CN102580496B - Liquid-phase oxidation multistage absorbed flue gas desulfurization and denitrification technology and device - Google Patents
Liquid-phase oxidation multistage absorbed flue gas desulfurization and denitrification technology and device Download PDFInfo
- Publication number
- CN102580496B CN102580496B CN201210067173.6A CN201210067173A CN102580496B CN 102580496 B CN102580496 B CN 102580496B CN 201210067173 A CN201210067173 A CN 201210067173A CN 102580496 B CN102580496 B CN 102580496B
- Authority
- CN
- China
- Prior art keywords
- flue gas
- spraying layer
- desulfurization
- oxidant
- tower
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Images
Classifications
-
- 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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
- Y02A50/20—Air quality improvement or preservation, e.g. vehicle emission control or emission reduction by using catalytic converters
Landscapes
- Treating Waste Gases (AREA)
Abstract
The invention discloses a liquid-phase oxidation multistage absorbed flue gas desulfurization and denitrification technology and a liquid-phase oxidation multistage absorbed flue gas desulfurization and denitrification device, and belongs to the technical field of flue gas treatment. The technology comprises the following steps of: performing pre-desulfurization by contact reaction of flue gas and a desulfurizing agent which absorbs a part of sulfur dioxide in the flue gas to obtain desulfurized slurry; performing liquid-phase oxidation and partial absorption on the pre-desulfurized flue gas, and oxidizing nitric oxide in the flue gas into nitrogen dioxide; and performing contact reaction on the oxidized flue gas and the desulfurized slurry to absorb the nitrogen dioxide and the rest sulfur dioxide in the flue gas. The device comprises a desulfurization and denitrification tower and a tower kettle arranged at the bottom of the desulfurization and denitrification tower, wherein a first spraying layer, a sieve plate layer, a second spraying layer and a third spraying layer are sequentially arranged above the tower kettle from bottom to top; and the sieve plate layer is communicated with the second spraying layer through an oxidant slurry tank positioned outside the desulfurization and denitrification tower, and the first spraying layer and the third spraying layer are communicated with the tower kettle through external circulating pumps respectively. The technology is simple and high in desulfurization and denitrification efficiency during desulfurization and denitrification of the flue gas.
Description
Technical field
The present invention relates to smoke gas treatment technical field, be specifically related to a kind of flue gas desulfurization and denitration technique and device of liquid phase oxidation multistage absorption.
Background technology
Along with improving constantly of national requirements for environmental protection, standard limit of smog release increasingly stringent, it is increasingly urgent that flue gas desulfurization and denitrification becomes.Main flue gas desulfurization technique has the wet processings such as lime/lime stone-gypsum, magnesium method, ammonia process and semidry method, dry desulfurizing process.And that denitration technology has is several below: selective catalytic reduction (SCR), SNCR method (SNCR), SNCR and SCR combination method (SNCR-SCR).But substep denitration sulfur removal technology complexity, equipment is various, and investment operating cost is high, safeguards inconvenience.Therefore increasing expert, in the technology of developmental research desulfurization and denitrification integral, is also the direction of national policy guiding simultaneously.
A kind of method and apparatus that utilizes hydrogen peroxide to reduce sulfur dioxide, nitrogen oxide and heavy metals emission in flue gas stream is disclosed in the Chinese patent literature that publication number is CN1950139A.The method of hydrogen peroxide denitration, is the hydrogenperoxide steam generator thermal activation gaseous oxidation NO that utilizes high concentration, and liquid phase absorbing and removing nitrogen oxide.But the complex process of this patented invention, the equipment that requirement is used is a lot; Secondly the necessary heat-activated of hydrogen peroxide, need to be heated to hydrogenperoxide steam generator about 500 ℃ and could be oxidized NO, and lot of energy, has increased operating cost.
Publication number is in the Chinese patent literature of CN101934191A, to disclose a kind of ammonia flue gas method of desulphurization denitration simultaneously, take ammoniacal liquor as absorption liquid, adopts Multi-layer sprinkling to absorb nitrogen oxide and the sulfur dioxide in flue gas.Although the method also can remove sulfur dioxide and nitrogen oxide in flue gas, but also there is following shortcoming: first, be that the simple ammoniacal liquor that passes through repeatedly absorbs flue gas, do not take the oxidation measure to flue gas, and in nitrogen oxides in effluent, have 95% to be the nitric oxide of more difficult absorption, not oxidised directly absorbs, and its denitration efficiency certainly will be not high; The second, the accessory substance sulfate and nitrate of desulphurization denitration mixes, and reclaims difficulty, certainly will increase the cost that by-product recovery is utilized.
Publication number is wet ammonia flue gas cleaning technology and the system thereof that discloses a kind of while desulphurization denitration in the Chinese patent of CN100496675C.This technique is used the NO in ozone gas phase oxidation flue gas, then utilizes sulfur dioxide and nitrogen oxide in ammonia absorption flue gas.This technique is carried out desulphurization denitration after the nitrogen oxide in flue gas is oxidized again, its denitration efficiency can increase, but the ozone gas phase oxidation that this technique is used, first, ozone need to generate with a large amount of electric power, every kilogram of ozone expends electric weight greatly about 10-16Kw, and this has improved operating cost undoubtedly; The second, ozone also may be oxidized SO in flue gas
2, causing the waste of oxidant, the sulfur trioxide simultaneously generating can generate acid mist; The 3rd, what adopt is gaseous oxidation, gaseous oxidation, owing to being to spray into gaseous oxidizer, has certain requirement to air-tightness, and careless slightly easy generation oxidizing gas is revealed and caused accident, secondly gaseous oxidation requires oxidizing gas and flue gas to mix fully rapidly, technical requirement is high, therefore, gaseous oxidation to equipment require high, the control of technique is more complicated, and enterprise's production cost is high.
Notification number is that the Chinese patent of CN101385945942B discloses a kind of liquid-phase oxidation-absorption two-stage wet method flue-gas denitration technique, adopt the solution of one or more mixtures in potassium permanganate, sodium chlorite, clorox, calcium hypochlorite, hydrogen peroxide, chlorine dioxide as oxidant, make nitric oxide and oxidant haptoreaction in flue gas, after partial oxygen changes into nitrogen dioxide, utilize alkali liquor absorption nitrogen oxide in flue gas after peroxidating, produce corresponding nitrite.The method adopts liquid phase oxidation, gaseous oxidation relatively, simplify technological process, reduced denitration cost, but the sulfur dioxide containing in flue gas can consume the oxidant of part, causes the waste of oxidant, sulfur dioxide is oxidized to sulfur trioxide and can forms acid mist simultaneously, in addition, the sulfur dioxide in flue gas can not well be removed simultaneously very much, also needs to increase corresponding sulfur removal technology.
Therefore, developing a kind of method for oxidation of efficient nitrogen oxide oxide, and manage to reduce the oxygenation efficiency of SO 2 from fume, reduce oxidant consumption, reduce operating cost, is the improved direction of combined desulfurization and denitrification process, is conducive to application and the popularization of this technique.
Summary of the invention
The invention provides a kind of flue gas desulfurization and denitration technique and device of liquid phase oxidation multistage absorption, strengthen the utilization rate of flue gas oxidant, improved the denitration efficiency of flue gas.
A flue gas desulfurization and denitration technique for liquid phase oxidation multistage absorption, comprising:
(1) desulfurizing agent and flue gas haptoreaction are carried out to pre-desulfurization, desulfurizing agent absorbs the part sulfur dioxide in flue gas, obtains desulfurization slurry;
(2) flue gas after pre-desulfurization is carried out to liquid phase oxidation and partially absorbs, the oxidation of nitric oxide in flue gas is become to nitrogen dioxide, the oxidant of described liquid phase oxidation is at least one the aqueous solution in hydrogen peroxide, chlorite and hypochlorite;
(3) by the desulfurization slurry haptoreaction in the flue gas after peroxidating and step (1), the nitrogen dioxide in absorption flue gas and remaining sulfur dioxide.
In flue gas from boiler flue, contain a large amount of sulfur dioxide and nitrogen oxide, nitrogen oxide is mainly take nitric oxide as main, nitric oxide is not easy to be absorbed, when its nitrogen oxide that is oxidized to high valence state is more easily absorbed during as nitrogen dioxide, first by desulfurizing agent, flue gas is carried out to one-level absorption, remove most sulfur dioxide in flue gas, after sulfur dioxide in the flue gas of desulfurizing agent absorption simultaneously, obtain being rich in the desulfurization slurry of inferior sulfate radical, and then flue gas is carried out to high efficiency liquid phase oxidation, oxidation of nitric oxide in flue gas is become to nitrogen dioxide, oxidized dose of absorption of part forms nitrate slurries, this nitrate can obtain byproduct as fertilizer etc. after by subsequent treatment, take chlorite as oxidant as example, the reaction equation of concrete oxidation reaction is as follows:
2NO+ClO
2 -→2NO
2+Cl
-
4NO
2+ClO
2 -+4OH
-→4NO
3 -+Cl
-+2H
2O
NO+ClO
2 -→NO
2+ClO
-
NO+ClO
-→NO
2+Cl
-
2NO
2+ClO
2 -+2OH
-→2NO
3 -+ClO
-+2H
2O
Finally utilize the desulfurization slurry after first grade desulfurizing to carry out secondary absorption to flue gas, nitrogen dioxide in removal flue gas and remaining sulfur dioxide, form sulfate slurries, these sulfate slurries obtain accessory substance as gypsum after subsequent treatment, and secondary absorbs nitrogen dioxide reaction equation while absorption is as follows:
4SO
3 2-+2NO
2+→N
2+4SO
4 2-
The nitrate slurries and the sulfate slurries that in flue gas desulfurization and denitrification process, obtain separate, and conveniently respectively it are reclaimed.
Described chlorite can select sodium chlorite, hypochlorite can select at least one in clorox, calcium hypochlorite.
In the time carrying out liquid phase oxidation, oxidant need to be diluted to the aqueous solution containing finite concentration the efficient oxidation composition, preferred as one, in the oxidant described in step (2), the efficient oxidation composition accounts for the 5-35% of gross mass, more preferably 5-10%.Described the efficient oxidation composition refers to the gross mass of solute in oxidant (aqueous solution), for example, when oxidant is the chlorite aqueous solution, the efficient oxidation composition is chloritic quality, in the time that oxidant is the mixed aqueous solution of chlorite and hypochlorite, the efficient oxidation composition is the gross mass of chlorite and hypochlorite.
For improving the oxidation characteristic of oxidant, in described oxidant, be also added with the metal ion that accounts for oxidant gross mass 0.001-0.01%, be preferably 0.001-0.005%.Described metal ion is at least one in iron ion, manganese ion, copper ion and magnesium ion.Described iron ion can be selected iron chloride, and described manganese ion can be selected manganese chloride, and described magnesium ion can be selected magnesium sulfate, and described copper ion can be selected copper sulphate.Add the catalyst such as micro-iron ion manganese ion copper ion, can effectively improve the efficiency of oxidation, hydrogen peroxide, hypochlorite, chlorite etc. can produce faster active hydroxyl free radical under the effect of catalyst, thereby cause and propagation radical chain reaction, accelerate the oxidation of nitrogen oxide, more than 95% oxidation of nitric oxide in flue gas can be become to the nitrogen oxide of high valence state.
As the preferred technical scheme of one, the pH value of described oxidant is 4-7.When higher than this scope, the oxidisability of oxidant reduces, and oxidation absorbs nitric oxide production effect and weakens.During lower than this scope, oxidant self decomposition is accelerated, and produces a large amount of chlorine, and the gases such as chlorine dioxide are overflowed, and cause the waste of oxidant.The control of pH value mainly reduces pH value by absorbing acid gas in flue gas sulfur dioxide and nitrogen oxide, and interpolation sodium chlorite or clorox etc. are alkaline oxidant and improve pH value.
In the process of liquid phase oxidation, need to control its reaction temperature, as the preferred technical scheme of one, the temperature of described liquid phase oxidation is 40-50 ℃.In this temperature range, absorption and the oxidizing reaction rate of oxidant to nitrogen oxide is moderate, and the side reaction of selfdecomposition does not occur substantially.Input gas temperature, generally at 80-150 ℃, by the liquid-gas ratio of suitably pre-desulfurization, and is incubated the pipeline tower tank at liquid phase oxidation reaction place, gets final product satisfied temperature requirement.
The liquid-gas ratio of liquid phase oxidation regulates according to the content of nitrogen oxides in effluent, preferred as one, the liquid-gas ratio control 3-7L/m of described liquid phase oxidation
3.In the time that the content of nitrogen oxides in effluent increases, suitably improve liquid-gas ratio, strengthen the Sprayer Circulation amount of oxidant, strengthen the absorption to nitrogen oxide.In the time that the content of nitrogen oxides in effluent declines, can reduce liquid-gas ratio, reduce the Sprayer Circulation amount of oxidant, save the consumption of oxidant.
Desulfurizing agent described in step (1) is ammoniacal liquor, seawater, magnesium hydroxide or lime stone slurry, the pH value of desulfurizing agent and liquid-gas ratio arrange according to the content of sulfur dioxide in flue gas and selected desulfurizing agent kind, as the preferred technical scheme of one, described desulfurizing agent is selected calcium hydroxide or lime stone slurry, its pH value is controlled within the scope of 4-6, and total liquid-gas ratio of step (1) and step (3) desulfurization is controlled at 3-15L/m
3in scope, than the liquid-gas ratio in step (3) slightly greatly once, removal sulfur dioxide as much as possible, prevents sulfur dioxide oxygen consumed agent to the liquid-gas ratio in general step (1), for example, when total liquid-gas ratio is 10L/m
3time, the liquid-gas ratio in step (1) is 6L/m
3, the liquid-gas ratio in step (3) is 4L/m
3.
The present invention also provide a kind of realize as described in the device of desulfurizing and denitrifying process, comprise desulphurization denitration tower, described desulphurization denitration tower bottom is provided with the tower reactor for holding described desulfurizing agent and desulfurization slurry, the top of described tower reactor sets gradually the first spraying layer that is useful on the described desulfurizing agent of spray from the bottom to top, for making flue gas contact the sieve plate layer that carries out liquid phase oxidation with oxidant, for spraying the second spraying layer of described oxidant and for spraying the 3rd spraying layer of described desulfurization slurry, between described sieve plate layer and the second spraying layer, be communicated with by the oxidizer slurry tank being positioned at outside desulphurization denitration tower, the first described spraying layer and the 3rd spraying layer are communicated with tower reactor by external circulating pump respectively.
Flue gas moves from the bottom to top, through the first spraying layer, desulfurizing agent in tower reactor is squeezed into the first spraying layer by external circulating pump, after circulated sprinkling, its desulfurization slurry that contains inferior sulfate radical falls in tower reactor, oxidizer slurry in oxidizer slurry tank is squeezed into the second spraying layer by circulating pump, spray downwards to sieve plate layer, flue gas continue to move upward through sieve plate layer with after oxidizer slurry blistering reaction on sieve plate layer, continue upwards lower with the second spraying layer spray oxidant continuation and react, flue gas continues upwards to spray the desulfurization slurry haptoreaction of getting off with the 3rd spraying layer, after crossing the demist of demist layer, discharge.
For the sulfate slurries and the nitrate slurries that make to obtain in flue gas processing procedure can carry out subsequent treatment more easily, both need to be separated, desulfurization slurry after the first spraying layer spray washing falls into tower reactor, slurries after the second spraying layer spray washing fall into sieve plate layer, then be back in oxidizer slurry tank by the return duct between sieve plate layer and oxidizer slurry tank, therefore need the slurries after the slurries after the 3rd spraying layer spray washing and the second spraying layer spray washing separate or be drained in tower reactor.As the preferred technical scheme of one, between the 3rd described spraying layer and the second spraying layer, be provided with dividing plate and the downspout that is communicated with dividing plate bottom and tower reactor to lower recess, by dividing plate and downspout, the slurries under the 3rd spraying layer spray are drained to tower reactor; A kind of preferred technical scheme, described dividing plate is by some layers of reducing annulus upper and lower nested composition, and leaves the space of passing for flue gas, and liquid flows to lower one deck annulus in annulus flows inside by last layer annulus, until in downspout, flue gas moves upward from the space between annulus.
In order to facilitate supplementing of oxidant, described oxidizer slurry tank top is provided with the oxidant storage tank by pipeline connection, and its pipeline is provided with valve.Oxidant medicament storage, in oxidant storage tank, is sent in oxidizer slurry tank and is diluted.
For meeting the technological requirement of flue gas desulfurization and denitration technique, as the preferred technical scheme of one, the number of plies of described the first spraying layer, the second spraying layer, the 3rd spraying layer and demist layer is some layers.
Beneficial effect of the present invention:
(1) integrate desulphurization denitration, and be integrated in an absorption tower, simplified greatly technological process, reduced the floor space of equipment, reduced investment cost.
(2) pre-desulfurization before denitration oxidation, removes after most sulfur dioxide carrying out denitration oxidation, and can reduce the side reaction of oxidant and sulfur dioxide, thereby reduce the consumption of oxidant, and the harmful effect of sulfur trioxide, save operating cost.
(3) adopt efficient liquid phase composite denitration oxidant, and add metal ion catalysis oxidation, more than 95% oxidation of nitric oxide in flue gas can be become to the nitrogen oxide of high valence state, and absorb through two-stage denitration, reach higher denitration efficiency.Desulfuration efficiency of the present invention can reach more than 95%, and denitration efficiency can reach more than 90%, can tackle the more and more stricter discharge standard of country.
(4) sulphite that utilizes desulfurization to produce, the nitrogen oxide after absorption oxidation and remaining sulfur dioxide, the treatment of wastes with processes of wastes against one another reduces the consumption of absorbent, and by thoroughly innoxious this part of nitrogen oxide, becomes clean nitrogen.
(5) desulfurizing byproduct and denitration accessory substance separately reclaim, and simplify the recovery process of accessory substance, reduce costs;
(6) adopt liquid phase oxidation technique to replace gaseous oxidation technique, reduce investment and operating cost, simplified technological process simultaneously, strengthen operability.
Accompanying drawing explanation
Fig. 1 is structural representation of the present invention.
The specific embodiment
As shown in Figure 1, the absorption tower that desulphurization denitration tower 9 adopts spray-sieve plate to combine, it is stainless steel material that absorption tower adopts material, acid and alkali-resistance is anti-oxidant, the top on absorption tower arranges exhanst gas outlet 8, absorption tower inner bottom part arranges tower reactor 12, top arranges demist layer 7, between the tower reactor 12 of bottom and the demist layer 7 at top, set gradually from the bottom to top the first spraying layer 2, sieve plate layer 3, the second spraying layer 4 and the 3rd spraying layer 6, the certain distance in interval between each layer, on the tower wall between tower reactor 12 and the first spraying layer 2, be provided with smoke inlet 1, between the second spraying layer 4 and the 3rd spraying layer 6, be provided with dividing plate 5, the periphery of dividing plate 5 is connected with the tower wall on absorption tower, center is protruded formation pit downwards, the bottom of pit is communicated with downspout 16, slurry pipe 16 is downwards successively through the second spraying layer 4, sieve plate layer 3 and the first spraying layer 2, slurries under being sprayed by the 3rd spraying layer 6 are drained in tower reactor 12.
Between tower reactor 12 and the first spraying layer 2, be communicated with by external circulating pump 1, the entrance of circulating pump 1 is communicated with tower reactor 12, and outlet is communicated with the first spraying layer 2; Between tower reactor 12 and the 3rd spraying layer 6, be communicated with by external circulating pump 2 15, the entrance of circulating pump 2 15 is communicated with tower reactor 12, and outlet is communicated with the 3rd spraying layer 6.
Oxidizer slurry tank 11 is set outside absorption tower, the installation site of oxidizer slurry tank 11 is lower than the sieve plate layer 3 in absorption tower, the interior agitator that arranges of oxidizer slurry tank 11, above oxidizer slurry tank 11 by the pipeline connection oxidant storage tank 10 with valve, between oxidizer slurry tank 11 and the second spraying layer 4, be communicated with by external circulating pump 3 14, the entrance of circulating pump 3 14 is communicated with oxidizer slurry tank 11, outlet is communicated with the second spraying layer 4, between oxidizer slurry tank 11 and sieve plate layer 3, is communicated with by return line.
Tower reactor 12 places are communicated with air and blast device and desulfurizing agent supplementary device, are also connected with successively (all not shown in figure) such as gypsum cyclone, gypsum dehydration equipment and drying equipments the final chimney (not shown) that is communicated with of exhanst gas outlet 8.
The percent opening (perforated area accounts for the ratio of the gross area) of sieve plate layer 3 is 10-30%, the first spraying layer 2, the second spraying layer 4 and the 3rd spraying layer 6 are by some pipelines and be arranged on pipeline and some nozzles compositions of pipeline connection, the number of plies of each spraying layer can be set to one deck as required, also can be set to multilayer, in the time being set to multilayer, corresponding increasing seeks circulating pump.
Technological process of the present invention is as follows:
Adopt absorption tower as shown in Figure 1, implement the desulfurizing and denitrifying process of liquid phase oxidation multistage absorption of the present invention.Flue gas enters from smoke inlet 1.Flue gas carries out first grade desulfurizing with the desulfurizing agent counter current contacting that the first spraying layer 2 sprays from bottom to top, sulfur dioxide in flue gas is absorbed, the desulfurization slurry of sulfite ion is rich in formation, desulfurization slurry drops among the tower reactor 12 at the bottom of tower, and through circulating pump one 13 circulated sprinklings, remove the flue gas of most sulfur dioxide.
Flue gas continues upwards, through sieve plate layer 3, after contacting with Oxygen in Liquid agent bubbling gas liquid, and carry out liquid phase oxidation with the absorption liquid spraying (oxidant) counter current contacting, nitric oxide in flue gas is oxidized to the nitrogen oxide of nitrogen dioxide and higher valence state, part is stayed in oxidant, and remaining few part is stayed in flue gas.Oxidant keeps the liquid level of 20-40cm on sieve plate, and unnecessary oxidant flows back in oxidizer slurry tank 11, then returns the second spraying layer 4 through circulating pump 3 14 and spray.
In snperoxiaized flue gas, contain nitrogen dioxide and a small amount of sulfur dioxide, desulfurization slurry counter current contacting spray through dividing plate 5 and the 3rd spraying layer 6 is carried out two-grade desulfurizing, and absorption remains sulfur dioxide and nitrogen oxide, reaches higher denitrification efficiency.In downspout 16 in the middle of collecting through dividing plate 5 after desulfurization slurry sulfur dioxide absorption and nitrogen dioxide, flow in tower reactor 12.
Through demist layer 7, remove entrained drip finally by clean flue gas after crossing desulphurization denitration, enter in atmosphere.
In tower reactor 12, supplement appropriate desulfurizing agent, proceed desulphurization circulating.
In tower reactor 12, pass into air, sulfite oxidation is become to sulfate, then sending into follow-up equipment processes, in slurries after oxidation, absorb part nitrogen oxide, there is nitrate to generate, these slurries are back in oxidizer slurry tank 11 by sieve plate layer 3, continue to participate in circulation after filling into oxidant, and the final slurries containing nitrate are delivered to follow-up equipment and processed.
In following examples, the data such as smoke components all adopt the infrared flue gas analyzer of madur to measure.
Embodiment 1
At 5m
3on the experimental simulation device of/h scale, simulate flue gas desulfurization and denitrification process.Exhaust gas volumn 5m
3/ h, flue gas composition is as follows: O
2be 5%, SO
2for 1000ppm, NO is 400ppm, and all the other are nitrogen, 100 ℃ of flue-gas temperatures, 1 atmospheric pressure of pressure.
Hydrogen peroxide and sodium chlorite are configured to the oxidant that the mass fraction of the efficient oxidation composition is 10% (in oxidant except hydrogen peroxide and sodium chlorite according to 1: 1 (mol ratio), surplus is water), control oxidant pH at 5-6 simultaneously, to add mass fraction be 0.005% iron chloride (be iron chloride account for oxidant gross mass 0.005%), the liquid-gas ratio of liquid phase oxidation is 3-6L/m
3.
Adopt calcium hydroxide as desulfurizing agent, the total liquid-gas ratio of first grade desulfurizing and two-grade desulfurizing is 10L/m
3(first grade desulfurizing is 6L/m
3, two-grade desulfurizing is 4L/m
3), utilize technique of the present invention, carry out desulphurization denitration.First grade desulfurizing efficiency can reach 70%, and after oxidation, in flue gas, NO is 3ppm, NO
2for 190ppm, after two-grade desulfurizing denitration, exit SO
2concentration 20ppm left and right, NOx is 10ppm left and right.Overall desulfuration efficiency 98%, denitration efficiency can reach 97.5%.
Embodiment 2
At 5m
3on the experimental simulation device of/h scale, simulate flue gas desulfurization and denitrification process.Exhaust gas volumn 5m
3/ h, flue gas composition is as follows: O
2be 5%, SO
2for 1000ppm, NO is 400ppm, and all the other are nitrogen, 100 ℃ of flue-gas temperatures, 1 atmospheric pressure of pressure.
Hydrogen peroxide and sodium chlorite are configured to the oxidant that the mass fraction of the efficient oxidation composition is 10% (in oxidant except hydrogen peroxide and sodium chlorite according to 2: 1 (mol ratio), surplus is water), control oxidant pH at 5-6 simultaneously, to add mass fraction be 0.005% iron chloride (be iron chloride account for oxidant gross mass 0.005%), the liquid-gas ratio of liquid phase oxidation is 3-6L/m
3.
Adopt calcium hydroxide as desulfurizing agent, the total liquid-gas ratio of first grade desulfurizing and two-grade desulfurizing is 10L/m
3(first grade desulfurizing is 6L/m
3, two-grade desulfurizing is 4L/m
3), utilize technique of the present invention, carry out desulphurization denitration.First grade desulfurizing efficiency can reach 70%, and after oxidation, in flue gas, NO is 8ppm, NO
2for 190ppm, after two-grade desulfurizing denitration, exit SO
2concentration 20ppm left and right, NOx is 15ppm left and right.Overall desulfuration efficiency 98%, denitration efficiency can reach 96.2%.
At 5m
3on the experimental simulation device of/h scale, simulate flue gas desulfurization and denitrification process.Exhaust gas volumn 5m
3/ h, flue gas composition is as follows: O
2be 5%, SO
2for 1000ppm, NO is 400ppm, and all the other are nitrogen, 100 ℃ of flue-gas temperatures, 1 atmospheric pressure of pressure.
Sodium chlorite solution and liquor natrii hypochloritis are configured to the oxidant that the mass fraction of the efficient oxidation composition is 5% (in oxidant except hydrogen peroxide and sodium chlorite according to 0.5: 1 (mol ratio), surplus is water), to add mass fraction be 0.001% manganese chloride (be manganese chloride account for oxidant gross mass 0.001%), regulate oxidant pH to 5-6, the liquid-gas ratio of liquid phase oxidation is 3-6L/m
3.
Adopt calcium hydroxide as desulfurizing agent, the total liquid-gas ratio of first grade desulfurizing and two-grade desulfurizing is 10L/m
3(first grade desulfurizing is 6L/m
3, two-grade desulfurizing is 4L/m
3), utilize technique of the present invention, carry out desulphurization denitration.First grade desulfurizing efficiency can reach 70%, and after oxidation, in flue gas, NO is 80ppm, NO
2for 187ppm, after two-grade desulfurizing denitration, exit SO
2concentration 20ppm left and right, NOx is 89ppm left and right.Overall desulfuration efficiency 98%, denitration efficiency can reach 77.8%.
Embodiment 4
At 5m
3on the experimental simulation device of/h scale, simulate flue gas desulfurization and denitrification process.Exhaust gas volumn 5m
3/ h, flue gas composition is as follows: O
2be 5%, SO
2for 1000ppm, NO is 400ppm, and all the other are nitrogen, 100 ℃ of flue-gas temperatures, 1 atmospheric pressure of pressure.
Oxidant that the mass fraction that sodium chlorite solution and liquor natrii hypochloritis are configured to the efficient oxidation composition according to 0.5: 1 mol ratio is 10% is (in oxidant except hydrogen peroxide and sodium chlorite, surplus is water), to add mass fraction be 0.001% manganese chloride (be manganese chloride account for oxidant gross mass 0.001%), regulate oxidant pH to 5-6, the liquid-gas ratio of liquid phase oxidation is 3-6L/m
3.
Adopt calcium hydroxide as desulfurizing agent, the total liquid-gas ratio of first grade desulfurizing and two-grade desulfurizing is 10L/m
3(first grade desulfurizing is 6L/m
3, two-grade desulfurizing is 4L/m
3), utilize technique of the present invention, carry out desulphurization denitration.First grade desulfurizing efficiency can reach 70%, and after oxidation, in flue gas, NO is 40ppm, NO
2for 195ppm, after two-grade desulfurizing denitration, exit SO
2concentration 10ppm left and right, NOx is 45ppm left and right.Overall desulfuration efficiency 99%, denitration efficiency can reach 88.7%.
The combined desulfurization and denitrification process of liquid phase oxidation multistage absorption of the present invention, at exhaust gas volumn 10000m
3/ h, SO
2for 3000mg/Nm
3left and right, O
2for 6-8%, NO is 200-300ppm, flue-gas temperature 120-150 ℃.
Set up as the desulfuring and denitrifying apparatus of Fig. 1, sodium chlorite solution and liquor natrii hypochloritis add according to 0.5: 1.5 ratio, in initial oxidation agent, the mass concentration of the efficient oxidation composition is controlled at 10% (in oxidant except hydrogen peroxide and sodium chlorite, surplus is water), pH is controlled at 5-6, to add mass fraction be 0.001% manganese chloride (be manganese chloride account for oxidant gross mass 0.001%), the liquid-gas ratio of oxidation is 3-6L/m
3.
Adopt lime stone as desulfurizing agent, the total liquid-gas ratio of first grade desulfurizing and two-grade desulfurizing is 10L/m
3(first grade desulfurizing is 6L/m
3, two-grade desulfurizing is 4L/m
3), carry out desulphurization denitration.First grade desulfurizing efficiency can reach 65%, and after oxidation, in flue gas, NO is 10ppm, NO
2for 80-90ppm, after two-grade desulfurizing denitration, exit SO
2concentration 100ppm left and right, NOx is about 15ppm.Overall desulfuration efficiency 97% left and right, denitration efficiency can reach more than 90%.
Claims (3)
1. a flue gas desulfurization and denitration technique for liquid phase oxidation multistage absorption, is characterized in that, comprising:
(1) desulfurizing agent and flue gas haptoreaction are carried out to pre-desulfurization, desulfurizing agent absorbs the part sulfur dioxide in flue gas, obtains desulfurization slurry;
(2) flue gas after pre-desulfurization is carried out to liquid phase oxidation and partially absorbs, oxidation of nitric oxide in flue gas is become to nitrogen dioxide, the oxidant of described liquid phase oxidation is at least one the aqueous solution in hydrogen peroxide, chlorite and hypochlorite, in described oxidant, the efficient oxidation composition accounts for the 5-35% of gross mass, in described oxidant, be added with the metal ion that accounts for oxidant gross mass 0.001-0.01%, metal ion is at least one in iron ion, manganese ion, copper ion and magnesium ion, and the liquid-gas ratio of liquid phase oxidation is 3-7 L/m
3, the temperature of described liquid phase oxidation is 40-50 ℃;
(3) by the desulfurization slurry haptoreaction in the flue gas after peroxidating and step (1), the nitrogen dioxide in absorption flue gas and remaining sulfur dioxide;
The pH value of described oxidant is 4-7;
Realize the device of described flue gas desulfurization and denitration technique: comprise desulphurization denitration tower (9), described desulphurization denitration tower (9) bottom is provided with the tower reactor (12) for holding described desulfurizing agent and desulfurization slurry, the top of described tower reactor (12) sets gradually the first spraying layer (2) that is useful on the described desulfurizing agent of spray from the bottom to top, the sieve plate layer (3) that carries out liquid phase oxidation for flue gas is contacted with oxidant, for spraying second spraying layer (4) of described oxidant and for spraying the 3rd spraying layer (6) of described desulfurization slurry, between described sieve plate layer (3) and the second spraying layer (4), be communicated with by being positioned at the outer oxidizer slurry tank (11) of desulphurization denitration tower (9), described the first spraying layer (2) and the 3rd spraying layer (6) are communicated with tower reactor (12) by external circulating pump respectively,
The center that is provided with between the 3rd described spraying layer (6) and the second spraying layer (4) is to the dividing plate (5) of lower recess and be communicated with the downspout (16) of dividing plate (5) bottom and tower reactor (12);
Described dividing plate (5) is by some layers of reducing annulus upper and lower nested composition, and leaves the space of passing for flue gas.
2. realize the device of flue gas desulfurization and denitration technique as claimed in claim 1 for one kind, comprise desulphurization denitration tower (9), it is characterized in that, described desulphurization denitration tower (9) bottom is provided with the tower reactor (12) for holding described desulfurizing agent and desulfurization slurry, the top of described tower reactor (12) sets gradually the first spraying layer (2) that is useful on the described desulfurizing agent of spray from the bottom to top, the sieve plate layer (3) that carries out liquid phase oxidation for flue gas is contacted with oxidant, for spraying second spraying layer (4) of described oxidant and for spraying the 3rd spraying layer (6) of described desulfurization slurry, between described sieve plate layer (3) and the second spraying layer (4), be communicated with by being positioned at the outer oxidizer slurry tank (11) of desulphurization denitration tower (9), described the first spraying layer (2) and the 3rd spraying layer (6) are communicated with tower reactor (12) by external circulating pump respectively,
The center that is provided with between the 3rd described spraying layer (6) and the second spraying layer (4) is to the dividing plate (5) of lower recess and be communicated with the downspout (16) of dividing plate (5) bottom and tower reactor (12);
Described dividing plate (5) is by some layers of reducing annulus upper and lower nested composition, and leaves the space of passing for flue gas.
3. device according to claim 2, is characterized in that, described oxidizer slurry tank (11) top is provided with the oxidant storage tank (10) by pipeline connection.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210067173.6A CN102580496B (en) | 2012-03-14 | 2012-03-14 | Liquid-phase oxidation multistage absorbed flue gas desulfurization and denitrification technology and device |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210067173.6A CN102580496B (en) | 2012-03-14 | 2012-03-14 | Liquid-phase oxidation multistage absorbed flue gas desulfurization and denitrification technology and device |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102580496A CN102580496A (en) | 2012-07-18 |
| CN102580496B true CN102580496B (en) | 2014-05-21 |
Family
ID=46470055
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201210067173.6A Active CN102580496B (en) | 2012-03-14 | 2012-03-14 | Liquid-phase oxidation multistage absorbed flue gas desulfurization and denitrification technology and device |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102580496B (en) |
Families Citing this family (28)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103230733B (en) * | 2013-04-17 | 2016-03-02 | 中悦浦利莱环保科技有限公司 | The device of a kind of liquid phase catalytic oxidation flue gas desulfurization and denitrification integration and technique |
| CN103768911A (en) * | 2014-02-11 | 2014-05-07 | 汤宁 | Flue gas purification device and method capable of realizing desulfurization, denitrification and respective recovery |
| CN103801178A (en) * | 2014-03-06 | 2014-05-21 | 汤宁 | Smoke purification device and method with integration of desulfuration, denitration, dust removal and mercury removal |
| CN103977679A (en) * | 2014-05-13 | 2014-08-13 | 东南大学 | Grading oxidation and absorption type method for simultaneous desulphurization and denitration of sintering flue gas, and system |
| CN104001419A (en) * | 2014-06-09 | 2014-08-27 | 鞍钢股份有限公司 | Seawater desulphurization and denitrification system and method for sintering flue gas |
| CN104190223A (en) * | 2014-09-22 | 2014-12-10 | 黄盛珠 | Liquid phase oxidation flue gas desulfurization, denitration and absorption technology and device |
| CN105032138B (en) * | 2015-06-05 | 2017-07-04 | 中晶环境科技股份有限公司 | Flue gas controller and method |
| CN105457475B (en) * | 2015-12-30 | 2016-08-17 | 江苏中建材环保研究院有限公司 | Flue gas desulfurization and denitrification systematization device |
| CN106390711B (en) * | 2016-06-21 | 2022-07-15 | 秦皇岛玻璃工业研究设计院有限公司 | Denitration oxidant, denitration equipment and denitration method for glass melting furnace flue gas |
| CN106621755A (en) * | 2017-01-11 | 2017-05-10 | 长春工业大学 | Integral technology using liquid phase to jointly absorb glue gas for simultaneous desulfurizing and denitration |
| CN106925097A (en) * | 2017-04-28 | 2017-07-07 | 陶汉中 | It is a kind of based on liquid phase oxidation to the combined column and its technique of flue gas desulfurization and denitrification |
| CN106975337A (en) * | 2017-04-28 | 2017-07-25 | 包训祥 | Chlorine dioxide gaseous oxidation denitration integrated device and its technique |
| CN107051168B (en) * | 2017-06-14 | 2023-10-13 | 中冶京诚工程技术有限公司 | Integrated device and method for low-temperature denitration of flue gas |
| CN107174931B (en) * | 2017-07-04 | 2020-09-25 | 苏州华商新能源有限公司 | High-efficient flue gas processing apparatus of power is regarded as to ethernet |
| CN107088355B (en) * | 2017-07-04 | 2020-10-23 | 苏州华商新能源有限公司 | Multistage waste gas treatment device and method using solar energy as power |
| CN107638778B (en) * | 2017-09-28 | 2020-11-20 | 华夏碧水环保科技有限公司 | Spraying deodorization device |
| CN107983133A (en) * | 2017-12-26 | 2018-05-04 | 上海亨远船舶设备有限公司 | A kind of system and method for flue gas wet type combined desulfurization and denitration |
| 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 |
| CN108452662A (en) * | 2018-06-13 | 2018-08-28 | 山西梵净环保工程有限公司 | Industrial smoke denitration desulfurization dedirt waste heat recovery integral method and equipment |
| CN109621669A (en) * | 2018-12-14 | 2019-04-16 | 四川龙蟒钛业股份有限公司 | A kind of method of promotor auxiliary sulfuric acid titanium white calcining tail gas desulfurization denitration |
| CN109621670A (en) * | 2018-12-14 | 2019-04-16 | 四川龙蟒钛业股份有限公司 | A kind of method of promotor aid in treatment sulfuric acid titanium white calcining tail gas |
| CN110237673A (en) * | 2019-06-24 | 2019-09-17 | 福建省锅炉压力容器检验研究院 | Sodium chlorate and lime stone mixed serum simultaneous SO_2 and NO removal method |
| CN113117498A (en) * | 2019-12-30 | 2021-07-16 | 中晶新材料有限公司 | Integrated process for flue gas treatment and cementing material preparation |
| CN113117481A (en) * | 2019-12-30 | 2021-07-16 | 中晶环境科技股份有限公司 | Method for desulfurization and denitrification by using chlorine dioxide |
| CN113117480A (en) * | 2019-12-30 | 2021-07-16 | 中晶环境科技股份有限公司 | Method for flue gas desulfurization and denitration by using calcium-based absorbent |
| CN114053854A (en) * | 2021-11-12 | 2022-02-18 | 湖南立泰环境工程有限公司 | VOCs desulfurization and concentration regulation jar |
| CN114288835B (en) * | 2021-12-02 | 2023-04-14 | 赛鼎工程有限公司 | Structure and method for improving oxidation degree and efficiency in 65% -68% high-concentration dilute acid preparation process |
| CN114259852A (en) * | 2021-12-23 | 2022-04-01 | 青岛蓝博环境科技有限公司 | Sludge carbonization waste gas treatment process |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101385942B (en) * | 2008-10-13 | 2011-04-13 | 浙江天蓝环保技术有限公司 | Liquid-phase oxidation-absorption two-stage wet method flue-gas denitration technique |
| CN101745305B (en) * | 2010-01-24 | 2013-03-20 | 华北电力大学（保定） | Method for removing various gaseous pollutants from smoke gas |
| CN201783286U (en) * | 2010-08-05 | 2011-04-06 | 杭州洁天环保科技有限公司 | Rotating-stream-tray tower |
-
2012
- 2012-03-14 CN CN201210067173.6A patent/CN102580496B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN102580496A (en) | 2012-07-18 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102580496B (en) | Liquid-phase oxidation multistage absorbed flue gas desulfurization and denitrification technology and device | |
| CN102343212B (en) | Denitration process combining co-oxidation of ozone and hydrogen peroxide with wet absorption | |
| CN103566725B (en) | A kind of circulating fluid bed semi-drying method combined desulfurization and denitration mercury removal device and method | |
| CN101352646B (en) | Flue gas denitration method using ultraviolet light double action | |
| CN203750390U (en) | Calcium and chlorine dioxide-based three-section flue gas simultaneous desulfurization and denitration system | |
| CN105311946A (en) | Flue gas denitration and desulfuration washing system and denitration and desulfuration method | |
| CN203108418U (en) | Wet process flue gas desulfurization and denitrification integrated device | |
| CN205832945U (en) | A kind of nitrous oxides exhaust gas that reclaims prepares the device of dust technology | |
| CN105148698A (en) | Boiler flue gas desulfurization and denitrification system | |
| CN104056538B (en) | Flue gas purifying system and method with integration of desulfurization and denitrification | |
| CN106540524A (en) | For the semi-dry desulfurization and denitrification device and desulfurizing and denitrifying process of high sulfur concentration flue gas | |
| CN209530493U (en) | A kind of system of Industrial Boiler flue gas desulfurization and denitrification | |
| CN203935765U (en) | A kind of flue gas purification system of integrated desulfurizing denitration | |
| CN111514736A (en) | Flue gas desulfurization and denitrification system and method combining ozone oxidation with ammonia spraying | |
| CN106925093B (en) | Composite ship ballast water and ship waste gas treatment system | |
| CN106731601B (en) | A kind of solwution method flue gas desulfurization and denitrification integrated apparatus | |
| CN105289236A (en) | Synchronous desulfurization and denitrification process for reinforcing sintered flue gas based on NO oxidization by hydrogen peroxide and potassium permanganate | |
| CN113117484A (en) | Dry-method integrated flue gas desulfurization and denitrification process | |
| CN109647146A (en) | A kind of system and method for Industrial Boiler flue gas desulfurization and denitrification | |
| CN106925117A (en) | The removing means and method of nitrate in a kind of industrial tail gas oxidation and denitration recirculated water | |
| CN105833693A (en) | Device for serial desulfurization and denitrification with limestone-gypsum process and SCR (selective catalytic reduction) process | |
| CN104941412A (en) | Flue gas desulphurization-denitration integrated device and method | |
| CN105457464A (en) | Sintering flue gas desulfurization and denitrification technology | |
| CN104941417A (en) | Flue gas treatment device and method | |
| CN212492355U (en) | Ozone oxidation is SOx/NOx control system of ammonia process in coordination |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |