CN104959010A - Desulphurization and denitration apparatus and method based on ozone - Google Patents
Desulphurization and denitration apparatus and method based on ozone Download PDFInfo
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- CN104959010A CN104959010A CN201510303396.1A CN201510303396A CN104959010A CN 104959010 A CN104959010 A CN 104959010A CN 201510303396 A CN201510303396 A CN 201510303396A CN 104959010 A CN104959010 A CN 104959010A
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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 desulphurization and denitration apparatus and method based on ozone. The apparatus comprises a flue gas desulphurization and denitration device; the interior of the flue gas desulphurization and denitration device is provided with more than two spraying absorption layers and more than one ozone spray reaction and absorption layer, wherein the ozone spray reaction and absorption layer oxidizes low-valency nitrogen oxide in flue gas into high-valency nitrogen oxide, and the spraying absorption layers absorb sulfur dioxide and nitrogen oxide in the flue gas by using an absorbent and allow absorption products to be formed. The desulphurization and denitration apparatus and method provided by the invention are applicable to desulphurization and denitration of NOX-containing flue gas of a coal-fired boiler, a steel sintering machine, a pelletizing machine, an industrial kiln, etc. and can overcome the problems of high operation cost and complex equipment in conventional desulphurization and denitration process for flue gas.
Description
Technical field
The present invention relates to a kind of flue gas desulfurization and denitrification device and method, be specifically related to a kind of desulfuring and denitrifying apparatus based on ozone and method.
Background technology
China is the energy resource consumption big country based on coal, simultaneously Ye Shi iron and steel big producing country.Can produce a large amount of sulfur dioxide, nitrogen oxide, the nuisances such as dust in fire coal and smelting process, wherein sulfur dioxide and nitrogen oxide are the main matter forming acid rain, and to environment, human body, society, economy all can produce huge harmful effect.To SO
2control, technology comparatively ripe is at present lime stone-gypsum, and removal efficiency can reach more than 95%.In addition, the technology such as furnace sorbent injection desulfurization, E-beam absorption is also had.The major technique being applied to denitrating flue gas is SCR (SCR) and SNCR (SNCR).By the end of the year 2008, the denitrating flue gas unit about 50 multiple stage 1957kW altogether put into operation in the whole nation, wherein SCR unit will account for 90.5%.SCR denitration efficiency is high, but equipment investment and operation expense high, expensive catalyst, easy inactivation, because reacting incomplete, the escaping of ammonia that is that cause can cause secondary pollution; Though SNCR invests and operating cost is less, denitration efficiency is lower, does not reach the discharge standard of increasingly stringent.The method reaction of these two kinds of denitrating flue gas all needs higher temperature, larger floor space, larger to existing electric power factory equipment transformation.Along with country is more and more stricter to the requirement of thermal power plant's pollutant emission, simultaneous SO_2 and NO removal has become the development trend of flue gas pollutant control technology.Widely used both at home and abroad is at present wet flue gas desulfurization and NH
3the combination of Selective catalytic reduction technology denitration.The denitrification efficiency of this technology is no doubt high, but investment and operation capital costliness.
Therefore, research and develop a kind of clean energy-saving, efficient stable, reliable desulphurization denitration new technology become the focus of this area research.CN1768902A discloses a kind of denitration method for flue gas, first using the ozone (O as oxidant
3) be injected in flue, the NO in boiler smoke is oxidized into NO soluble in water
2or N
2o
5, then with water or alkali liquid washing flue gas, remove the nitrogen oxide in flue gas.Although this method for oxidizing and denitrating can reach the object removing nitrogen oxide, boiler smoke elder generation and ozone (O
3) carry out base extraction operation again after reaction, namely zoneofoxidation is separated with uptake zone, ozone (O
3) in the cigarette temperature environment more than 130 DEG C and at dustiness 50 ~ 200mg/Nm
3flue gas condition under, very easily to decompose or adsorption of dust loses activity, cause that denitration efficiency reduces, ozone (O
3) consumption is excessive, increases the operating cost of denitrating system.Patent like this also has CN103736373A, CN103933841A, CN 203227412 U etc., is faced with above-mentioned problem equally.
Summary of the invention
In view of this, in order to overcome the deficiency of existing desulphurization denitration technology, the invention provides a kind of desulfuring and denitrifying apparatus based on ozone and method, can effectively reduce ozone (O
3) consumption, reduce costs.In addition, the present invention also provides a kind of desulfuring and denitrifying apparatus based on ozone and method, can improve the efficiency of denitrating flue gas.
The invention provides a kind of desulfuring and denitrifying apparatus based on ozone, comprising:
Flue gas desulfurization and denitrification equipment, its inside is provided with: two-layer above spray-absorption layer, ozone steam reaction more than one deck and absorbed layer, lower nitrogen oxides in flue gas is become the nitrogen oxide of high price by wherein said ozone steam reaction and absorbed layer, sulfur dioxide in described spray-absorption layer employing absorbent absorption flue gas and nitrogen oxide, and form absorption product;
Ozone supply apparatus, for reacting and absorbed layer ozone supply to described ozone steam.
According to device of the present invention, preferably, at least one deck spray-absorption layer in described two-layer above spray-absorption layer is arranged on described ozone steam reaction and the below of absorbed layer, for pretreated fumes to absorb the sulfur dioxide in flue gas; With
At least one deck spray-absorption layer in described two-layer above spray-absorption layer is arranged on described ozone steam reaction and the top of absorbed layer, for absorbing the nitrogen oxide in flue gas.
According to device of the present invention, preferably, arrange ground floor spray-absorption layer, second layer spray-absorption layer and third layer spray-absorption layer from top to bottom at flue gas desulfurization and denitrification device interior, the reaction of described ozone steam and absorbed layer are arranged on ground floor spray-absorption layer, any position between second layer spray-absorption layer and third layer spray-absorption layer.
According to device of the present invention, preferably, described ozone steam reaction and absorbed layer are arranged between ground floor spray-absorption layer and second layer spray-absorption layer, ozone steam reaction and 0.8 ~ 2.8 meter, absorbed layer distance ground floor spray-absorption layer, and 1.0 ~ 2.3 meters, distance second layer spray-absorption layer.
According to device of the present invention, more preferably, described ozone steam reaction and absorbed layer are arranged between ground floor spray-absorption layer and second layer spray-absorption layer, ozone steam reaction and 1.2 ~ 2.0 meters, absorbed layer distance ground floor spray-absorption layer, and 1.3 ~ 1.8 meters, distance second layer spray-absorption layer.
According to device of the present invention, preferably, described ozone steam reaction and absorbed layer are arranged between second layer spray-absorption layer and third layer spray-absorption layer, ozone steam reaction and 0.8 ~ 2.8 meter, absorbed layer distance second layer spray-absorption layer, and 1.0 ~ 2.3 meters, distance third layer spray-absorption layer.
According to device of the present invention, preferably, described device also comprises:
Serum recycle equipment, for receiving the absorption product formed from flue gas desulfurization and denitrification equipment, and will described absorption product be circulated in spray-absorption layer at least partially;
Demister, for carrying out dedusting demist to flue gas, described demister is positioned at the top of whole spray-absorption layer.
The present invention also provides a kind of method utilizing said apparatus to carry out flue gas desulfurization and denitrification, comprises the steps:
Flue gas oxidation step, in ozone steam reaction and absorbed layer, utilizes the lower nitrogen oxides in ozone oxidation flue gas, forms higher nitrogen oxides;
Wet absorption step, the sulfur dioxide in the absorbent utilizing spray-absorption layer to spray absorption flue gas and nitrogen oxide, and form absorption product;
Ozone supply step, is reacted and absorbed layer ozone supply to described ozone steam by ozone supply apparatus.
According to method of the present invention, preferably, in flue gas oxidation step, the process conditions of ozone steam reaction and absorbed layer are: flue-gas temperature is 40 ~ 70 DEG C, and dust content is 30 ~ 50mg/Nm
3, relative humidity is greater than 30%, humidity of flue gas is between 10% ~ 15%.
According to method of the present invention, preferably, in flue gas oxidation step, the flow control of flue gas is being less than 5m/s.
Adopt device and method of the present invention, the sulfur dioxide in flue gas can be removed.In addition, adopt device and method of the present invention, flue gas can also be made simultaneously to carry out oxidation reaction and absorption reaction, the ozone sprayed into, as oxidant, containing under the environment of hydroxide ion, causes chain reaction, accounts for NO in ozone initiation chain reaction flue gas
xthe NO being insoluble in water of main component is converted into NO
2or N
2o
5etc. the nitrogen oxide of high-valence state, then absorbed by water or alkaline matter, complete denitrification process, thus avoid ozone (O
3) be decomposed or lost activity before oxidation flue gas, thus reduce ozone (O
3) consumption.Further, adopt device and method of the present invention, can ensure that oxidation reaction and absorption reaction can react completely, improve denitrification efficiency.
Accompanying drawing explanation
Fig. 1 is the device schematic diagram of the embodiment of the present invention 1.
In figure, l is desulphurization denitration tower, and 2 is ground floor spray-absorption layer, and 3 is second layer spray-absorption layer, 4 is third layer spray-absorption layer, 5 is ozone steam reaction and absorbed layer, and 6 is demister, and 7 is slurries circulating slot in tower, 8 is exhanst gas outlet, 9 is slurry circulating pump, and 10 is the outer slurry pool of tower, and 11 is ozone conveying fan, 12 is ozone generator, 13 is excavationg pump, and 14 is plate and frame filter press, and 15 is desulphurization denitration rear slurry pond, 16 is flue gas accident spraying layer, 17 is flue gas accident spray pump, and 18 is flue gas accident water tank, and 20 is gas approach.
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 equipment." equipment " of the present invention can be still the system set of multiple " equipment ", does not limit to single " equipment ".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 denitration technique 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.
" desulphurization denitration " of the present invention is not sulfur dioxide, the nitrogen oxide that strict restriction only removes in flue gas, and also comprising can the oxidized or material that absorbs containing other in some other common acidic oxide and common flue gas, as mercury, dust etc.
" top " of the present invention, " below ", " from top to bottom " etc. represent that the word of relative position only represents relative position and is in " top " or " below ", can be set directly at " top " or " below ", also can indirectly be arranged on " top " or " below ", be arranged on " top " or " below " namely non-conterminously, as being provided with B layer above A layer, only represent that B layer is above A layer, can be adjacent, also can be non-conterminous, unrestricted.
< desulfuring and denitrifying apparatus >
Desulfuring and denitrifying apparatus of the present invention comprises flue gas desulfurization and denitrification equipment, and wherein flue gas desulfurization and denitrification equipment is preferably desulphurization denitration tower.Be provided with at flue gas desulfurization and denitrification device interior: the spray-absorption layer more than two-layer, ozone steam reaction more than one deck and absorbed layer, lower nitrogen oxides in flue gas is become the nitrogen oxide of high price by wherein said ozone steam reaction and absorbed layer, described spray-absorption layer adopts nitrogen oxide in absorbent dominant absorption flue gas, (absorbent can absorb other materials in flue gas to sulfur dioxide, such as dust etc., but do not do any restriction to whether absorbing other materials), and form absorption product.Optionally, desulfuring and denitrifying apparatus of the present invention also comprises serum recycle equipment, demister, slurries device for transferring, the outer plate filter of tower or vacuum filter, DCS or PLC control appliance.
Flue gas desulfurization and denitrification device interior of the present invention is provided with ozone steam reaction and the absorbed layer of more than one deck, the arranging the number of plies and can determine the requirement of denitrating flue gas according to reality of the reaction of described ozone steam and absorbed layer, preferably one deck ozone steam reacts and absorbed layer.Ozone steam reaction of the present invention and absorbed layer comprise ozone atomizer.By being arranged on the ozone atomizer ejection ozone of this layer, the ozone that lower nitrogen oxides (as NO) in flue gas and ozone steam react and spray in absorbed layer reacts, and becomes the higher nitrogen oxides that easily absorbed by absorbent (as NO after completing oxidation reaction
2, N
2o
5).Ozone steam reaction and the atomizing spray parts that adopt of absorbed layer have no particular limits, can use well known in the art those.As preferably, atomizing spray parts of the present invention are high-voltage-resistant anti-corrosion atomizing spray parts, are more preferably high pressure resistant acid-fast alkali-proof corrosion atomizing spray parts.According to an embodiment of the invention, described atomizing spray parts are preferably high-pressure atomization nozzle, are more preferably stainless steel nozzle.The pressure limit of the ozone sprayed in high-pressure atomization nozzle is preferably 0.8 ~ 0.9MPa, described ozone atomization jet expansion direction can be 60 ~ 120 degree with the angle in flow of flue gas direction, be preferably 80 ~ 100 degree, be more preferably 90 degree, be sprayed in tower coverage for 100% with what ensure ozone ejection pipeline.
The crucial part of the present invention is that the ozone sprayed into is as oxidant, and containing under the environment of hydroxide ion, ozone causes chain reaction, then chain reaction transmission, the hydroxyl radical free radical that generation oxidisability is extremely strong.Hydroxyl radical free radical is as strong oxidizer, and oxidation NO becomes NO
2more higher nitrogen oxides, reacts with water and generates nitric acid and nitrous acid, and the alkali substance reaction in the nitric acid of generation and nitrous acid and slurries generates nitrate, reaches denitration object, and drastically increases the reaction efficiency of ozone, and reduce the consumption of ozone.
The absorbent adopted for spray-absorption layer is for magnesium hydroxide slurry, and its reaction principle is:
(1) magnesium oxide powder is dissolved in water and generates magnesium hydroxide slurry, as absorbent.
(2) sulfur dioxide is absorbed by water and alkali salt.
Mg(OH)
2+H
2SO
3→MgSO
3↓+2H
2O
(3) ozone sprayed into, 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
(4) ozone is in humidity under the appropriate environment with containing hydroxide ion, causes chain reaction.
Chain initiation reaction
O
3+OH
-→HO
2·+O
2·
Chain transfer reaction
HO
2·→O
2 -·+H
+
O
3+O
2 -·→O
3 -·+O
2
O
3 -·+H
+→HO
3·
HO
3·→HO·+O
2
Generate the hydroxyl radical free radical that oxidisability is extremely strong.
(5) hydroxyl radical free radical is as strong oxidizer, oxidation NO.
HO·+NO→HONO
HO·+HONO→NO
2+H
20
HO·+NO
2→HNO
3
HO·+HONO→HNO
3+H·
(6) magnesium sulfite is in slurry pool, is oxidized by oxygen into magnesium sulfate, reaches desulfurization object.
(7) hydroxyl ion of the alkaline matter in the nitric acid generated and nitrous acid and slurries reacts and generates nitrate, reaches denitration object.
HNO
3+OH
-→NO
3 -+HO
2
Flue gas desulfurization and denitrification device interior of the present invention be provided with two-layer more than spray-absorption layer, described spray-absorption layer adopts absorbent to absorb sulfur dioxide, nitrogen oxide in flue gas, and forms absorption product.Absorbent of the present invention can be alkaline slurry, described alkaline slurry can by oxide or hydroxide formulated, one or more being more preferably in calcium oxide, magnesia, sodium oxide molybdena, calcium hydroxide, magnesium hydroxide, NaOH, ammoniacal liquor are formulated, most preferably are magnesia or the formulated slurries of magnesium hydroxide.The number of plies of spray-absorption layer can be determined according to the content of the material to be removed such as nitrogen oxides in effluent, sulfur dioxide.
According to the preferred embodiment of the present invention, at flue gas desulfurization and denitrification device interior, at least one deck spray-absorption layer is provided with in the below of ozone steam reaction and absorbed layer, for pretreated fumes to absorb the sulfur dioxide in flue gas, with ensure flue gas by ozone steam reaction and absorbed layer before, first pass through at least one deck spray-absorption layer, the alkaline slurry of spray-absorption layer ejection can not only remove the sulfur dioxide (can also remove the dust in flue gas) in flue gas, suitably can also reduce the temperature of high-temperature flue gas, prevent part ozone from decomposing when contacting with high-temperature flue gas, there is provided part OH simultaneously
-, ensure the generation of chain reaction.In whole desulphurization denitration process, O
3to SO
2oxygenation efficiency lower than 10% because NO and O
3reaction activity is far below SO
2with O
3reaction activity, its preferential reaction level is much larger than SO
2.Confirm through test, SO in flue gas
2existence can not to O
3oxidation NO produces too much impact, can not cause O
3too much consumption.But first effectively can reduce flue-gas temperature through at least one deck spray-absorption layer, prevent part O
3decomposition and consumption is wasted.
According to the preferred embodiment of the present invention, at flue gas desulfurization and denitrification device interior of the present invention, at least one deck spray-absorption layer is provided with above ozone steam reaction and absorbed layer, for absorbing the nitrogen oxide in flue gas, to ensure that the nitrogen oxide in the flue gas after there is oxidation reaction is absorbed by the alkaline slurry that this spray-absorption layer sprays.Preferably, by ozone steam reaction with absorbed layer above arrange two-layer more than spray-absorption layer, be more preferably two, three or four layers, to absorb NO
2or N
2o
5etc. higher nitrogen oxides, the SO that do not absorbed
2or other impurity.
At flue gas desulfurization and denitrification device interior of the present invention, preferably, ground floor spray-absorption layer, second layer spray-absorption layer and third layer spray-absorption layer are set from top to bottom, described ozone steam reacts and absorbed layer is arranged on ground floor spray-absorption layer, any position between second layer spray-absorption layer and third layer spray-absorption layer, to ensure that hydroxide ion and ozone fully cause chain reaction and chain transfer reaction, and generate the extremely strong hydroxyl radical free radical of oxidisability.According to device of the present invention, preferably, ozone steam reaction and absorbed layer are arranged on 0.8 ~ 2.8 meter of above ground floor spray-absorption layer, and 1.0 ~ 2.3 meters, distance second layer spray-absorption layer.According to device of the present invention, more preferably, ozone steam reaction and absorbed layer are arranged on 1.2 ~ 2.0 meters of above ground floor spray-absorption layer, and 1.3 ~ 1.8 meters, distance second layer spray-absorption layer.
As the preferred detailed description of the invention of the present invention, described ozone steam reaction and absorbed layer are arranged between ground floor spray-absorption layer, second layer spray-absorption layer.Ozone steam reaction of the present invention and absorbed layer are arranged on 0.8 ~ 2.8 meter of above ground floor spray-absorption layer, are preferably 1.2 ~ 2.0 meters of, are more preferably 1.8 meters of; Ozone steam reaction of the present invention and absorbed layer are arranged on 1.0 ~ 2.3 meters of below second layer spray-absorption layer, are preferably 1.1 ~ 1.8 meters of, are more preferably 1.3 meters of.
As the present invention's another detailed description of the invention preferred, described ozone steam reaction and absorbed layer are arranged between second layer spray-absorption layer, third layer spray-absorption layer.Ozone steam reaction of the present invention and absorbed layer are arranged on 0.8 ~ 2.8 meter of above second layer spray-absorption layer, are preferably 1.2 ~ 2.0 meters of, are more preferably 1.8 meters of; Ozone steam reaction of the present invention and absorbed layer are arranged on 1.0 ~ 2.3 meters of below third layer spray-absorption layer, are preferably 1.1 ~ 1.8 meters of, are more preferably 1.3 meters of.
In desulfuring and denitrifying apparatus of the present invention, ozone steam reaction and absorbed layer are provided with ozone atomizer, ozone is generated by the ozone generator in Ozone generation and supply arrangement, via Pipeline transport to the described ozone atomizer be arranged in the reaction of described ozone steam and absorbed layer, preferably, after ozone generator generates ozone, by pressurization after through by Pipeline transport to be arranged in described ozone steam react and absorbed layer in described ozone atomizer, more preferably, pressurizeed by ozone conveying fan.The pipeline material of described ozone generator is preferably the fiberglass of surface coverage carbon fiber.
In desulfuring and denitrifying apparatus of the present invention, in ozone steam reaction and absorbed layer, flue-gas temperature can be 40 ~ 70 DEG C, and be preferably 50 ~ 60 DEG C, be more preferably 55 DEG C, dust content is 30 ~ 50mg/Nm
3, be preferably 35 ~ 45mg/Nm
3, relative humidity is greater than 30%, is preferably greater than 40%, between humidity of flue gas 10% ~ 15%, is preferably 12% ~ 13%.Under these conditions, ozone decomposed is slow, spray-absorption layer slurries are that alkalescence provides hydroxide ion, humidity, temperature and hydroxide ion content are suitable especially decomposites more hydroxyl radical free radical, and hydroxyl radical free radical is the material stronger than ozone oxidation performance, faster lower nitrogen oxides can be become the nitrogen oxide of high price, thus ozone and NO are provided
xbest reaction environment, improves denitration efficiency to greatest extent, and save ozone usage, present invention process method denitration efficiency can reach more than 85%, and ozone-depleting can reduce by more than 30%.Further, the reaction of nitrogen oxides in hydroxyl radical free radical and flue gas generates nitric acid and nitrous acid.
In desulfuring and denitrifying apparatus of the present invention, the temperature of desulphurization denitration flue gas (flue gas namely in desulphurization denitration process) preferably controls within 70 DEG C, to prevent ozone from decomposing too early, preferably controlling between 40 ~ 70 DEG C, between being preferably 50 ~ 65 DEG C; The flow control of desulphurization denitration flue gas is being less than 5m/s, is more preferably 2m/s ~ 4m/s, most preferably is 3.5m/s, and to ensure that the nitrogen oxide in flue gas is substantially oxidized, the sulfur dioxide in flue gas is fully absorbed.
In desulfuring and denitrifying apparatus of the present invention, the ozone concentration that described ozone generator produces is between 1wt% ~ 15wt% in scope, and from economic considerations, preferred ozone concentration used is 5wt% ~ 10wt%, to ensure that ozone is fully utilized.
In desulfuring and denitrifying apparatus of the present invention, the time of described oxidation reaction is determined by the size of denitration zoneofoxidation, desulphurization denitration flue gas flows through ozone steam reaction and absorbed layer, oxidation reaction is carried out with ozone in denitration oxidation reaction zone, the time of described oxidation reaction is generally between 0.1 ~ 10s, is preferably 0.2 ~ 5s; Be more preferably 0.5 ~ 2s.
In desulfuring and denitrifying apparatus of the present invention, also comprise serum recycle equipment, for receive formed from spray-absorption layer containing sulfate, nitrate slurries, and by the serum recycle of described containing sulfate, nitrate at least partially in spray-absorption layer.Preferably, slurries in spray-absorption layer adopt the slurries of magnesia or magnesium hydroxide preparation, described serum recycle equipment for receive formed from flue gas desulfurization and denitrification equipment containing magnesium sulfate, magnesium nitrate slurries, and by the serum recycle of described containing magnesium sulfate, magnesium nitrate in spray-absorption layer.
In desulfuring and denitrifying apparatus of the present invention, can also comprise demister, described demister is positioned at (i.e. the top of the spray-absorption layer of most top layer) above all spray-absorption layers.Demister of the present invention is Conventional tablet or ridge type, preferably flat, for the droplet carried secretly in flue gas after removing denitration.
In desulfuring and denitrifying apparatus of the present invention, also comprise the outer plate filter of tower or vacuum filter, in order to filter out the solid particulate matter in slurries, as the dust carried in magnesium sulfite, calcium sulfate, flue gas.Clean desulphurization denitration liquid after filtration is sent in settling tank or water treating pond.
In desulfuring and denitrifying apparatus of the present invention, also comprise slurries device for transferring, reach the slurries after the desulphurization denitration of setting to discharge pH value in tower.
In desulfuring and denitrifying apparatus of the present invention, also comprise DCS or PLC control appliance, by complete equipment automation as far as possible, to save manpower, improve the automatization level of instrument and supplies, reduce the artificial operate miss produced.
According to desulfuring and denitrifying apparatus of the present invention, preferably, described flue gas meets one of following condition:
(1) flue gas described in is from coal-burning power plant, the flue gas of sintering machine, pelletizing or kiln;
(2) content of sulfur dioxide of described flue gas is 300mg/Nm
3~ 20000mg/Nm
3, NO
xcontent is 100mg/Nm
3~ 500mg/Nm
3and oxygen content is 8 ~ 20vt%.
Under these conditions, flue gas desulfurization and denitrification efficiency improves further, and nitrate, sulfate product quality are more stable.
< desulfurization denitration method >
Utilize said apparatus of the present invention to carry out desulfurization denitration method, comprise the steps: flue gas oxidation step, wet absorption step, ozone supply step.Optionally, desulfurization denitration method of the present invention also comprises serum recycle step, demist step, slurries discharge step and filtration step etc.
Flue gas oxidation step of the present invention is utilize the lower nitrogen oxides in the ozone oxidation flue gas in ozone steam reaction and absorbed layer, form higher nitrogen oxides, the arranging the number of plies and can determine the requirement of denitrating flue gas according to reality of the reaction of described ozone steam and absorbed layer, preferably one deck ozone steam reacts and absorbed layer.Preferably, flue gas oxidation step of the present invention comprises: in ozone steam reaction and absorbed layer, eject ozone by being provided with ozone atomizer.The process conditions of ozone steam reaction and absorbed layer as previously mentioned, are no longer applied here and are stated.
Wet absorption step of the present invention is that the absorbent utilizing spray-absorption layer to spray absorbs sulfur dioxide in flue gas and nitrogen oxide, and forms absorption product.Preferably, described absorbent is alkaline slurry, described alkaline slurry by oxide or hydroxide formulated, one or more being more preferably in calcium oxide, magnesia, sodium oxide molybdena, calcium hydroxide, magnesium hydroxide, NaOH, ammoniacal liquor are formulated, most preferably are magnesia or the formulated slurries of magnesium hydroxide.The number of plies of spray-absorption layer can be determined according to the content of the material to be removed such as nitrogen oxides in effluent, sulfur dioxide.In flue gas desulfurization and denitrification equipment of the present invention, above and below ozone steam reaction and absorbed layer, be equipped with at least one deck spray-absorption layer.Other are concrete as previously mentioned, no longer apply here and state.
Ozone supply step of the present invention is reacted and absorbed layer ozone supply to described ozone steam by ozone supply apparatus.Particularly, ozone is generated by the ozone generator in ozone supply apparatus, after pressurization through by Pipeline transport to be arranged in described ozone steam react and absorbed layer in described ozone atomizer, and then be injected in flue gas desulfurization and denitrification equipment, preferably, the pipeline material of described ozone generator is the fiberglass of surface coverage carbon fiber.The ozone concentration that ozone generator produces is between 1wt% ~ 15wt% in scope, and from economic considerations, preferred ozone concentration used is 5wt% ~ 10wt%, to ensure that ozone is fully utilized.
Optionally, method of the present invention also comprises serum recycle step, the containing sulfate adopting the reception of serum recycle equipment to be formed from flue gas desulfurization and denitrification equipment, the slurries of nitrate, and by the serum recycle of described containing sulfate, nitrate in spray-absorption layer.
Optionally, method of the present invention also comprises demist step, the droplet carried secretly in flue gas after adopting demister removing desulphurization denitration.The set-up mode of demister as previously mentioned, repeats no more here.
Optionally, method of the present invention also comprises filtration step, adopts the outer plate filter of tower or vacuum filter, filters out the solid particulate matter in slurries, as the dust carried in magnesium sulfite, calcium sulfate, flue gas.Clean desulphurization denitration liquid after filtration is sent in settling tank or water treating pond.
Optionally, method of the present invention also comprises slurries and discharges step, reaches the slurries after the desulphurization denitration of setting to discharge pH value in tower.
The process conditions that above-mentioned serum recycle step, demist step, slurries discharge step and filtration step have no particular limits, and can use process conditions known in the art.
When using desulfuring and denitrifying apparatus of the present invention and method, when described desulphurization denitration exhaust gas volumn is 1,000,000Nm
3the flow velocity of/h, flue gas is less than 5m/s, NO in flue gas
xconcentration is 500mg/Nm
3left and right, to require after denitration process NO in flue gas
xconcentration is 100mg/Nm
3during left and right, adopt O
3as denitration oxidant, the consumption of described denitration oxidant is preferably 260 ~ 460kg/h, is preferably 300 ~ 360kg/h.
Be below be described apparatus and method of the present invention by reference to the accompanying drawings, example, only for explaining the present invention, is not for limiting the scope of the invention.
The raw material used in following examples of the present invention is described as follows:
Alkaline slurry is magnesium hydroxide slurry;
O
3the ozone concentration of product is 10wt%.
embodiment 1
Fig. 1 is the device schematic diagram of the embodiment of the present invention 1.As seen from the figure, desulfuring and denitrifying apparatus of the present invention comprises desulphurization denitration tower 1, ozone supply apparatus.Ozone supply apparatus comprises ozone generator 12, ozone conveying fan 11.Three layers of spray-absorption layer (ground floor spray-absorption layer 2, second layer spray-absorption layer 3, third layer spray-absorption layer 4), ozone steam reaction and absorbed layer 5 and Ta Nei slurries circulating slot 7 is comprised in desulphurization denitration tower 1.Desulphurization denitration tower 1 is provided with ground floor spray-absorption layer 2, ozone steam reaction and absorbed layer 5, second layer spray-absorption layer 3, third layer spray-absorption layer 4 from top to bottom successively.Desulphurization denitration flue gas enters in desulphurization denitration tower 1 from gas approach 20, the sulfur dioxide in flue gas is absorbed through ground floor spray-absorption layer 2, then the nitrogen oxide in flue gas is oxidized through ozone steam reaction and absorbed layer 5, the sulfur dioxide that the nitrogen oxide that the flue gas after oxidation absorbs in flue gas further by second layer spray-absorption layer 3 and third layer spray-absorption layer 4 is remaining with possibility.Ozone steam reaction and absorbed layer 5 are 1.8m apart from ground floor spray-absorption layer 2, and distance second layer spray-absorption layer 3 is 1.3m.Spacing between second spray-absorption layer 2 and third layer spray-absorption layer 3 is 2.8m.In tower, slurries circulating slot 7 is built with alkaline slurry, is delivered to each spray-absorption layer (ground floor spray-absorption layer 2, second layer spray-absorption layer 3, third layer spray-absorption layer 4) through slurry circulating pump 9 by alkaline slurry transfer pipeline.Ozone generates in ozone generator 12, is delivered in the nozzle of ozone steam reaction and absorbed layer 5 through pipeline by ozone conveying fan 11.In desulphurization denitration tower 1, above third layer spray-absorption layer 4,0.6m place is provided with demister 6, and the top of demister 6 is provided with exhanst gas outlet 8.In tower, slurries circulating slot 7 is located at bottom denitrating tower 1, and the outer slurry pool 10 of tower is connected with slurries circulating slot 7 in tower, for supplementing slurries to slurries circulating slot 7 in tower.Desulphurization denitration rear slurry pond 15 is connected with slurries circulating slot 7 in tower by excavationg pump 13, plate and frame filter press 14.Also be provided with flue gas accident spraying layer 16 below ground floor spray-absorption layer 2 in desulphurization denitration tower 1, flue gas accident spraying layer 16 is connected with flue gas accident water tank 18 by pipeline through flue gas accident spray pump 17.
The technological process of the embodiment of the present invention 1 is:
Contain alkaline alkali lye in slurries circulating slot 7 in the tower of a, desulphurization denitration tower 1, be delivered to ground floor spray-absorption layer 2, second layer spray-absorption layer 3 and third layer spray-absorption layer 4 and Jet with downward flow direction by slurry circulating pump 9 through alkaline slurry transfer pipeline.
B, desulphurization denitration flue gas enter desulphurization denitration tower 1 inside from the gas approach 20 in desulphurization denitration tower 1 and rise, the alkaline slurry counter current contacting generation neutralization reaction that flue gas ejects with ground floor spray-absorption layer 2 in uphill process, the most of SO in removing flue gas
2and dust, form the flue gas of preliminary purification, the temperature of flue gas is minimized;
C, the O produced by ozone generator
3product is pressurizeed by ozone conveying fan 11, is delivered to ozone steam reaction and absorbed layer 5 Jet with downward flow direction through ozone transfer pipeline, flue gas in uphill process with O
3counter current contacting generation oxidation reaction, the lower nitrogen oxides in oxidation flue gas, the NO in removing flue gas
x, form ozone oxidation flue gas;
D, ozone oxidation flue gas continue to rise, the alkaline slurry counter current contacting generation neutralization reaction ejected with second layer spray-absorption layer 3, obtain the absorption product containing sulfate, sulphite, NO3-N and NO2-N, and form ozone oxidation desulphurization denitration flue gas, ozone oxidation desulphurization denitration flue gas continues to rise, there is neutralization reaction further in the alkaline slurry counter current contacting ejected with third layer spray-absorption layer 4, obtain the absorption product of containing sulfate, sulphite, NO3-N and NO2-N, and form ozone oxidation desulphurization denitration flue gas again;
E, ozone oxidation again desulphurization denitration flue gas continue to rise, and remove by demister 6 droplet that ozone oxidation carries secretly in desulphurization denitration flue gas again, qualified flue gas is discharged by exhanst gas outlet 8;
Slurries circulating slot 7 in the tower that the absorption product of the containing sulfate that f, whole oxidation and denitration process generate, sulphite, NO3-N and NO2-N falls into bottom desulphurization denitration tower 1, in nitrite and environment, oxygen generation oxidation reaction generates nitrate, in sulphite and environment, oxygen generation oxidation reaction generates sulfate, then sulfate, nitrate to fall in tower in slurries circulating slot 7 with slurries, reach the object removing sulfur dioxide and nitrogen oxide; When the slurries of slurries circulating slot 7 in tower are not enough, the outer slurry pool 10 of tower supplements slurries to slurries circulating slot 7 in tower;
React in slurries circulating slot 7 in g, tower saturated after slurries discharge via excavationg pump 13, obtain solid through plate and frame filter press 14 press filtration, the slurries after press filtration enter desulphurization denitration rear slurry pond 15.
H, when occur flue gas accident time, automatically will start flue gas accident spray pump 17, close slurry circulating pump 9 and ozone conveying fan 11, the water in flue gas accident water tank 18 or slurries deliver to flue gas accident spraying layer 16 through flue gas accident spray pump 17 simultaneously, for flue gas cool-down, to ensure device security.
Above-mentioned desulfuring and denitrifying apparatus and method are applied in 1,500,000 tons of pelletizing denitration projects, operational factor is as shown in table 1.
Table 1 1,500,000 tons of pelletizing desulfuring and denitrifying apparatus operational factor tables
| Sequence number | Parameter | Unit | Numerical value |
| 1 | Exhaust gas volumn (operating mode) | m 3/h | 780000 |
| 2 | Entrance sulfur dioxide concentration | mg/Nm 3 | 1600 |
| 3 | Outlet sulfur dioxide concentration | mg/Nm 3 | 60 |
| 4 | Inlet nitrogen oxides concentration | mg/Nm 3 | 450 |
| 5 | Outlet nitrous oxides concentration | mg/Nm 3 | 70 |
| 6 | Inlet dust | mg/Nm 3 | 115 |
| 7 | Outlet dust | mg/Nm 3 | 22 |
| 8 | Flue-gas temperature | ℃ | 110～160 |
| 9 | Operating cost | Yuan/ton pellet | 4.4 |
The exhaust gas volumn of this project is 780,000 m
3/ h, at O
3after dropping into, 10min test, terminates to 70min, and in this process, outlet amount of nitrogen oxides is basically stable at 60 ~ 75mg/Nm
3between, sulfur dioxide concentration maintains 60mg/Nm
3left and right, average denitration efficiency is up to 84%, and mean efficiency of desulfurization is 99.5%, and higher than design load, discharge content is lower than emission limit.O
3consumption with traditional O
3desulphurization denitration technology is compared, and lack 25 ~ 33%.The technical indicators such as this project denitrification efficiency are as shown in table 2.
Table 2 1,500,000 tons of pelletizing denitrification apparatus running technology indexs
comparative example 1
Desulfuring and denitrifying apparatus described in embodiment 1 and method are applied in 1,500,000 tons of pelletizing desulphurization denitration projects, difference to be only ground floor spray-absorption layer by layer 2, second layer spray-absorption layer 3 and third layer spray-absorption layer 4 close 1 hour 10 points, the reaction of record ozone steam and absorbed layer cigarette temperature, as shown in table 3.
The reaction of table 3 ozone steam and absorbed layer cigarette temperature
| Time (min) | 10 | 20 | 30 | 40 | 50 | 60 | 70 |
| Cigarette temperature (DEG C) | 78 | 76 | 82 | 74 | 79 | 73 | 78 |
Its average cigarette temperature is: 77.1 DEG C
At O
3after dropping into, 10min test, terminates to 70min, and in this process, outlet amount of nitrogen oxides is basically stable between 325 ~ 389, and average denitration efficiency only has 15.7%, and far below design load, discharge content obviously exceeds standard.The technical indicators such as this project denitrification efficiency are as shown in table 4.
Table 4 1,500,000 tons of pelletizing denitrification apparatus running technology indexs
By ground floor spray-absorption layer by layer 2, second layer spray-absorption layer 3 and third layer spray-absorption layer 4 close, the liquid-gas ratio of slurries declines and causes desulfuration efficiency to be reduced to 88.1%; In addition, cigarette temperature rises, and its mean temperature is 77.1 DEG C, and now temperature can cause O
3decomposed, simultaneously hydroxyl oxidize agent content reduces, and efficiency obviously reduces, and does not have providing of hydroxyl ion absorption reaction to be close to cannot carry out simultaneously.Now just can cause outlet NO
xobviously exceed standard.Compared with embodiment 1, O
3consumption wants many 50 ~ 55%.
The above is only the preferred embodiment of the present invention; it should be pointed out that for those skilled in the art, under the premise without departing from the principles of the invention; can also make some improvements and modifications, these improvements and modifications also should be considered as protection scope of the present invention.
Claims (10)
1. based on a desulfuring and denitrifying apparatus for ozone, it is characterized in that, comprising:
Flue gas desulfurization and denitrification equipment, its inside is provided with: two-layer above spray-absorption layer, ozone steam reaction more than one deck and absorbed layer, lower nitrogen oxides in flue gas is become the nitrogen oxide of high price by wherein said ozone steam reaction and absorbed layer, sulfur dioxide in described spray-absorption layer employing absorbent absorption flue gas and nitrogen oxide, and form absorption product;
Ozone supply apparatus, for reacting and absorbed layer ozone supply to described ozone steam.
2. device according to claim 1, it is characterized in that, at least one deck spray-absorption layer in described two-layer above spray-absorption layer is arranged on described ozone steam reaction and the below of absorbed layer, for pretreated fumes to absorb the sulfur dioxide in flue gas; With
At least one deck spray-absorption layer in described two-layer above spray-absorption layer is arranged on described ozone steam reaction and the top of absorbed layer, for absorbing the nitrogen oxide in flue gas.
3. device according to claim 1, it is characterized in that, be provided with ground floor spray-absorption layer, second layer spray-absorption layer and third layer spray-absorption layer from top to bottom at flue gas desulfurization and denitrification device interior, the reaction of described ozone steam and absorbed layer are arranged on ground floor spray-absorption layer, any position between second layer spray-absorption layer and third layer spray-absorption layer.
4. device according to claim 3, it is characterized in that, described ozone steam reaction and absorbed layer are arranged between ground floor spray-absorption layer and second layer spray-absorption layer, ozone steam reaction and 0.8 ~ 2.8 meter, absorbed layer distance ground floor spray-absorption layer, and 1.0 ~ 2.3 meters, distance second layer spray-absorption layer.
5. device according to claim 3, it is characterized in that, described ozone steam reaction and absorbed layer are arranged between ground floor spray-absorption layer and second layer spray-absorption layer, ozone steam reaction and 1.2 ~ 2.0 meters, absorbed layer distance ground floor spray-absorption layer, and 1.3 ~ 1.8 meters, distance second layer spray-absorption layer.
6. device according to claim 3, it is characterized in that, described ozone steam reaction and absorbed layer are arranged between second layer spray-absorption layer and third layer spray-absorption layer, ozone steam reaction and 0.8 ~ 2.8 meter, absorbed layer distance second layer spray-absorption layer, and 1.0 ~ 2.3 meters, distance third layer spray-absorption layer.
7. the device according to any one of claim 1 ~ 6, is characterized in that, described device also comprises:
Serum recycle equipment, for receiving the absorption product formed from flue gas desulfurization and denitrification equipment, and will described absorption product be circulated in spray-absorption layer at least partially;
Demister, for carrying out dedusting demist to flue gas, described demister is positioned at the top of whole spray-absorption layer.
8. utilize the device described in any one of claim 1 ~ 7 to carry out a method for flue gas desulfurization and denitrification, it is characterized in that, comprise the steps:
Flue gas oxidation step, in ozone steam reaction and absorbed layer, utilizes the lower nitrogen oxides in ozone oxidation flue gas, forms higher nitrogen oxides;
Wet absorption step, the sulfur dioxide in the absorbent utilizing spray-absorption layer to spray absorption flue gas and nitrogen oxide, and form absorption product;
Ozone supply step, is reacted and absorbed layer ozone supply to described ozone steam by ozone supply apparatus.
9. method according to claim 8, is characterized in that, in flue gas oxidation step, the process conditions of ozone steam reaction and absorbed layer are: flue-gas temperature is 40 ~ 70 DEG C, and dust content is 30 ~ 50mg/Nm
3, relative humidity is greater than 30%, humidity of flue gas is between 10% ~ 15%.
10. method according to claim 9, is characterized in that, in flue gas oxidation step, the flow control of flue gas is being less than 5m/s.
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| CN201510303396.1A CN104959010A (en) | 2015-06-05 | 2015-06-05 | Desulphurization and denitration apparatus and method based on ozone |
| HK16103115.6A HK1215216A1 (en) | 2015-06-05 | 2016-03-17 | Ozone-based desulphurization and denitration device and method |
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| CN201510303396.1A CN104959010A (en) | 2015-06-05 | 2015-06-05 | Desulphurization and denitration apparatus and method based on ozone |
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| WO2019062453A1 (en) * | 2017-09-30 | 2019-04-04 | 中晶环境科技股份有限公司 | Ozonation-based method for manufacturing cementitious material |
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| CN101745305A (en) * | 2010-01-24 | 2010-06-23 | 华北电力大学（保定） | Method for removing various gaseous pollutants from smoke gas |
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