet 31 of oxidation reactor, a venturi aditus laryngis 32 is established below smoke inlet 31, hydrogenperoxide steam generator is sprayed in the middle of venturi aditus laryngis 32 by hydrogen peroxide atomizer 33, oxidation reactor interlude establishes ozone injection pipe network 34, spray into ozone, the back segment of oxidation reactor is provided with static mixer 35, for cutting steam, produces turbulent flow, allows the various components in air-flow mix;
Flue gas after b, oxidation reaction is discharged from exhanst gas outlet 36, enters wet desulfuration tower, utilizes the nitrogen oxide in lime slurry absorption flue gas and sulfur dioxide.
The main technologic parameters of comparative example 3 refers to table 3.According to H
2o
2with NO
xmol ratio is 1, O
3with NO
xmol ratio is 0.5, and reaching efficiency described in table needs to remove NO
x112kg/h, totally need expend operating cost 1106.7 yuan/h.
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 | Average inlet sulfur dioxide concentration | mg/m 3 | 1500 |
| 4 | Average inlet nitrous oxides concentration | mg/m 3 | 450 |
| 5 | O 3With NO XMol ratio | O 3/NO X | 0.5 |
| 6 | H 2O 2With NO XMol ratio | H 2O 2/NO X | 1 |
| 7 | Oxidization time | s | 0.5 |
| 8 | Average outlet sulfur dioxide concentration | mg/m 3 | 84 |
| 9 | Average outlet nitrous oxides concentration | mg/m 3 | 100 |
| 10 | Most high desulfurization efficiency | ％ | 94.4 |
| 11 | The highest denitration efficiency | ％ | 77.7 |
The raw material used in following examples of the present invention is described as follows:
Alkaline slurry is magnesium hydroxide slurry;
H
2o
2solution is aqueous hydrogen peroxide solution, and concentration of hydrogen peroxide is wherein 27.5wt%;
O
3the ozone concentration of product is 10wt%;
Hydrogen peroxide decomposition catalyst is manganese dioxide.
embodiment 1
Fig. 4-1 shows the device schematic diagram of the embodiment of the present invention 1.As seen from the figure, flue gas desulfurization and denitrification integrated apparatus of the present invention comprises flue gas desulfurization and denitrification equipment 41, ozone supply apparatus 45 and hydrogen peroxide supply arrangement 48.Flue gas desulfurization and denitrification equipment 41 comprises ozone steam oxidation reaction floor 44, hydrogen peroxide spraying oxidation reaction floor 47, absorbs spray district 42 and slurries memory block 410, wherein, ozone steam oxidation reaction floor 44 and hydrogen peroxide spraying oxidation reaction floor 47 are all located at and absorb in spray district 42.Absorb spray district 42 and comprise the first absorption spraying layer 413, second absorption spraying layer 414 and the 3rd absorption spraying layer 415.Hydrogen peroxide spraying oxidation reaction layer 47 absorbs spraying layer 413 and second first and absorbs between spraying layer 414.Ozone steam oxidation reaction layer 44 absorbs spraying layer 414 and the 3rd second and absorbs between spraying layer 415.It is 1.0m that hydrogen peroxide spraying oxidation reaction layer 47 absorbs spraying layer 413 apart from first; It is 1.6m that ozone steam oxidation reaction layer 44 absorbs spraying layer 415 apart from the 3rd, and it is 1.5m that distance second absorbs spraying layer 414.Store alkaline slurry in slurries memory block 410, adding in described alkaline slurry has hydrogen peroxide decomposition catalyst 412.Alkaline slurry in slurries memory block 410 is delivered to the first absorption spraying layer 413, second by desulphurization denitration circulating pump 416 through alkaline slurry transfer pipeline and absorbs spraying layer 414 and the 3rd absorption spraying layer 415.Ozone supply apparatus 45 is connected with ozone steam oxidation reaction layer 44 through ozone transfer pipeline 46.Hydrogen peroxide supply arrangement 48 is connected through hydrogen peroxide transfer pipeline and hydrogen peroxide oxidation reaction layer 47 of spraying by syringe pump 49.
The technological process of the embodiment of the present invention 1 is:
Alkaline slurry containing hydrogen peroxide decomposition catalyst in the slurries memory block 410 of a, flue gas desulfurization and denitrification equipment 41, is delivered to through alkaline slurry transfer pipeline the first absorption spraying layer 413, the second absorption spraying layer 414 and the 3rd absorbing spray district 42 by desulphurization denitration circulating pump 416 and absorbs spraying layer 415 and Jet with downward flow direction;
B, flue gas from coal-burning boiler or sintering machine, enter inner also rising of flue gas desulfurization and denitrification equipment 41 from the gas approach 411 of flue gas desulfurization and denitrification equipment 41 and enter absorption spray district 42, flue gas absorbs the alkaline slurry counter current contacting generation neutralization reaction that spraying layer 413 ejects in uphill process with first, the most of SO in removing flue gas
2and dust, obtain the absorption product containing sulphite, and form the flue gas of preliminary purification;
H in c, hydrogen peroxide supply arrangement 48
2o
2solution, hydrogen peroxide spraying oxidation reaction layer 47 is delivered to and Jet with downward flow direction through hydrogen peroxide transfer pipeline by syringe pump 49, the flue gas of preliminary purification is sprayed with hydrogen peroxide the hydrogen peroxide counter current contacting generation oxidation reaction that oxidation reaction layer 47 ejects in uphill process, the part NO in oxidation flue gas
x, form hydrogen peroxide oxidation flue gas, the unreacted hydrogen peroxide that hydrogen peroxide spraying oxidation reaction layer 47 ejects falls into slurries memory block 410, contacts produce water and oxygen with hydrogen peroxide decomposition catalyst;
D, hydrogen peroxide oxidation flue gas continue to rise, the alkaline slurry counter current contacting that spraying layer 414 ejects is absorbed with second, nitrogen oxide in hydrogen peroxide oxidation flue gas and the sulfur dioxide do not eliminated and alkaline slurry generation neutralization reaction, obtain the absorption product containing nitrite, nitrate and sulphite, and form hydrogen peroxide oxidation desulphurization denitration flue gas;
The O that e, ozone supply apparatus 45 produce
3product is delivered to ozone steam oxidation reaction layer 44 Jet with downward flow direction after pressurizeing in ozone transfer pipeline 46 course of conveying, hydrogen peroxide oxidation desulphurization denitration flue gas in uphill process with O
3counter current contacting generation oxidation reaction, the NO further in oxidation flue gas
x, form ozone oxidation flue gas, the unreacted O that ozone steam oxidation reaction layer 44 ejects
3enter hydrogen peroxide spraying oxidation reaction layer 47 downwards, activate H further
2o
2;
F, ozone oxidation flue gas continue to rise, the alkaline slurry counter current contacting that spraying layer 415 ejects is absorbed with the 3rd, nitrogen oxide in ozone oxidation flue gas and the sulfur dioxide do not eliminated and alkaline slurry generation neutralization reaction, obtain the absorption product containing nitrite, nitrate and sulphite, and form ozone oxidation desulphurization denitration flue gas;
The sulphite that g, whole oxidation sweetening denitrification process generate, sulfate, nitrite and nitrate fall into the slurries memory block 410 of flue gas desulfurization and denitrification equipment 41, and sulphite, nitrite and oxygen generation oxidation reaction generate sulfate, nitrate.
Main technologic parameters refers to table 4.According to H
2o
2with NO
xmol ratio is 0.7, O
3with NO
xmol ratio is 0.4, and reaching efficiency described in table needs to remove NO
x114.56kg/h, totally need expend operating cost 858.38 yuan/h.
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 | Average inlet sulfur dioxide concentration | mg/m 3 | 1500 |
| 4 | Average inlet nitrous oxides concentration | mg/m 3 | 450 |
| 5 | O 3With NO XMol ratio | O 3/NO X | 0.4 |
| 6 | H 2O 2With NO XMol ratio | H 2O 2/NO X | 0.7 |
| 7 | Oxidization time | s | 0.5 |
| 8 | Average outlet sulfur dioxide concentration | mg/m 3 | 64 |
| 9 | Average outlet nitrous oxides concentration | mg/m 3 | 92 |
| 10 | Most high desulfurization efficiency | ％ | 95.7 |
| 11 | The highest denitration efficiency | ％ | 79.5 |
embodiment 2
Fig. 4-2 shows the device schematic diagram of the embodiment of the present invention 2.As seen from the figure, flue gas desulfurization and denitrification integrated apparatus of the present invention comprises flue gas desulfurization and denitrification equipment 41, ozone supply apparatus 45 and hydrogen peroxide supply arrangement 48.Flue gas desulfurization and denitrification equipment 41 comprises ozone steam oxidation reaction floor 44, hydrogen peroxide spraying oxidation reaction floor 47, absorbs spray district 42 and slurries memory block 410, wherein, ozone steam oxidation reaction floor 44 and hydrogen peroxide spraying oxidation reaction floor 47 are all located at and absorb in spray district 42.Absorb spray district 42 and comprise the first absorption spraying layer 413, second absorption spraying layer 414 and the 3rd absorption spraying layer 415.Ozone steam oxidation reaction layer 44 absorbs spraying layer 413 and second first and absorbs between spraying layer 414.Hydrogen peroxide spraying oxidation reaction layer 47 absorbs spraying layer 414 and the 3rd second and absorbs between spraying layer 415.It is 1.0m that ozone steam oxidation reaction layer 44 absorbs spraying layer 413 apart from first; It is 1.6m that hydrogen peroxide spraying oxidation reaction layer 47 absorbs spraying layer 415 apart from the 3rd, and it is 1.5m that distance second absorbs spraying layer 414.Store alkaline slurry in slurries memory block 410, adding in described alkaline slurry has hydrogen peroxide decomposition catalyst 412.Alkaline slurry in slurries memory block 410 is delivered to the first absorption spraying layer 413, second by desulphurization denitration circulating pump 416 through alkaline slurry transfer pipeline and absorbs spraying layer 414 and the 3rd absorption spraying layer 415.Ozone supply apparatus 45 is connected with ozone steam oxidation reaction layer 44 through ozone transfer pipeline 46.Hydrogen peroxide supply arrangement 48 is connected through hydrogen peroxide transfer pipeline and hydrogen peroxide oxidation reaction layer 47 of spraying by syringe pump 49.
The technological process of the embodiment of the present invention 2 is:
Alkaline slurry containing hydrogen peroxide decomposition catalyst in the slurries memory block 410 of a, flue gas desulfurization and denitrification equipment 41, is delivered to through alkaline slurry transfer pipeline the first absorption spraying layer 413, the second absorption spraying layer 414 and the 3rd absorbing spray district 42 by desulphurization denitration circulating pump 416 and absorbs spraying layer 415 and Jet with downward flow direction;
B, flue gas from coal-burning boiler or sintering machine, enter inner also rising of flue gas desulfurization and denitrification equipment 41 from the gas approach 411 of flue gas desulfurization and denitrification equipment 41 and enter absorption spray district 42, flue gas absorbs the alkaline slurry counter current contacting generation neutralization reaction that spraying layer 413 ejects in uphill process with first, the most of SO in removing flue gas
2and dust, obtain the absorption product containing sulphite, and form the flue gas of preliminary purification;
The O that c, ozone supply apparatus 45 produce
3product is delivered to ozone steam oxidation reaction layer 44 Jet with downward flow direction after pressurizeing in ozone transfer pipeline 46 course of conveying, the flue gas of preliminary purification in uphill process with O
3counter current contacting generation oxidation reaction, the part NO in oxidation flue gas
x, form ozone oxidation flue gas;
D, ozone oxidation flue gas continue to rise, the alkaline slurry counter current contacting that spraying layer 414 ejects is absorbed with second, nitrogen oxide in ozone oxidation flue gas and the sulfur dioxide do not eliminated and alkaline slurry generation neutralization reaction, obtain the absorption product containing nitrite, nitrate and sulphite, and form ozone oxidation desulphurization denitration flue gas;
H in e, hydrogen peroxide supply arrangement 48
2o
2solution, is delivered to hydrogen peroxide spraying oxidation reaction layer 47 and Jet with downward flow direction by syringe pump 49 through hydrogen peroxide transfer pipeline, the unreacted O that ozone steam oxidation reaction layer 44 ejects
3enter hydrogen peroxide spraying oxidation reaction layer 47 with ozone oxidation desulphurization denitration flue gas, activate H further
2o
2, ozone oxidation desulphurization denitration flue gas is sprayed with hydrogen peroxide the hydrogen peroxide counter current contacting generation oxidation reaction that oxidation reaction layer 47 ejects in uphill process, the NO further in oxidation flue gas
x, form hydrogen peroxide oxidation flue gas, the unreacted hydrogen peroxide that hydrogen peroxide spraying oxidation reaction layer 47 ejects falls into slurries memory block 410, contacts produce water and oxygen with hydrogen peroxide decomposition catalyst;
F, hydrogen peroxide oxidation flue gas continue to rise, the alkaline slurry counter current contacting that spraying layer 415 ejects is absorbed with the 3rd, nitrogen oxide in hydrogen peroxide oxidation flue gas and the sulfur dioxide do not eliminated and alkaline slurry generation neutralization reaction, obtain the absorption product containing NO3-N and NO2-N, and form hydrogen peroxide oxidation desulphurization denitration flue gas;
The sulphite that g, whole oxidation sweetening denitrification process generate, sulfate, nitrite and nitrate fall into the slurries memory block 410 of flue gas desulfurization and denitrification equipment 41, and sulphite, nitrite and oxygen generation oxidation reaction generate sulfate, nitrate.
Main technologic parameters refers to table 5.According to H
2o
2with NO
xmol ratio is 0.5, O
3with NO
xmol ratio is 0.3, and reaching efficiency described in table needs to remove NO
x130.24kg/h, totally need expend operating cost 718.92 yuan/h.
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 | Average inlet sulfur dioxide concentration | mg/m 3 | 1500 |
| 4 | Average inlet nitrous oxides concentration | mg/m 3 | 450 |
| 5 | O 3With NO XMol ratio | O 3/NO X | 0.3 |
| 6 | H 2O 2With NO XMol ratio | H 2O 2/NO X | 0.5 |
| 7 | Oxidization time | s | 0.5 |
| 8 | Average outlet sulfur dioxide concentration | mg/m 3 | 17 |
| 9 | Average outlet nitrous oxides concentration | mg/m 3 | 43 |
| 10 | Most high desulfurization efficiency | ％ | 98.9 |
| 11 | The highest denitration efficiency | ％ | 90.4 |
By finding out the contrast of embodiment of the present invention 1-2 and comparative example 1-3, ozone of the present invention and hydrogen peroxide synergistic oxidation can reach more than 98% in conjunction with the flue gas desulfurization and denitrification integrated apparatus of wet absorption and the desulfuration efficiency of method, denitration efficiency can reach more than 90%, O
3with NO
xmol ratio, H
2o
2with NO
xmol ratio is lower, has saved the ozone usage of nearly 50%, and overall operation cost is significantly less than makes oxidant, separately with H with ozone separately
2o
2for the traditional handicraft that oxidant, ozone are combined with hydrogen peroxide.Therefore, denitrification apparatus of the present invention and method can reach environmental emission standard the strictest at present, again reduce initial cost and denitrating system operating cost while realizing minimum discharge.
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. ozone and hydrogen peroxide synergistic oxidation are in conjunction with a flue gas desulfurization and denitrification integrated apparatus for wet absorption, it is characterized in that, comprising:
Flue gas desulfurization and denitrification equipment, its inside is provided with:
Ozone steam oxidation reaction layer and hydrogen peroxide spraying oxidation reaction layer, for the lower nitrogen oxides in synergistic oxidation flue gas, and form higher nitrogen oxides;
Absorbing spray district, for adopting sulfur dioxide in alkaline slurry wet absorption flue gas and nitrogen oxide, and forming absorption product; With
Slurries memory block, for supplying alkaline slurry to absorption spray district, and receives the absorption product in self-absorption spray district;
Ozone supply apparatus, for ozone steam oxidation reaction layer ozone supply; With
Hydrogen peroxide supply arrangement, for supplying hydrogen peroxide to hydrogen peroxide spraying oxidation reaction layer;
Wherein, described ozone steam oxidation reaction floor and hydrogen peroxide spraying oxidation reaction floor are all arranged in described absorption spray district.
2. flue gas desulfurization and denitrification integrated apparatus according to claim 1, it is characterized in that, described absorption spray district comprises at least three and absorbs spraying layer, and described at least three absorption spraying layers do not adjoin each other, and separated by described ozone steam oxidation reaction layer and hydrogen peroxide spraying oxidation reaction interlayer.
3. flue gas desulfurization and denitrification integrated apparatus according to claim 2, is characterized in that, described absorption spray district comprises the first absorption spraying layer, second from the bottom to top successively and absorbs spraying layer and the 3rd absorption spraying layer; Ozone steam oxidation reaction layer is arranged on the first absorption spraying layer and second and absorbs between spraying layer; Hydrogen peroxide spraying oxidation reaction layer is arranged on the second absorption spraying layer and the 3rd and absorbs between spraying layer.
4. flue gas desulfurization and denitrification integrated apparatus according to claim 3, is characterized in that, described ozone steam oxidation reaction layer distance first absorbs spraying layer 0.5 ~ 1.5m; Described hydrogen peroxide spraying oxidation reaction floor distance second absorbs spray district 0.8 ~ 1.8m, and distance the 3rd absorbs spraying layer 1 ~ 2.2m.
5. flue gas desulfurization and denitrification integrated apparatus according to claim 2, is characterized in that, described absorption spray district comprises the first absorption spraying layer, second from the bottom to top successively and absorbs spraying layer and the 3rd absorption spraying layer; Hydrogen peroxide spraying oxidation reaction layer is arranged on the first absorption spraying layer and second and absorbs between spraying layer; Ozone steam oxidation reaction layer is arranged on the second absorption spraying layer and the 3rd and absorbs between spraying layer.
6. flue gas desulfurization and denitrification integrated apparatus according to claim 5, is characterized in that, described hydrogen peroxide spraying oxidation reaction layer distance first absorbs spraying layer 0.5 ~ 1.5m; Described ozone steam oxidation reaction floor distance second absorbs spray district 0.8 ~ 1.8m, and distance the 3rd absorbs spraying layer 1 ~ 2.2m.
7. utilize the flue gas desulfurization and denitrification integrated apparatus described in any one of claim 1-6 to carry out a method for flue gas and desulfurizing and denitrifying, it is characterized in that, comprise the steps:
Flue gas oxidation step, in ozone steam oxidation reaction layer and hydrogen peroxide spraying oxidation reaction layer, utilizes the lower nitrogen oxides in ozone and hydrogen peroxide synergistic oxidation flue gas, and forms higher nitrogen oxides;
Wet absorption step, adopts the sulfur dioxide in alkaline slurry wet absorption flue gas and nitrogen oxide, and forms absorption product;
Alkaline slurry supplying step, supplies alkaline slurry by slurries memory block to absorption spray district;
Ozone supply step, by ozone supply apparatus to ozone steam oxidation reaction layer ozone supply; With
Hydrogen peroxide supplying step, supplies hydrogen peroxide by hydrogen peroxide supply arrangement to hydrogen peroxide spraying oxidation reaction layer.
8. method according to claim 7, is characterized in that, in described flue gas oxidation step, the process conditions of ozone steam oxidation reaction layer are: flue-gas temperature is 50 ~ 80 DEG C, and dust content is 30 ~ 50mg/Nm
3, relative humidity is greater than 30%, and humidity of flue gas is 10% ~ 15%; The process conditions of hydrogen peroxide spraying oxidation reaction layer are: flue-gas temperature is 40 ~ 70 DEG C, and moisture content is 10% ~ 13%, and relative humidity is 30% ~ 40%.
9. method according to claim 7, is characterized in that, in described flue gas oxidation step, the ozone concentration in the aliment that described ozone supply step provides is 2wt% ~ 12wt%; Concentration of hydrogen peroxide in the aliment that described hydrogen peroxide supplying step provides is 3wt% ~ 35wt%.
10. the method according to any one of claim 7-9, is characterized in that, described alkaline slurry supplying step is also included in described alkaline slurry and adds hydrogen peroxide decomposition catalyst.
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| HK16103111.0A HK1215214A1 (en) | 2015-06-05 | 2016-03-17 | Flue gas desulphurization and denitration integrated device and method |
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| CN106823747A (en) * | 2017-03-08 | 2017-06-13 | 湖南云平环保科技有限公司 | Calcium and magnesium base desulphurization denitration absorbent |
| CN108246085A (en) * | 2018-03-01 | 2018-07-06 | 新疆乾坤环能投资有限公司 | A kind of desulphurization denitration synergistic effect system |
| CN112999844A (en) * | 2021-03-05 | 2021-06-22 | 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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| HK1215214A1 (en) | 2016-08-19 |
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