CN104524935A - Single-tower type double-circulation sprinkling composite absorption device and method - Google Patents
Single-tower type double-circulation sprinkling composite absorption device and method Download PDFInfo
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- CN104524935A CN104524935A CN201410707429.4A CN201410707429A CN104524935A CN 104524935 A CN104524935 A CN 104524935A CN 201410707429 A CN201410707429 A CN 201410707429A CN 104524935 A CN104524935 A CN 104524935A
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Abstract
The invention discloses a single-tower type double-circulation desulfurization denitration composite absorption device which comprises an absorption tower; the absorption tower is internally successively provided with a desulfurization section, an ozone oxidation section and a denitration section from bottom to top; the desulfurization section comprises a flue gas inlet penetrating through the side wall of the absorption tower, a desulfurization slurry circulating pool arranged at the bottom of the absorption tower, desulfurization sprinkling absorption layers arranged above the desulfurization slurry circulating pool, a desulfurization slurry circulatory system making the desulfurization slurry circulating pool and the desulfurization sprinkling absorption layers mutually connected; the ozone oxidation section is arranged above the desulfurization sprinkling absorption layers; the denitration section comprises a flue gas outlet at the top of the absorption tower, a denitration slurry circulating pool arranged above the ozone oxidation section, denitration sprinkling absorption layers arranged above the denitration slurry circulating pool, a demister arranged between the denitration sprinkling absorption layers and the flue gas outlet, and a denitration slurry circulatory system making the denitration slurry circulating pool and the denitration sprinkling absorption layers mutually connected.
Description
Technical field
The present invention relates to a kind of flue gas treating reactor of coal-burning boiler, specifically a kind of single tower type double-cycle spray composite absorption device and process system.
Background technology
Nitrogen oxide (NOx) is one of air primary pollution source, is also a great problem of current air contaminant treatment.Usually said nitrogen oxide (NOx) comprises N
2o, NO, NO
2, N
2o
3deng, wherein mainly NO and NO of atmosphere pollution
2.
Although the NOx of mankind's activity discharge is only about 1/10 of the NOx of natural formation, because concentration of emission is high, place is concentrated, and endangers very large.The discharge of NOx mainly comprises to the harm brought of living of natural environment and human being's production: NOx has intoxicating effect to human body; Detrimental effect to plant: NOx is the main cause forming acid rain, acid mist; NOx and hydrocarbon form chemical fumes, cause secondary pollution.So various countries have formulated containing NOx toxic emission index in succession, the discharge capacity of NOx and concentration of emission are limited.Along with the mankind are to the raising of environmental requirement, can be more and more stricter to the emission request of NOx.From 20 century 70s, Europe, the United States, Deng developed country have done restriction to the discharge of coal-fired power station boiler NOx in succession, and with the development of technology and economy, limit increasingly strict.China is the developing country based on fire coal, and along with the fast development of economy, the environmental pollution that fire coal causes is on the rise, the NOx particularly in coal-fired flue-gas, has become a problem that can not be ignored to the pollution of air.Power plants coal-fired boiler NOx annual emissions is increased to 8,400,000 tons in 2007 from 2003 597.3 ten thousand tons, adds nearly 40.6%.According to the CH INA-MAP project that NASA subsidizes, the pollutant emission situation that 29, China is regional by PAINS-ASIA mode detection, result shows, if do not controlled, the discharge expecting the year two thousand twenty NOx will be increased to 2660 ~ 2,970 ten thousand tons.Given this, China has done further restriction in 2011 to the NOx emission of coal-fired power station boiler.Now, China's " fossil-fuel power plant atmospheric pollutant emission standard " is 100mg/m to the NOx emission mass concentration maximum limit in coal steam-electric plant smoke
3.For this reason, China is in the flourish stage for the control of NOx since 12.
The typical technique of flue gas and desulfurizing and denitrifying technology has dry method and wet method two class.Current China adopts SNCR, SCR denitration technology usually, but SCR method is with NH
3for reducing gases, have that transport difficult, investment and operating cost are high, catalyst easy in inactivation, a discharge N
2o and NH
3the defects such as, complex process narrow Deng secondary pollution, operating temperature range; It is low to there is denitration efficiency in SNCR method, and operating temperature is high, and the shortcoming such as NH_3 leakage, and investment operating cost is high.Therefore, there is new dry method simultaneous SO_2 and NO removal technique, having comprised: active carbon absorption process, high energy electron active oxidation method etc.
At present, wet desulphurization device has higher desulfuration efficiency, but denitration efficiency almost can be ignored.This mainly because more than 95% be NO in flue gas, is insoluble in water, very difficult absorb by absorbent.So feasible gas denitrifying technology of developing the economy is imperative.The desulfurization and denitrification integral technology of research and development high-efficiency and economic has become the focus of attention of domestic and international many research institutions.
If but NO can be oxidized to NO
2etc. absorbable high-valence state NOx, so likely realize denitration, reach process equipment simple, reduce energy consumption, disposal cost low, save the effects such as space.
Current NO oxidation technology mainly contains ozone oxidation, plasma oxidation, chemical addition agent oxidation etc.
Chemical addition agent oxidative absorption technique is relatively more simple ripe.
Product after adopting sodium alkali combined desulfurization and denitration can utilize NaOH desulfurization just can become the reactant of denitration, the basis of original desulfurizer can realize denitration, not only economically feasible, and the system of bulk devulcanization denitration greatly simplifies.Compared with other technique, simply ripe, can be used in the transformation of original wet desulphurization device.Therefore for a lot of medium-sized and small enterprises, a kind of beyond doubt desirable denitration is selected.
Summary of the invention
The technical problem to be solved in the present invention is to provide a kind of single tower type double-cycle spray desulphurization denitration composite absorption device and process system.
The present invention provides a kind of single tower type double-cycle desulphurization denitration composite absorption device, comprises absorption tower; Set gradually as desulfurization section, ozone oxidation section and denitration section in described absorption tower from bottom to top; Described desulfurization section comprise run through absorption tower sidewall gas approach, be arranged on desulfurization slurry circulatory pool bottom absorption tower, be arranged on desulfurization spray-absorption layer above desulfurization slurry circulatory pool, by desulfurization slurry circulatory pool and the interconnective desulfurization slurry circulatory system of desulfurization spray-absorption layer; Directly over described desulfurization spray-absorption layer, ozone oxidation section is set; Described denitration section comprise top, absorption tower exhanst gas outlet, be arranged on denitration grout circulatory pool above ozone oxidation section, be arranged on denitration spray-absorption layer above denitration grout circulatory pool, be arranged on demister between denitration spray-absorption layer and exhanst gas outlet, by denitration grout circulatory pool and the interconnective denitration grout circulatory system of denitration spray-absorption layer.
Improvement as to single tower type double-cycle desulphurization denitration composite absorption device of the present invention: described ozone oxidation section comprises the ozone generator and oxidation panel that are interconnected; Be provided with between described ozone oxidation section and denitration grout circulatory pool and rise device of air; The described device of air that rises comprises the riser that at least two are arranged on oxidation panel top; Be communicated with after described riser import runs through the sidewall on absorption tower above ozone oxidation section, be communicated with above denitration grout circulatory pool after riser outlet runs through the sidewall on absorption tower.
Further improvement as to single tower type double-cycle desulphurization denitration composite absorption device of the present invention: in space, described oxidation panel place and riser import is respectively arranged with the ozone nozzle sets I and ozone nozzle sets II that are interconnected with ozone generator; Ozone nozzle I in described ozone nozzle sets I is evenly distributed on the same cross section of oxidation panel with the spacing of 0.1 meter, and the layout quantity of described ozone nozzle sets I is at least one deck; Any one riser import described is distributed with the ozone nozzle II in 3 ~ 5 ozone nozzle sets II; Ozone nozzle in described ozone nozzle sets II is all arranged along flow level direction.
Further improvement as to single tower type double-cycle desulphurization denitration composite absorption device of the present invention: the quantity of described desulfurization spraying layer is 2 ~ 3 layers; The described desulfurization slurry circulatory system comprises desulfuration recycle pump and desulfurization slurry case; Described desulfurization slurry circulatory pool is provided with desulfuration recycle pump slurries being squeezed into desulfurization spray-absorption layer; Described desulfurization slurry case is connected with desulfurization slurry circulatory pool and/or desulfurization spray-absorption layer respectively; The quantity of described denitration spray-absorption layer is 1 ~ 2 layer; The described denitration grout circulatory system comprises denitration circulating pump; Described denitration grout circulatory pool and desulfurization slurry circulatory pool are equipped with denitration circulating pump slurries being squeezed into denitration spraying layer; The denitration circulating pump of described denitration grout circulatory pool is connected with denitration spray-absorption layer upper strata; The denitration circulating pump of described desulfurization slurry circulatory pool is connected with denitration spray-absorption layer lower floor.
A desulfurization denitration method for single tower type double-cycle desulphurization denitration composite absorption, comprises sweetening process, NO oxidizing process, denitrification process; Described sweetening process comprises the steps: that (1.1) are input between desulfurization slurry circulatory pool and desulfurization spray-absorption layer by gas approach after flue gas is carried out degree of depth dedusting; (1.2) NaOH is squeezed into desulfurization spraying layer from desulfurization slurry circulatory pool by desulfuration recycle pump, spray NaOH absorbing liquid by desulfurization spraying layer; (1.3) SO in flue gas
2absorption reaction: 2NaOH+SO is there is with NaOH
2=Na
2sO
3+ H
2o, completes high-efficiency desulfurization; (1.4) final, the accessory substance Na produced in this step
2sO
3get back to desulfurization slurry circulatory pool, and the flue gas after desulfurization enters oxidation panel; Described NO oxidizing process comprises the steps: that the flue gas after desulfurization is passed into ozone oxidation section by (2.1); (2.2) be injected in the flue gas at oxidation panel place by the ozone that ozone generator produces by ozone nozzle, ozone fully contacts with NO in flue gas after desulfurization, and part NO is oxidized to NO
2: NO+O
3=NO
2+ O
2; (2.3) flue gas after oxidation enters denitration section by rising device of air, simultaneously in the raw oxidation reaction of riser relaying supervention; Described denitrification process comprises the steps: the accessory substance Na that (3.1) are produced by sweetening process
2sO
3directly squeeze into denitration spray-absorption layer lower floor by denitration circulating pump from doctor solution circulatory pool, and sprayed by denitration spray-absorption layer lower floor, now accessory substance Na
2sO
3fall back to after reaction in denitration grout circulatory pool, and squeeze into denitration spray-absorption layer upper strata by the denitration circulating pump in denitration grout circulatory pool, proceed spray; (3.2) NO and NO
2at denitration spray-absorption layer and Na
2sO
3abundant contact, Na
2sO
3and NO
2there is redox reaction: 4Na
2sO
3+ 2NO
2=4Na
2sO
4+ N
2, finally complete NO_x Reduction by Effective; NaOH and NOx of non-complete reaction reacts simultaneously: 2NaOH+NO+NO
2=2NaNO
2+ H
2o and 2NaOH+2NO
2=NaNO
2+ NaNO
3+ H
2o; (3.3) accessory substance in denitration rear slurry pond is regularly discharged to the further oxidation reaction of aerator, is converted into Na completely
2sO
4, NaHSO
4and NaNO
3after carry out waste water dis posal again; (3.4) denitration complete after flue gas remove large quantity of moisture through demister, finally got rid of by exhanst gas outlet, then through serial gas composition detection, finally flue gas up to standard discharged from chimney.
Improvement as the desulfurization denitration method to single tower type double-cycle desulphurization denitration composite absorption of the present invention: in described step 1.2, the mol ratio of NaOH and SO2 controls at 2.05:1, liquid-gas ratio 8 ~ 10; In described step 2.2, it is 1% ~ 2% that ozone concentration controls, with O
3the ratio uniform of/NO=1:1 injects flue gas after desulfurization; In described step 3.2, Na
2sO
3control at 1 ~ 2:1 with the mol ratio of NOx, liquid-gas ratio 5 ~ 8.
To a method for flue gas desulfurization and denitrification, comprise the steps: one, desulfurization: by the flue gas after degree of depth dedusting, with NaOH spray, the SO in flue gas
2absorption reaction: 2NaOH+SO is there is with NaOH
2=Na
2sO
3+ H
2o, completes high-efficiency desulfurization; Two, NO oxidation: with O
3ozone is injected in the flue gas in step one after desulfurization by the ratio of/NO=1:1, and the NO in the flue gas after ozone processes with step one fully contacts, and part NO is oxidized to NO
2: NO+O
3=NO
2+ O
2; Three, the removing of NOx: by the desulfurizing byproduct Na produced in step one
2sO
3in the reacted flue gas of steps for importing two, NO and NO
2with Na
2sO
3abundant contact, now: on the one hand, Na
2sO
3and NO
2there is redox reaction, finally complete NO_x Reduction by Effective: 4Na
2sO
3+ 2NO
2=4Na
2sO
4+ N
2; The NaOH of non-complete reaction also can participate in absorption reaction on the other hand, and side reaction: 2NaOH+NO+NO occurs
2=2NaNO
2+ H
2o; Control Na
2sO
3be 1 ~ 2:1 with the mol ratio of NOx, finally complete denitrification process; Four, waste water, exhaust-gas treatment: above reacted accessory substance is carried out oxidation reaction by aerator, after being converted into Na2SO4, NaHSO4 and NaNO3 completely, carries out waste water dis posal.
Improvement as the method to flue gas desulfurization and denitrification of the present invention: in described step one, NaOH and SO
2mol ratio remain 2.05:1, liquid-gas ratio 8 ~ 10; In described step 2, the mass concentration of ozone is 1% ~ 2%; In described step 3, Na
2sO
31 ~ 2:1 is remained, liquid-gas ratio 5 ~ 8 with the mol ratio of NOx.
Single tower type double-cycle spray composite absorption tower of the present invention compared with the prior art, has following beneficial effect:
(1) realize single tower height effect desulphurization denitration, greatly reduce investment and operating cost, simple and reliable process;
(2) adopt Na base mixed liquor to carry out desulfurization, then adopt the Na of reaction gained
2sO
3as denitration absorbent, not only absorbent utilization rate is high, and Na
2sO
3denitration performance is good;
(3) structure of syllogic, by SO
2absorb in purifier desulfurization spray section and purification denitration spray section respectively with NOx, decrease competitive reaction;
(4) changeover portion temperature reduces, and for the oxidation of ozone to NO, decreases the decomposition of ozone, improves NO oxidation efficiency;
(5) after desulfurization spray section, cigarette temperature declines, and flue gas volume greatly reduces, and under certain absorbing liquid spray, contributes to improving denitration efficiency.
Accompanying drawing explanation
Below in conjunction with accompanying drawing, the specific embodiment of the present invention is described in further detail.
Fig. 1 is primary structure schematic diagram of the present invention;
The plan structure figure rising device of air of Fig. 2 Fig. 1;
The structure chart rising the ozone nozzle II 18 of device of air of Fig. 3 Fig. 1;
The layout drawing of the ozone nozzle I 19 of the ozone oxidation section of Fig. 4 Fig. 1.
Detailed description of the invention
Embodiment 1, Fig. 1 give a kind of single tower type double-cycle desulphurization denitration composite absorption device, and its agent structure is absorption tower, on absorption tower, is connected with aerator 2, chimney device 16 etc.
Set gradually from bottom to top in above-described absorption tower as desulfurization section 5 (flue gas desulfurization), ozone oxidation section 7 (the flue gas oxidation after desulfurization) and denitration section 10 (after oxidation denitrating flue gas).
Desulfurization section 5 comprise run through absorption tower sidewall gas approach, be arranged on desulfurization slurry circulatory pool 3 bottom absorption tower, be arranged on 2 ~ 3 pull-up sulphur spray-absorption layers 4 (setting of multi-layer desulfurization spray-absorption layer 4, guarantees reaction effect) above desulfurization slurry circulatory pool 3, by desulfurization slurry circulatory pool 3 and the interconnective desulfurization slurry circulatory system of desulfurization spray-absorption layer 4; The desulfurization slurry circulatory system comprises desulfuration recycle pump and desulfurization slurry case 1 (built-in NaOH absorbing liquid); In desulfurization slurry circulatory pool 3, desulfuration recycle pump is set, is all connected with each pull-up sulphur spray-absorption layer 4 by pipeline; Desulfurization slurry case 1 (built-in NaOH absorbing liquid) is all connected with each pull-up sulphur spray-absorption layer 4 by pipeline, in order to ensure reaction efficiency, when reality uses, also desulfurization slurry case 1 can be interconnected by pipeline and desulfurization slurry circulatory pool 3.NaOH absorbing liquid is to SO
2absorption rate be 2 ~ 3 times of lime stone slurry, so reach certain SO in NaOH absorption process
2the time of staying needed for absorption efficiency is shorter, and required spraying layer height is also lower.Under the prerequisite ensureing assimilation effect, adopt 2 ~ 3 layers of spraying layer will reduce absorption tower whole height, cost of reducing investment outlay.
Directly over desulfurization spray-absorption layer 4, ozone oxidation section 7 is set; Ozone oxidation section 7 comprises ozone generator 13 (generation ozone) and oxidation panel (space at the raw oxidation reaction place of flue gas hybrid concurrency after ozone and desulfurization).
Denitration section 10 comprise run through top, absorption tower exhanst gas outlet, be arranged on denitration grout circulatory pool 15 directly over ozone oxidation section, be arranged on 1 ~ 2 pull-up nitre spray-absorption layer 8 directly over denitration grout circulatory pool (due to Na
2sO
3and NO
2reaction rate very fast, and NO concentration is at 300 ~ 400mg/m
3, so only need 1 ~ 2 pull-up nitre spray-absorption layer 8), be arranged on demister 9 between denitration spray-absorption layer 8 and exhanst gas outlet, by denitration grout circulatory pool 15 and the interconnective denitration grout circulatory system of denitration spray-absorption layer 8; The denitration grout circulatory system is two denitration circulating pumps, and two denitration circulating pumps are separately positioned on denitration grout circulatory pool 15 and desulfurization slurry circulatory pool 3 (supplements Na by desulfurization slurry circulatory pool 3
2sO
3absorbing liquid) in, the denitration circulating pump of denitration grout circulatory pool 15 is connected with the denitration spray-absorption layer on upper strata by pipeline, and the denitration circulating pump of desulfurization slurry circulatory pool 3 is connected with the denitration spray-absorption layer of lower floor by pipeline.Denitration grout circulatory pool 15 is upper outside is equipped with aerator 2, discharges reacted final accessory substance, and pass through Air Exposure by this aerator 2.
Be provided with between oxidation panel 7 and denitration grout circulatory pool 15 and rise device of air 6; Rise the effect of device of air 6 be by desulfurization after flue gas introduce denitration section 10.Rise device of air 6 and comprise the riser that at least two are arranged on both sides above oxidation panel 7; After riser exit end runs through the sidewall on absorption tower, by riser road rises, until relative to the position of denitration grout circulatory pool 15, then run through the sidewall on absorption tower, be passed into above denitration grout circulatory pool 15 that (this mode makes denitration clearly be separated with sweetening process, prevents SO
2with NOx to Na
2sO
3there is competitive reaction, thus improve the overall removal efficiency of NOx).In space, oxidation panel 7 place and riser mouth be respectively arranged with the ozone nozzle sets I and ozone nozzle sets II that are interconnected with ozone generator 13; Ozone nozzle I 19 in ozone nozzle sets I at oxidation panel, and distributes uniformly with the spacing of 0.1 meter on oxidation panel cross section; Any one riser inlets even is distributed with the ozone nozzle II 18 in 3 ~ 5 ozone nozzle sets II; Ozone nozzle II 18 in described ozone nozzle sets II is all arranged along flow level direction.
A desulfurization denitration method for single tower type double-cycle desulphurization denitration composite absorption, realize according to above-described single tower type double-cycle desulphurization denitration composite absorption device, its step comprises sweetening process, NO oxidizing process, denitrification process.
One, sweetening process comprises the steps:
(1) first degree of depth dedusting is carried out through dust arrester from boiler 17 flue gas I (namely without the flue gas of any process) out, then flue gas II (namely flue gas I is by the flue gas after dust arrester dedusting) enters gas approach of the present invention, at desulfurization section 5, absorption reaction (these absorption reaction concrete steps are as step 2) occurs.
(2) by the desulfuration recycle pump in desulfurization slurry circulatory pool 3 by desulfurization slurry (NaOH/Na
2sO
3/ NaHSO
3mixed liquor; First add in desulfurization slurry circulatory pool 3 for NaOH absorbing liquid, due to after continuous reaction, produce Na
2sO
3and accessory substance NaHSO
3, so the absorbing liquid in this desulfurization slurry circulatory pool 3 becomes NaOH/Na gradually
2sO
3/ NaHSO
3mixed liquor) squeeze into desulfurization spray-absorption layer 4 from desulfurization slurry circulatory pool 3 and carry out spray absorber, and the NaOH drop sprayed out by with SO
2after reaction, again drop onto in desulfurization slurry circulatory pool 3; Simultaneously, a certain amount of mass concentration is that the fresh NaOH of 20 ~ 30% is from desulfurization slurry case 2 directly access desulfurization spraying layer 4; In above-described course of reaction, need NaOH and SO
2mol ratio remain on the optimum response state of 2.05:1, and due to NaOH and SO
2constantly Na is generated after reaction
2sO
3and H
2o and accessory substance NaHSO
3, so the NaOH mass concentration in desulfurization slurry circulatory pool 3 constantly reduces, cause NaOH and SO
2mol ratio can not be stabilized in the optimum response state of 2.05:1, so now, by desulfurization slurry case 2, (addition of this fresh NaOH absorbing liquid is according to SO by a certain amount of
2the gauge that removes calculate, guarantee NaOH and SO
2mol ratio be stabilized in 2.05:1) mass concentration be 20% ~ 30% NaOH absorbing liquid squeeze into desulfurization spray-absorption layer 4 or directly add in desulfurization slurry circulatory pool 3 that (that directly come up in desulfurization slurry circulatory pool 3 is NaOH/Na
2sO
3/ NaHSO
3mixed liquor, actual NaOH concentration is low, and in order to ensure assimilation effect, liquid-gas ratio is larger, and general control is at liquid-gas ratio 8 ~ 10; And due to desulfurization slurry case 2 NaOH be out high concentration, so NaOH flow is very little.So fresh NaOH can be added in pipeline, directly bring spraying layer 4 into; Also serum recycle pond 3 can directly be added).
(3) SO in flue gas II
2there is absorption reaction with NaOH, complete high-efficiency desulfurization, generate desulfurizing byproduct Na simultaneously
2sO
3.
In this sweetening process step, main chemical reaction process is as follows:
2NaOH+SO
2=Na
2sO
3+ H
2o (sweetening process key reaction);
NaOH+SO
2=NaHSO
3(sweetening process side reaction).
Two, described NO oxidizing process comprises the steps:
(1) (oxidation panel is for depositing flue gas III container flue gas III (flue gas by after flue gas II desulfurization) to be passed into the oxidation panel of ozone oxidation section 7, the space at the raw oxidation reaction place of the flue gas hybrid concurrency namely after ozone and desulfurization), NO partial oxidation is become NO
2(concrete as step 2);
(2) it is about 1% ~ 2% that the ozone mass concentration produced by ozone generator 13 controls; According to the concentration of NO in flue gas, by ozone with O
3the ratio of/NO=1:1 is injected in the flue gas III at oxidation panel place by the ozone nozzle I 19 in the ozone nozzle sets I that is evenly arranged, and ozone fully contacts with NO in flue gas III, and part NO is oxidized to NO
2;
(3) flue gas IV (namely flue gas III be oxidized in previous step after flue gas) by rising the relevant position (namely above denitration grout circulatory pool 15) that device of air 6 imports denitration section 10, simultaneously, ozone nozzle II 18 in ozone nozzle sets II sprays ozone to riser mouth, makes flue gas IV in the raw oxidation reaction of riser relaying supervention.
(4) in addition, along with flue gas III passes in the oxidation panel space of ozone oxidation section 7, the Na contained in this flue gas III
2sO
3drop (the Na that desulfurization produces
2sO
3drop) react with NOx at this moment, so without the need to carrying out demist at desulfurization section.
In this NO oxidation step, main chemical reaction process is as follows:
NO+O
3=NO
2+ O
2(oxidation panel key reaction);
NO+H
2o
2=NO
2+ H
2o (oxidation panel side reaction).
Wherein, described H
2o
2be only absorbed by the water by ozone:: O
3+ H
2o=H
2o
2+ O
2.
Three, the subtractive process of described NOx comprises the steps:
(1) flue gas IV enters denitration section 10 by rising device of air 6;
(2) by the denitration circulating pump in desulfurization slurry circulatory pool 3 from desulfurization slurry circulatory pool 3 by slurries (Na
2sO
3, Na
2sO
4, NaNO
3) (that mainly utilize is the accessory substance Na that sweetening process produces directly to squeeze into denitration spraying layer 8 lower floor
2sO
3), simultaneously the upper strata of denitration spraying layer 8 by the denitration circulating pump in denitration grout circulatory pool 15 from denitration grout circulatory pool 15 by slurries (slurries mainly Na herein
2sO
3, Na
2sO
4, NaNO
3, after the slurries use of denitration spraying layer 8 lower floor, enter denitration grout circulatory pool 15) squeeze into;
(3) NO and NO in flue gas IV
2at denitration spraying layer 8 and Na
2sO
3abundant contact, and by Na
2sO
3control, at 1 ~ 2:1, to make Na with the mol ratio of NOx
2sO
3and NO
2there is redox reaction, finally complete NO_x Reduction by Effective;
(4), after denitration, the accessory substance in denitration grout circulatory pool 15 is regularly discharged to aerator 2 oxidation reaction further, is converted into Na completely
2sO
4, NaHSO
4and NaNO
3deng after carry out waste water dis posal again;
(5) denitration complete after flue gas remove large quantity of moisture through demister 9, finally discharged by exhanst gas outlet, then through serial gas composition detection, finally flue gas up to standard discharged from chimney 16.
In the subtractive process step of this NOx, main chemical reaction process is as follows:
4Na
2sO
3+ 2NO
2=4Na
2sO
4+ N
2(denitration key reaction);
2NaOH+NO+NO
2=2NaNO
2+ H
2o (denitration side reaction);
2NaOH+2NO
2=NaNO
2+ NaNO
3+ H2O (denitration side reaction).
A kind of method to flue gas desulfurization and denitrification; Comprise the steps to realize:
One, desulfurization:
After the dedusting of the flue gas degree of depth, with a certain amount of NaOH spray, (amount of NaOH passes through SO
2determine, namely keep NaOH and SO
2mol ratio remain on 2.05:1; ), now, the SO in flue gas
2absorption reaction: 2NaOH+SO is there is with NaOH
2=Na
2sO
3+ H
2o (sweetening process key reaction), completes high-efficiency desulfurization;
Meanwhile, side reaction is carried out: NaOH+SO
2=NaHSO
3(sweetening process side reaction).
Two, NO oxidation:
Be that the ozone of 1% ~ 2% is according to O by concentration
3the ratio of/NO=1:1 is injected in the flue gas in step one after desulfurization, and the NO that ozone and step one process in rear flue gas fully contacts, and part NO is oxidized to NO
2: NO+O
3=NO
2+ O
2(oxidation panel key reaction).
Meanwhile, side reaction is carried out: NO+H
2o
2=NO
2+ H
2o (oxidation panel side reaction).
Three, the removing of NOx:
By the desulfurizing byproduct Na produced in step one
2sO
3in the reacted flue gas of steps for importing two, NO and NO2 and Na
2sO
3abundant contact, and control Na
2sO
3be 1 ~ 2:1 with the mol ratio of NOx, liquid-gas ratio 5 ~ 8, now, Na
2sO
3and NO
2there is redox reaction, finally complete NO_x Reduction by Effective: 4Na
2sO
3+ 2NO
2=4Na
2sO
4+ N
2(denitration key reaction);
Owing to also having NO in now flue gas, so also can following side reaction be carried out: 2NaOH+NO+NO
2=2NaNO
2+ H
2o and 2NaOH+2NO
2=NaNO
2+ NaNO
3+ H2O (denitration side reaction);
Four, waste water, exhaust-gas treatment:
Above reacted accessory substance is carried out oxidation reaction by aerator, is converted into Na completely
2sO
4, NaHSO
4and NaNO
3after, carry out waste water dis posal.
Case study on implementation:
There is the coal-burning boiler simultaneous SO_2 and NO removal demonstration project of an employing list tower type double-cycle spray composite absorption device and process system, treatment quantity 2000Nm
3/ h, SO2 initial concentration 2400mg/Nm
3, NOx initial concentration 380mg/Nm
3.Under different technology conditions, the result of demonstration project experiment is as follows:
Finally, it is also to be noted that what enumerate above is only a specific embodiment of the present invention.Obviously, the invention is not restricted to above embodiment, many distortion can also be had.All distortion that those of ordinary skill in the art can directly derive from content disclosed by the invention or associate, all should think protection scope of the present invention.
Claims (8)
1. single tower type double-cycle desulphurization denitration composite absorption device, comprises absorption tower; It is characterized in that: set gradually as desulfurization section, ozone oxidation section and denitration section in described absorption tower from bottom to top;
Described desulfurization section comprise run through absorption tower sidewall gas approach, be arranged on desulfurization slurry circulatory pool bottom absorption tower, be arranged on desulfurization spray-absorption layer above desulfurization slurry circulatory pool, by desulfurization slurry circulatory pool and the interconnective desulfurization slurry circulatory system of desulfurization spray-absorption layer;
Above described desulfurization spray-absorption layer, ozone oxidation section is set;
Described denitration section comprise top, absorption tower exhanst gas outlet, be arranged on denitration grout circulatory pool above ozone oxidation section, be arranged on denitration spray-absorption layer above denitration grout circulatory pool, be arranged on demister between denitration spray-absorption layer and exhanst gas outlet, by denitration grout circulatory pool and the interconnective denitration grout circulatory system of denitration spray-absorption layer.
2. single tower type double-cycle desulphurization denitration composite absorption device according to claim 1, is characterized in that: described ozone oxidation section comprises the ozone generator and oxidation panel that are interconnected;
Be provided with between described ozone oxidation section and denitration grout circulatory pool and rise device of air;
The described device of air that rises comprises the riser that at least two are arranged on oxidation panel top;
Be communicated with after described riser import runs through the sidewall on absorption tower above ozone oxidation section, be communicated with above denitration grout circulatory pool after riser outlet runs through the sidewall on absorption tower.
3. single tower type double-cycle desulphurization denitration composite absorption device according to claim 2, is characterized in that: in space, described oxidation panel place and riser import is respectively arranged with the ozone nozzle sets I and ozone nozzle sets II that are interconnected with ozone generator;
Ozone nozzle I in described ozone nozzle sets I is evenly distributed on the same cross section of oxidation panel with the spacing of 0.1 meter, and the layout quantity of described ozone nozzle sets I is at least one deck;
Any one riser import described is distributed with the ozone nozzle II in 3 ~ 5 ozone nozzle sets II; Ozone nozzle in described ozone nozzle sets II is all arranged along flow level direction.
4. single tower type double-cycle desulphurization denitration composite absorption device according to claim 3, is characterized in that: the quantity of described desulfurization spraying layer is 2 ~ 3 layers;
The described desulfurization slurry circulatory system comprises desulfuration recycle pump and desulfurization slurry case;
Described desulfurization slurry circulatory pool is provided with desulfuration recycle pump slurries being squeezed into desulfurization spray-absorption layer;
Described desulfurization slurry case is connected with desulfurization slurry circulatory pool or desulfurization spray-absorption layer respectively;
The quantity of described denitration spray-absorption layer is 1 ~ 2 layer;
The described denitration grout circulatory system comprises denitration circulating pump;
Described denitration grout circulatory pool and desulfurization slurry circulatory pool are equipped with denitration circulating pump slurries being squeezed into denitration spraying layer;
The denitration circulating pump of described denitration grout circulatory pool is connected with denitration spray-absorption layer upper strata;
The denitration circulating pump of described desulfurization slurry circulatory pool is connected with denitration spray-absorption layer lower floor.
5. a desulfurization denitration method for single tower type double-cycle desulphurization denitration composite absorption, according to described claim 1, is characterized in that: comprise sweetening process, NO oxidizing process, denitrification process;
Described sweetening process comprises the steps:
(1.1) be passed between desulfurization slurry circulatory pool and desulfurization spray-absorption layer by gas approach after flue gas being carried out degree of depth dedusting;
(1.2) NaOH absorbing liquid is squeezed into desulfurization spraying layer from desulfurization slurry circulatory pool by desulfuration recycle pump, spray NaOH absorbing liquid by desulfurization spraying layer;
(1.3) SO in flue gas
2there is absorption reaction with NaOH, complete high-efficiency desulfurization;
(1.4) final, the accessory substance Na produced in this step
2sO
3get back to desulfurization slurry circulatory pool, and the flue gas after desulfurization enters oxidation panel;
Described NO oxidizing process comprises the steps:
(2.1) flue gas after desulfurization is passed into ozone oxidation section;
(2.2) be injected in the flue gas at oxidation panel place by the ozone that ozone generator produces by ozone nozzle, ozone fully contacts with NO in flue gas after desulfurization, and part NO is oxidized to NO
2;
(2.3) flue gas after oxidation enters denitration section by rising device of air, simultaneously in the raw oxidation reaction of riser relaying supervention;
Described denitrification process comprises the steps:
(3.1) the accessory substance Na produced by sweetening process
2sO
3directly squeeze into denitration spray-absorption layer lower floor by denitration circulating pump from desulfurization slurry circulatory pool, and sprayed by denitration spray-absorption layer lower floor, now accessory substance Na
2sO
3fall back to after reaction in denitration grout circulatory pool, and squeeze into denitration spray-absorption layer upper strata by the denitration circulating pump in denitration grout circulatory pool, proceed spray;
(3.2) NO and NO
2at denitration spray-absorption layer and Na
2sO
3abundant contact, Na
2sO
3and NO
2there is redox reaction, finally complete NO_x Reduction by Effective; NaOH and NOx of non-complete reaction reacts simultaneously;
(3.3) accessory substance in denitration rear slurry pond is regularly discharged to the further oxidation reaction of aerator, is converted into Na completely
2sO
4, NaHSO
4and NaNO
3after carry out waste water dis posal again;
(3.4) denitration complete after flue gas remove large quantity of moisture through demister, finally got rid of by exhanst gas outlet, then through serial gas composition detection, finally flue gas up to standard discharged from chimney.
6. the desulfurization denitration method of single tower type double-cycle desulphurization denitration composite absorption according to claim 5, it is characterized in that: in described step 1.2, the mol ratio of NaOH and SO2 controls at 2.05:1, and liquid-gas ratio is 8 ~ 10;
In described step 2.2, it is 1% ~ 2% that ozone concentration controls, with O
3the ratio uniform of/NO=1:1 injects flue gas after desulfurization.
In described step 3.2, Na
2sO
3control at 1 ~ 2:1 with the mol ratio of NOx; Liquid-gas ratio 5 ~ 8;
7. to a method for flue gas desulfurization and denitrification, it is characterized in that, comprise the steps:
One, desulfurization:
By the flue gas after degree of depth dedusting with NaOH absorbing liquid spray, control the addition of fresh NaOH absorbing liquid, the SO in flue gas simultaneously
2absorption reaction is there is with NaOH:, complete high-efficiency desulfurization, generate Na simultaneously
2sO
3;
Control Na
2sO
3be 1 ~ 2:1 with the mol ratio of NOx, liquid-gas ratio is 8 ~ 10;
Two, NO oxidation:
With O
3ozone is injected in the flue gas in step one after desulfurization by the ratio of/NO=1:1, and the NO in the flue gas after ozone processes with step one fully contacts, and part NO is oxidized to NO
2;
Three, the removing of NOx:
By the desulfurizing byproduct Na produced in step one
2sO
3in the reacted flue gas of blend absorbent steps for importing two, NO and NO
2with Na
2sO
3blend absorbent fully contacts, now:
On the one hand, Na
2sO
3and NO
2there is redox reaction, finally complete NO_x Reduction by Effective;
The NaOH of non-complete reaction also can participate in absorption reaction on the other hand, and side reaction occurs;
Control Na
2sO
3be 1 ~ 2:1 with the mol ratio of NOx, liquid-gas ratio is 5 ~ 8, finally completes denitrification process;
Four, waste water, exhaust-gas treatment:
Above reacted accessory substance is carried out oxidation reaction by aerator, after being converted into Na2SO4, NaHSO4 and NaNO3 completely, carries out waste water dis posal.
8. the method to flue gas desulfurization and denitrification according to claim 7, is characterized in that: in described step one, NaOH and SO
2mol ratio remain 2.05:1;
In described step 2, the mass concentration of ozone is 1% ~ 2%;
In described step 3, Na
2sO
31 ~ 2:1 is remained with the mol ratio of NOx.
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| 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 |
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