CN102580496A - 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
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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 the smoke gas treatment technical field, be specifically related to the flue gas desulfurization and denitration technique and the device of the multistage absorption of a kind of liquid phase oxidation.
Background technology
Along with improving constantly of national requirements for environmental protection, standard limit of smog release increasingly stringent, flue gas desulfurization and denitrification become urgent day by day.Main flue gas desulfurization technique has wet processings such as lime/lime stone-gypsum method, magnesium method, ammonia process and semidry method, dry desulfurizing process.And denitration technology has following several kinds: selective catalytic reduction (SCR), SNCR method (SNCR), SNCR and SCR combination method (SNCR-SCR).But substep denitration sulfur removal technology is complicated, and equipment is various, and the investment operating cost is high, safeguards inconvenience.Therefore increasing expert also is simultaneously the direction of national policy guiding in the technology of developmental research desulfurization and denitrification integral.
Publication number is for disclosing a kind of method and apparatus that utilizes hydrogen peroxide to reduce sulfur dioxide, nitrogen oxide and heavy metals emission in the flue gas stream in the Chinese patent document of 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 be heated to ability oxidation NO about 500 ℃ with hydrogenperoxide steam generator, consumes significant amount of energy, has increased operating cost.
Publication number is to disclose a kind of ammonia flue gas method of desulphurization denitration simultaneously in the Chinese patent document of CN101934191A, is absorption liquid with ammoniacal liquor, adopts the multilayer spray to absorb nitrogen oxide and sulfur dioxide in the flue gas.Though this method also can remove sulfur in smoke and nitrogen oxide; But also there is following shortcoming: first; Be that the simple ammoniacal liquor that passes through repeatedly absorbs flue gas, do not take oxidation measure, and have 95% to be the nitric oxide of difficult absorption in the flue gas in the nitrogen oxide flue gas; Not oxidised directly absorbs, and its denitration efficiency certainly will be not high; The second, the accessory substance sulfate and the nitrate of desulphurization denitration mix, and reclaim 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 technology is used the NO in the ozone gas phase oxidation flue gas, utilizes ammoniacal liquor to absorb sulfur in smoke and nitrogen oxide then.This technology carries out the nitrogen oxide in the flue gas to carry out desulphurization denitration again after the oxidation; Its denitration efficiency can increase; But the ozone gas phase oxidation that this technology is used, the first, ozone need use a large amount of electric power to generate; Every kilogram of ozone expends electric weight greatly about 10-16Kw, and this has improved operating cost undoubtedly; The second, ozone also may the oxidation flue gas in SO
2, causing the waste of oxidant, the sulfur trioxide that generates simultaneously then can generate acid mist; The 3rd, employing be gaseous oxidation, gaseous oxidation is owing to be to spray into gaseous oxidizer; Air-tightness is had certain requirement, and careless slightly easy generation oxidizing gas is revealed and is caused accident, and secondly gaseous oxidation requires oxidizing gas and flue gas to mix fully rapidly; Specification requirement is high, and therefore, gaseous oxidation is high to the requirement of equipment; The control of technology is complicated, and the enterprise 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 technology; The solution that adopts one or more mixtures in potassium permanganate, sodium chlorite, clorox, calcium hypochlorite, hydrogen peroxide solution, the chlorine dioxide is as oxidant; Make nitric oxide and oxidant haptoreaction in the flue gas; Partial oxygen changes into after the nitrogen dioxide, utilizes alkali lye to absorb the nitrogen oxide in the flue gas after peroxidating, produces corresponding nitrite.This method adopts liquid phase oxidation, and technological process has been simplified in gaseous oxidation relatively; Reduced the denitration cost, but the sulfur dioxide that contains in the 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, sulfur in smoke can not well be removed simultaneously very much, also need increase corresponding sulfur removal technology.
Therefore, developing a kind of method for oxidation of the oxide of nitrogen oxide efficiently, and manage to reduce the oxygenation efficiency of SO 2 from fume, reduce the oxidant consumption, reduce operating cost, is the improved direction of combined desulfurization and denitrification process, helps the application and the popularization of this technology.
Summary of the invention
The invention provides the flue gas desulfurization and denitration technique and the device of the multistage absorption of a kind of liquid phase oxidation, strengthen the utilization rate of flue gas oxidant, improved the denitration efficiency of flue gas.
The flue gas desulfurization and denitration technique of the multistage absorption of a kind of liquid phase oxidation comprises:
(1) desulfurizing agent and flue gas haptoreaction are carried out preparatory desulfurization, desulfurizing agent absorbs the part sulfur dioxide in the flue gas, obtains desulfurization slurry;
(2) flue gas after the preparatory desulfurization is carried out liquid phase oxidation and partially absorb, the oxidation of nitric oxide in the flue gas is become nitrogen dioxide, the oxidant of described liquid phase oxidation is at least a aqueous solution in hydrogen peroxide solution, chlorite and the hypochlorite;
(3) flue gas that will be after peroxidating and the desulfurization slurry haptoreaction in the step (1) absorb nitrogen dioxide and remaining sulfur dioxide in the flue gas.
Contain a large amount of sulfur dioxide and nitrogen oxide in the flue gas from boiler flue, nitrogen oxide is main with nitric oxide mainly, and nitric oxide is not easy to be absorbed;, it is absorbed more easily when being oxidized to nitrogen oxide such as the nitrogen dioxide of high valence state; At first flue gas is carried out one-level and absorb, remove most sulfur dioxide in the flue gas, obtain being rich in the desulfurization slurry of inferior sulfate radical after the sulfur in smoke of desulfurizing agent absorption simultaneously through desulfurizing agent; And then flue gas carried out efficient liquid phase oxidation; Oxidation of nitric oxide in the flue gas is become nitrogen dioxide, and oxidized dose of part absorbs and forms the nitrate slurries, and this nitrate can obtain byproduct such as fertilizer etc. after through subsequent treatment; Is example with chlorite as oxidant, and the reaction equation of concrete oxidation reaction is following:
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
Utilizing desulfurization slurry after the first grade desulfurizing that flue gas is carried out secondary at last absorbs; Remove nitrogen dioxide and remaining sulfur dioxide in the flue gas; Form the sulfate slurries; These sulfate slurries obtain accessory substance such as gypsum through after the subsequent treatment, and the reaction equation that when secondary absorbs nitrogen dioxide is following:
4SO
3 2-+2NO
2+→N
2+4SO
4 2-
The nitrate slurries and the sulfate slurries that obtain in the flue gas desulfurization and denitrification process separate, and conveniently respectively it are reclaimed.
Described chlorite can select for use sodium chlorite, hypochlorite can select at least a in clorox, the calcium hypochlorite for use.
When carrying out liquid phase oxidation, need oxidant be diluted to the aqueous solution that contains finite concentration the efficient oxidation composition, as a kind of preferred, the efficient oxidation composition accounts for the 5-35% of gross mass, more preferably 5-10% in the oxidant described in the step (2).Described the efficient oxidation composition is meant the gross mass of solute in the oxidant (aqueous solution); When for example oxidant is the chlorite aqueous solution; The efficient oxidation composition promptly is chloritic quality; When oxidant was the mixed aqueous solution of chlorite and hypochlorite, the efficient oxidation composition promptly was the gross mass of chlorite and hypochlorite.
For improving the oxidation characteristic of oxidant, also be added with the metal ion that accounts for oxidant gross mass 0.001-0.01% in the said oxidant, be preferably 0.001-0.005%.Described metal ion is at least a in iron ion, manganese ion, copper ion and the magnesium ion.Described iron ion can be selected iron chloride for use, and described manganese ion can be selected manganese chloride for use, and described magnesium ion can be selected magnesium sulfate for use, and described copper ion can be selected copper sulphate for use.The catalyst such as iron ion manganese ion copper ion that add trace; Can effectively improve the efficient of oxidation; Hydrogen peroxide, hypochlorite, chlorite etc. can produce active hydroxyl free radical faster under the effect of catalyst; Thereby cause and the propagation radical chain reaction, accelerate the oxidation of nitrogen oxide, can the oxidation of nitric oxide more than 95% in the flue gas be become the nitrogen oxide of high valence state.
As a kind of optimized technical scheme, the pH value of described oxidant is 4-7.When being higher than this scope, the oxidisability of oxidant reduces, and the effect of oxidation NO Absorption weakens.When being lower than this scope, oxidant self decomposes acceleration, produces a large amount of chlorine, and gases such as chlorine dioxide are overflowed, and cause the waste of oxidant.Mainly through absorbing sour gas sulfur dioxide and nitrogen oxide reduction pH value in the flue gas, the oxidant that interpolation sodium chlorite or clorox etc. are alkalescence improves the pH value in the control of pH value.
In the process of liquid phase oxidation, need its reaction temperature of control, as a kind of optimized technical scheme, the temperature of described liquid phase oxidation is 40-50 ℃.In this temperature range, oxidant is moderate to the absorption and the oxidizing reaction rate of nitrogen oxide, and the side reaction of selfdecomposition does not take place basically.Input gas temperature is generally at 80-150 ℃, through the suitable liquid-gas ratio of desulfurization in advance, and the pipeline tower jar at liquid phase oxidation reaction place is incubated, and gets final product satisfied temperature requirement.
The liquid-gas ratio of liquid phase oxidation is regulated according to the content of nitrogen oxide in the flue gas, as a kind of preferred, and the liquid-gas ratio control 3-7L/m of described liquid phase oxidation
3When the content of nitrogen oxide in the flue gas increases, suitably improve liquid-gas ratio, strengthen the spray internal circulating load of oxidant, strengthen absorption to nitrogen oxide.When the content of nitrogen oxide in the flue gas descends, can reduce liquid-gas ratio, reduce the spray internal circulating load of oxidant, practice thrift the consumption of oxidant.
Desulfurizing agent described in the step (1) is ammoniacal liquor, seawater, magnesium hydroxide or lime stone slurry; The pH value of desulfurizing agent and liquid-gas ratio are provided with according to the content and the selected desulfurizing agent kind of sulfur dioxide in flue gas; As a kind of optimized technical scheme; Described desulfurizing agent is selected calcium hydroxide or lime stone slurry, and its pH value is controlled in the 4-6 scope, and total liquid-gas ratio of step (1) and step (3) desulfurization is controlled at 3-15L/m
3In the scope, the liquid-gas ratio in the general step (1) than the liquid-gas ratio in the step (3) slightly greatly once, removal sulfur dioxide as much as possible prevents that sulfur dioxide from consuming oxidant, for example when total liquid-gas ratio be 10L/m
3The time, the liquid-gas ratio in the step (1) is 6L/m
3, the liquid-gas ratio in the step (3) is 4L/m
3
The present invention also provides a kind of device of realizing like said desulfurizing and denitrifying process; Comprise the desulphurization denitration tower; Said desulphurization denitration tower bottom is provided with the tower still that is used to hold said desulfurizing agent and desulfurization slurry; The top of described tower still sets gradually first spraying layer that is useful on the said desulfurizing agent of spray, be used to that flue gas is contacted with the oxidant sieve plate layer that carries out liquid phase oxidation, the 3rd spraying layer that is used to spray second spraying layer of said oxidant and is used to spray said desulfurization slurry from the bottom to top; Be communicated with through being positioned at the outer oxidizer slurry jar of desulphurization denitration tower between the described sieve plate layer and second spraying layer, described first spraying layer and the 3rd spraying layer are communicated with the tower still through external circulating pump respectively.
Flue gas moves from the bottom to top; Through first spraying layer; Desulfurizing agent in the tower still is squeezed into first spraying layer through external circulating pump, and its desulfurization slurry that contains inferior sulfate radical falls in the tower still behind the circulated sprinkling, and the oxidizer slurry in the oxidizer slurry jar is squeezed into second spraying layer through circulating pump; Spray downwards to the sieve plate layer; Flue gas continues to move upward and upwards continues reaction with second spraying layer spray oxidant down through sieve plate layer and oxidizer slurry blistering reaction continued on the sieve plate layer, and flue gas continues to make progress and the 3rd spraying layer sprays the desulfurization slurry haptoreaction of getting off, and discharges after the demist of the layer of process demist at last.
In order to make the sulfate slurries and the nitrate slurries that obtain in the flue gas processing procedure can carry out subsequent treatment more easily; Need both be separated; Desulfurization slurry through behind the first spraying layer spray washing falls into the tower still; Slurries through behind the second spraying layer spray washing fall into the sieve plate layer; Therefore be back in the oxidizer slurry jar through the return duct between sieve plate layer and the oxidizer slurry jar then, need to separate through the slurries behind the slurries behind the 3rd spraying layer spray washing and the second spraying layer spray washing perhaps in drainage to the tower still.As a kind of optimized technical scheme, be provided with between described the 3rd spraying layer and second spraying layer to the dividing plate of lower recess with is communicated with the downspout of dividing plate bottom, slurries drainage to the tower still under through dividing plate and downspout the 3rd spraying layer being sprayed with the tower still; A kind of preferred technical scheme; Described dividing plate is by several layers reducing annulus nested composition up and down, and leaves the space that supplies flue gas to pass, and liquid flows to one deck annulus down in the annulus flows inside by the last layer annulus; In downspout, flue gas then moves upward from the space between the annulus.
Replenishing of oxidant is provided with the oxidant storage tank through pipeline connection above the described oxidizer slurry jar for ease, and its pipeline is provided with valve.The oxidant medicament storage is sent in the oxidizer slurry jar and is diluted in the oxidant storage tank.
For satisfying the technological requirement of flue gas desulfurization and denitration technique, as a kind of optimized technical scheme, the number of plies of described first spraying layer, second spraying layer, the 3rd spraying layer and demist layer is several layers.
Beneficial effect of the present invention:
(1) integrates desulphurization denitration, and be integrated in the absorption tower, simplified technological process greatly, reduced the floor space of equipment, reduced investment cost.
(2) desulfurization in advance before the denitration oxidation is removed behind the most sulfur dioxide carrying out the 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, the saving operating cost.
(3) adopt liquid phase composite denitration oxidant efficiently, and add the metal ion catalysis oxidation, can the oxidation of nitric oxide more than 95% in the flue gas be become the nitrogen oxide of high valence state, and absorb, reach higher denitration efficiency through the two-stage denitration.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, nitrogen oxide after the absorption oxidation and remaining sulfur dioxide, the treatment of wastes with processes of wastes against one another reduces the consumption of absorbent, and the nitrogen oxide that this is a part of is thoroughly innoxious, becomes clean nitrogen.
(5) desulfurizing byproduct and denitration accessory substance separately reclaim, and simplify the recovery technology of accessory substance, reduce cost;
(6) adopt liquid phase oxidation technique to replace gaseous oxidation technology, reduce investment and operating cost, simplified technological process simultaneously, enhancing operability.
Description of drawings
Fig. 1 is a structural representation of the present invention.
The specific embodiment
Absorption tower as shown in Figure 1, that desulphurization denitration tower 9 adopts spray-sieve plate to combine, it is stainless steel material that material is adopted on the absorption tower; Acid and alkali-resistance is anti-oxidant, and the top on absorption tower is provided with exhanst gas outlet 8, and the absorption tower inner bottom part is provided with tower still 12; The top is provided with demist layer 7; Between the demist layer 7 at the tower still 12 of bottom and top, set gradually first spraying layer 2, sieve plate layer 3, second spraying layer 4 and the 3rd spraying layer 6 from the bottom to top, certain at interval distance between each layer is provided with smoke inlet 1 on the tower wall between the tower still 12 and first spraying layer 2; Between 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, and the center is protruded the formation pit downwards, and the bottom of pit is communicated with downspout 16; Slurry pipe 16 passes second spraying layer 4, sieve plate layer 3 and first spraying layer 2 downwards successively, will be by in slurries drainage to the tower still 12 under the 3rd spraying layer 6 sprays.
Dividing plate 5 is made up of multilayer reducing annulus, and is nested up and down, and reserves a part of space, and liquid flows to one deck annulus down in the annulus flows inside by the last layer annulus, and until downspout 16, flue gas then moves upward from the space between the annulus.
Be communicated with through external circulating pump 1 between tower still 12 and first spraying layer 2, the inlet of circulating pump 1 is communicated with tower still 12, and outlet is communicated with first spraying layer 2; Be communicated with through external circulating pump 2 15 between tower still 12 and the 3rd spraying layer 6, the inlet of circulating pump 2 15 is communicated with tower still 12, and outlet is communicated with the 3rd spraying layer 6.
Oxidizer slurry jar 11 is set outside the absorption tower; The installation site of oxidizer slurry jar 11 is lower than the sieve plate layer 3 in the absorption tower; In the oxidizer slurry jar 11 agitator is set; Above oxidizer slurry jar 11,, be communicated with the inlet connection oxidizer slurry jar 11 of circulating pump 3 14 between oxidizer slurry jar 11 and second spraying layer 4 through external circulating pump 3 14 through the pipeline connection oxidant storage tank 10 of band valve; Outlet is communicated with second spraying layer 4, is communicated with through return line between oxidizer slurry jar 11 and the sieve plate layer 3.
Tower still 12 places are communicated with air and blast device and desulfurizing agent supplementary device, also are connected with (all not shown among the figure) such as gypsum cyclone, gypsum dehydration equipment and drying equipments the exhanst gas outlet 8 final chimney (not shown)s that are communicated with successively.
The percent opening of sieve plate layer 3 (perforated area accounts for the ratio of the gross area) is 10-30%; First spraying layer 2, second spraying layer 4 and the 3rd spraying layer 6 are by plurality of pipelines and be arranged on the pipeline and form with the plurality of nozzles 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, when being set to multilayer, corresponding increasing seeks circulating pump.
Demist layer 7 is made up of upper and lower layer demist net and the cleaning fluid parts between upper and lower layer demist net, and the moisture with in the flue gas that can be in full force and effect is separated, and the number of plies of demist layer can be set to one deck as required, also can be set to multilayer.
Technological process of the present invention is following:
Adopt absorption tower as shown in Figure 1, the desulfurizing and denitrifying process of the multistage absorption of liquid phase oxidation of embodiment of the present invention.Flue gas gets into from smoke inlet 1.Flue gas carries out first grade desulfurizing with the desulfurizing agent counter current contacting that first spraying layer 2 sprays from bottom to top; Sulfur in smoke is absorbed; The desulfurization slurry of sulfite ion is rich in formation; Desulfurization slurry then drops among the tower still 12 at the bottom of the tower, and through circulating pump one 13 circulated sprinklings, removes the flue gas of most sulfur dioxide.
Flue gas then continues upwards; Pass sieve plate layer 3; After liquid phase oxidation agent bubbling gas-liquid contacts, and carry out liquid phase oxidation with the absorption liquid that sprays (oxidant) counter current contacting, the nitric oxide in the flue gas is oxidized to the nitrogen oxide of nitrogen dioxide and higher valence state; Part is stayed in the oxidant, and remaining few part is stayed in the flue gas.Oxidant keeps the liquid level of 20-40cm on sieve plate, excess oxidant flows back in the oxidizer slurry jar 11, returns second spraying layer, 4 sprays through circulating pump 3 14 again.
In the flue gas of peroxidating, contain nitrogen dioxide and a spot of sulfur dioxide, pass the desulfurization slurry counter current contacting that dividing plate 5 and the 3rd spraying layer 6 spray and carry out the secondary desulfurization, absorb residue sulfur dioxide and nitrogen oxide, reach higher denitrification efficiency.Collect in the middle downspout 16 through dividing plate 5 behind desulfurization slurry absorbing sulfur dioxide and the nitrogen dioxide, flow in the tower still 12.
Through clean flue gas process demist layer 7 behind the desulphurization denitration, remove entrained drip at last, enter in the atmosphere.
In tower still 12, replenish an amount of desulfurizing agent, proceed desulphurization circulating.
Bubbling air in tower still 12; Sulfite oxidation is become sulfate, send into follow-up equipment then and handle, absorbed the part nitrogen oxide in the slurries after the oxidation; There is nitrate to generate; These slurries are back in the oxidizer slurry jar 11 by sieve plate layer 3, mend the oxidant continued and participate in circulation, and the final slurries that contain nitrate are delivered to follow-up equipment and handled.
Data such as smoke components all adopt the infrared flue gas analyzer of madur to measure in following examples.
Embodiment 1
At 5m
3Simulation flue gas desulfurization and denitrification process on the experimental simulation device of/h scale.Exhaust gas volumn 5m
3/ h, flue gas composition is following: O
2Be 5%, SO
2Be 1000ppm, NO is 400ppm, and all the other are nitrogen, 100 ℃ of flue-gas temperatures, 1 atmospheric pressure of pressure.
The mass fraction that hydrogen peroxide and sodium chlorite are configured to the efficient oxidation composition according to 1: 1 (mol ratio) is that 10% oxidant is (in the oxidant except that hydrogen peroxide and sodium chlorite; Surplus is a water); Control oxidant pH simultaneously at 5-6; Add mass fraction and be 0.005% iron chloride (be iron chloride account for the 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 secondary desulfurization is 10L/m
3(first grade desulfurizing is 6L/m
3, the secondary desulfurization is 4L/m
3), utilize technology of the present invention, carry out desulphurization denitration.First grade desulfurizing efficient can reach 70%, after the oxidation in the flue gas NO be 3ppm, NO
2Be 190ppm, behind the secondary desulphurization denitration, exit SO
2About concentration 20ppm, NOx is about 10ppm.Overall desulfuration efficiency 98%, denitration efficiency can reach 97.5%.
Embodiment 2
At 5m
3Simulation flue gas desulfurization and denitrification process on the experimental simulation device of/h scale.Exhaust gas volumn 5m
3/ h, flue gas composition is following: O
2Be 5%, SO
2Be 1000ppm, NO is 400ppm, and all the other are nitrogen, 100 ℃ of flue-gas temperatures, 1 atmospheric pressure of pressure.
The mass fraction that hydrogen peroxide and sodium chlorite are configured to the efficient oxidation composition according to 2: 1 (mol ratio) is that 10% oxidant is (in the oxidant except that hydrogen peroxide and sodium chlorite; Surplus is a water); Control oxidant pH simultaneously at 5-6; Add mass fraction and be 0.005% iron chloride (be iron chloride account for the 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 secondary desulfurization is 10L/m
3(first grade desulfurizing is 6L/m
3, the secondary desulfurization is 4L/m
3), utilize technology of the present invention, carry out desulphurization denitration.First grade desulfurizing efficient can reach 70%, after the oxidation in the flue gas NO be 8ppm, NO
2Be 190ppm, behind the secondary desulphurization denitration, exit SO
2About concentration 20ppm, NOx is about 15ppm.Overall desulfuration efficiency 98%, denitration efficiency can reach 96.2%.
Embodiment 3
At 5m
3Simulation flue gas desulfurization and denitrification process on the experimental simulation device of/h scale.Exhaust gas volumn 5m
3/ h, flue gas composition is following: O
2Be 5%, SO
2Be 1000ppm, NO is 400ppm, and all the other are nitrogen, 100 ℃ of flue-gas temperatures, 1 atmospheric pressure of pressure.
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 that 5% oxidant is (in the oxidant except that hydrogen peroxide and sodium chlorite; Surplus is a water); Add mass fraction and be 0.001% manganese chloride (be manganese chloride account for the 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 secondary desulfurization is 10L/m
3(first grade desulfurizing is 6L/m
3, the secondary desulfurization is 4L/m
3), utilize technology of the present invention, carry out desulphurization denitration.First grade desulfurizing efficient can reach 70%, after the oxidation in the flue gas NO be 80ppm, NO
2Be 187ppm, behind the secondary desulphurization denitration, exit SO
2About concentration 20ppm, NOx is about 89ppm.Overall desulfuration efficiency 98%, denitration efficiency can reach 77.8%.
Embodiment 4
At 5m
3Simulation flue gas desulfurization and denitrification process on the experimental simulation device of/h scale.Exhaust gas volumn 5m
3/ h, flue gas composition is following: O
2Be 5%, SO
2Be 1000ppm, NO is 400ppm, and all the other are nitrogen, 100 ℃ of flue-gas temperatures, 1 atmospheric pressure of pressure.
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 that 10% oxidant is (in the oxidant except that hydrogen peroxide and sodium chlorite; Surplus is a water); Add mass fraction and be 0.001% manganese chloride (be manganese chloride account for the 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 secondary desulfurization is 10L/m
3(first grade desulfurizing is 6L/m
3, the secondary desulfurization is 4L/m
3), utilize technology of the present invention, carry out desulphurization denitration.First grade desulfurizing efficient can reach 70%, after the oxidation in the flue gas NO be 40ppm, NO
2Be 195ppm, behind the secondary desulphurization denitration, exit SO
2About concentration 10ppm, NOx is about 45ppm.Overall desulfuration efficiency 99%, denitration efficiency can reach 88.7%.
Embodiment 5
The combined desulfurization and denitrification process of the multistage absorption of liquid phase oxidation according to the invention is at exhaust gas volumn 10000m
3/ h, SO
2Be 3000mg/Nm
3About, O
2Be 6-8%, NO is 200-300ppm, flue-gas temperature 120-150 ℃.
Set up desulfuring and denitrifying apparatus like Fig. 1; Sodium chlorite solution and liquor natrii hypochloritis add according to 0.5: 1.5 ratio; The mass concentration of the efficient oxidation composition is controlled at 10% (except that hydrogen peroxide and sodium chlorite, surplus is a water in the oxidant) in the initial oxidation agent, and pH is controlled at 5-6; Add mass fraction and be 0.001% manganese chloride (be manganese chloride account for the 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 secondary desulfurization is 10L/m
3(first grade desulfurizing is 6L/m
3, the secondary desulfurization is 4L/m
3), carry out desulphurization denitration.First grade desulfurizing efficient can reach 65%, after the oxidation in the flue gas NO be 10ppm, NO
2Be 80-90ppm, behind the secondary desulphurization denitration, exit SO
2About concentration 100ppm, NOx is about 15ppm.Overall desulfuration efficiency about 97%, denitration efficiency can reach more than 90%.
Claims (10)
1. the flue gas desulfurization and denitration technique of the multistage absorption of liquid phase oxidation is characterized in that, comprising:
(1) desulfurizing agent and flue gas haptoreaction are carried out preparatory desulfurization, desulfurizing agent absorbs the part sulfur dioxide in the flue gas, obtains desulfurization slurry;
(2) flue gas after the preparatory desulfurization is carried out liquid phase oxidation and partially absorb, the oxidation of nitric oxide in the flue gas is become nitrogen dioxide, the oxidant of described liquid phase oxidation is at least a aqueous solution in hydrogen peroxide solution, chlorite and the hypochlorite;
(3) flue gas that will be after peroxidating and the desulfurization slurry haptoreaction in the step (1) absorb nitrogen dioxide and remaining sulfur dioxide in the flue gas.
2. flue gas desulfurization and denitration technique according to claim 1 is characterized in that, the efficient oxidation composition accounts for the 5-35% of gross mass in the oxidant described in the step (2).
3. flue gas desulfurization and denitration technique according to claim 1 is characterized in that, also is added with the metal ion that accounts for oxidant gross mass 0.001-0.01% in the said oxidant.
4. flue gas desulfurization and denitration technique according to claim 3 is characterized in that, the pH value of said oxidant is 4-7.
5. flue gas desulfurization and denitration technique according to claim 1 is characterized in that, the temperature of said liquid phase oxidation is 40-50 ℃.
6. flue gas desulfurization and denitration technique according to claim 1 is characterized in that, the liquid-gas ratio of said liquid phase oxidation is 3-7L/m
3
7. device of realizing flue gas desulfurization and denitration technique as claimed in claim 1; Comprise desulphurization denitration tower (9); It is characterized in that; Said desulphurization denitration tower (9) bottom is provided with the tower still (12) that is used to hold said desulfurizing agent and desulfurization slurry; The top of said tower still (12) sets gradually first spraying layer (2) that is useful on the said desulfurizing agent of spray, be used to that flue gas is contacted with the oxidant sieve plate layer (3) that carries out liquid phase oxidation, the 3rd spraying layer (6) that is used to spray second spraying layer (4) of said oxidant and is used to spray said desulfurization slurry from the bottom to top; Be communicated with through being positioned at the outer oxidizer slurry jar (11) of desulphurization denitration tower (9) between described sieve plate layer (3) and second spraying layer (4), described first spraying layer (2) and the 3rd spraying layer (6) are communicated with tower still (12) through external circulating pump respectively.
8. device according to claim 7 is characterized in that, the center that is provided with between described the 3rd spraying layer (6) and 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 still (12).
9. device according to claim 7 is characterized in that, described dividing plate (5) is by several layers reducing annulus nested composition up and down, and leaves the space that supplies flue gas to pass.
10. device according to claim 7 is characterized in that, described oxidizer slurry jar (11) top is provided with the oxidant storage tank (10) through pipeline connection.
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