CN104056538A - Flue gas purifying system and method with integration of desulfurization and denitrification - Google Patents
Flue gas purifying system and method with integration of desulfurization and denitrification Download PDFInfo
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- CN104056538A CN104056538A CN201410325672.XA CN201410325672A CN104056538A CN 104056538 A CN104056538 A CN 104056538A CN 201410325672 A CN201410325672 A CN 201410325672A CN 104056538 A CN104056538 A CN 104056538A
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Abstract
The invention provides a flue gas purifying system with integration of desulfurization and denitrification. The flue gas purifying system comprises an ozone generator, a washing absorption tower and a chimney, wherein the washing absorption tower comprises a demisting layer, spraying layers and a tower kettle which are sequentially arranged from top to bottom; the tower kettle is externally provided with a circulation pump; the ozone generator is communicated with a flue gas inlet of the washing absorption tower by a first pipeline, so that flue gas is mixed with ozone before entering the washing absorption tower; the ozone generator is communicated with the spraying layers by a second pipeline, and guides ozone into spraying pipelines, so that ozone is mixed with an absorption liquid, and then is sprayed out from the spraying layers; the tower kettle is communicated with the spraying layers by the circulation pumps; a purified flue gas outlet of the washing absorption tower is communicated with the chimney. According to the invention, the process is simple; the occupied area is small; the cost of investment is low; the absorption effect is improved by combining ozone gas phase and liquid phase oxidation; the desulfurization and denitrification rate of the system is improved.
Description
Technical field
The present invention relates to the smoke gas treatment technical fields such as smelting, sintering machine, coal-burning boiler, chemical industry, be specifically related to a kind of flue gas purification system and flue gas purifying method of integrated desulfurizing denitration.
Background technology
The discharge new standard of thermal power plant's atmosphere pollution has significantly tightened up the emission limit of nitrogen oxide, sulfur dioxide and flue dust, formulate the special emission limit of stricter atmosphere pollution for emphasis environment and environmentally sensitive area, and set up the emission limit of mercury and gas fired-boiler.
Along with the increasingly stringent of pollutant control criterion, must remove multiple pollutant simultaneously, if but multi-pollutant is removed respectively, need to introduce many complete equipments, and the problem such as it is huge to face investment, and floor space is many.Multi-pollutant is removed simultaneously and can effectively avoid the problems referred to above, thereby worldwide extensively carried out the research to smoke multi-pollutant control technology.
Various flue gas multiple pollutant new control technologies continue to bring out in recent years, at NOx and SO
2remove, NOx removes than SO
2much more difficult, therefore, mainly from the angle of NO_x removal, study the integrated purified treatment that removes of flue gas multiple pollutant.Based on the angle of NO_x removal, while desulphurization denitration technology can be divided into two classes: a class is catalytic reduction method, mainly utilizes catalyst, reducing agent etc. that NOx is reduced, desulfurization simultaneously; Another kind of is oxidation absorption process, utilizes various strong oxidizers and living radical that water-fast NO oxidation is generated to NO
2thereby, and SO
2absorb in the later stage simultaneously.
(1) catalytic reduction method:
Power plants denitration generally adopts selective catalytic reduction (SCR) technique, and SCR device having relatively high expectations to operating temperature (flue-gas temperature), but under unit underload, exhaust gas temperature reduces, the work cigarette temperature of SCR can not maintain higher temperature, and cold operation easily causes catalyst poisoning to lose efficacy.
(2) oxidation absorption process:
What in oxidation absorption process, commonly use is Ozonation, the problem that can effectively avoid above-mentioned catalytic reduction method to produce, and application prospect is more extensive.It is mainly to remove after utilizing the strong oxidizing property of ozone that the multiple pollutant in flue gas is oxidized to high valence state.The relative additive method energy consumption of Ozonation is low, and in subtractive process, does not need to introduce other materials and cause secondary pollution, and operating temperature is lower simultaneously, is the more promising flue gas desulfurization and denitrification technology of one.Prior art also has more concrete application to Ozonation, and for example patent CN102350190A discloses a kind of flue gas integrated purifying technique and device of while desulphurization denitration.It adds strong oxidizer ozone after air-introduced machine, nitric oxide in flue gas is processed, and by the agent of spray ammonia absorption, the sulfur dioxide in flue gas and nitrogen oxide are removed, utilize strong oxidizer to carry out oxidation processes to sulphite in absorption tower and nitrite simultaneously., there is sulfite oxidation difficulty in the process of this traditional " first and rear oxidation ", oxidation not thoroughly and the problem such as accessory substance complicated component, has limited applying of Ozonation.
To sum up, how solving the technical problem that above-mentioned " first in and rear oxidation " method produces the application of further promoting Ozonation is the problem that those skilled in the art need emphasis to solve.
Summary of the invention
The object of this invention is to provide a kind of flue gas purification system and flue gas purifying method of integrated desulfurizing denitration, can carry out sufficient oxidation processes to the nitrogen oxide in flue gas and oxysulfide, effectively solve the halfway problem of oxidation.
Technical scheme provided by the invention is as follows:
A flue gas purification system for integrated desulfurizing denitration, comprising:
Ozone generating-device, washing absorption tower, chimney,
Wherein, described washing absorption tower comprises the demist layer, spraying layer and the tower reactor that set gradually from top to bottom, outer setting one circulating pump of described tower reactor;
Described ozone generating-device is communicated with the gas approach of described washing absorption tower by the first pipeline, and flue gas was mixed with ozone before entering described washing absorption tower; Described ozone generating-device is communicated with described spraying layer by second pipe, and imports ozone in described spray piping, ozone is mixed with absorption liquid after from the ejection of described spraying layer;
Described tower reactor is communicated with described spraying layer by described circulating pump;
The clean exhanst gas outlet of described washing absorption tower is communicated with described chimney.
The flue gas purification system of further preferably, described integrated desulfurizing denitration further comprises:
Air-introduced machine, described the first device for cleaning pipeline is crossed described air-introduced machine and is communicated with the gas approach of described washing absorption tower, and the entrance of described air-introduced machine is communicated with a flue simultaneously, so that the flue gas in the ozone of described the first pipeline and described flue mixed before entering described air-introduced machine.
Further preferably, in described flue, be provided with uniform device;
Further preferably, the gas approach of described washing absorption tower is positioned at the top of described tower reactor;
Further preferably, described spraying layer comprises shower, nozzle, and described shower is multilayer; Described nozzle has hollow cone tangent type structure;
Further preferably, described circulating pump is by the spray flux of spraying layer described in a flow control valve control;
Further preferably, the outside of described tower reactor is also provided with an acid solution excavationg pump, and the interface position of described acid solution excavationg pump and described tower reactor is higher than the interface position of described circulating pump and described tower reactor.
Further preferably, in described tower reactor, be provided with the pH value sensor for monitoring pH in described tower reactor;
Described tower reactor place is communicated with one for supplement the absorption liquid pipeline of absorption liquid to described tower reactor, and an absorption liquid replenishment valve is set in described absorption liquid pipeline.
Further preferably, described demist layer comprises demist filter screen and washer jet, and described washer jet has hollow-core construction.
Further preferably, described ozone generating-device comprises liquid oxygen storage tank, vaporizer and ozone generator;
Further preferably, described second pipe is communicated with described spraying layer by a pair of fluid line, and this two-fluid pipeline is sleeve pipe, comprises inner tube and is placed on the outer tube outside this inner tube, and offering uniform aperture on the tube wall of described inner tube.
The present invention also provides a kind of flue gas purifying method of integrated desulfurizing denitration, and it adopts the flue gas purification system of integrated desulfurizing denitration as the aforementioned, comprises the following steps:
Ozone and flue gas mix entering before the gas approach of described washing absorption tower, and ozone carries out gaseous oxidation to flue gas;
Ozone mixes with the liquid of described circulating-pump outlet, forms ozone-water blend absorbent;
Enter described washing absorption tower with the mixed flue gas of ozone, described ozone-water blend absorbent carries out further liquid phase oxidation through spraying layer spray to flue gas, simultaneously to flue gas desulfurization and denitrification;
Flue gas after desulphurization denitration carries out after demist is dried entering described smoke stack emission through described demister.
Further preferably, after ozone mixes with flue gas, be introduced into described washing absorption tower by air-introduced machine;
Further preferably, ozone mixes with flue gas, and enters described washing absorption tower after uniform in pipeline;
Further preferably, described ozone-water blend absorbent flue gas is oxidized and desulphurization denitration after, reclaim discharging the extraction of carrying out nitrogen and sulphur after tower reactor falling after rise to the solution in described tower reactor.
Further preferably, monitor the pH value of the absorption liquid in described tower reactor, in the time of its pH≤5, the absorption liquid in described tower reactor is discharged;
Further preferably, by described absorption liquid pipeline to described tower reactor supplement absorption liquid, and by described absorption liquid replenishment valve control absorption liquid the liquid level in described tower reactor.
Further preferably, in mixing before described ozone and flue gas are entering the gas approach of described washing absorption tower, the mol ratio of the NO in ozone and the flue gas passing into is 0.8-1.2;
Further preferably, in described ozone mixes with the absorption liquid at described spraying layer place, the SO in ozone and the flue gas passing into
2mol ratio be 0.8-1.2;
Further preferably, the liquid-gas ratio in described washing absorption tower is 7～10L/m
3.
By flue gas purification system and the flue gas purifying method of integrated desulfurizing denitration provided by the invention, can bring following at least one beneficial effect:
1. the present invention, by the gas phase of ozone and two kinds of mode combinations of liquid phase oxidation, strengthens assimilation effect.A part of ozone in ozone generating-device mixes with the flue gas entering before washing absorption tower by the first pipeline, and the NO in flue gas is carried out to sufficient gaseous oxidation; Simultaneously some ozone mixes with the absorption liquid phase in spraying layer in washing absorption tower by second pipe, can be to water-soluble SO in the time spraying
2carry out liquid phase oxidation, oxidation product is SO
4 2-.Ozone can be by SO in liquid-phase oxidation process
2the paramount valence state compound of direct oxidation, without increasing extra oxidation unit, oxidation effectiveness is more abundant, efficiently solves the halfway problem of oxidation of the prior art.
2. oxidation effect.The present invention introduces the use of the uniform device in air-introduced machine and flue, and the oxidation effectiveness of ozone in gas phase oxidation process strengthened in the eddy current effect of the uniform and air-introduced machine by flue gas.Meanwhile, the second pipe that the present invention is also communicated with spraying layer ozone generating-device adopts the form of sleeve pipe, makes gas-liquid mixed more abundant, strengthens the liquid phase oxidation effect to flue gas.
3. whole system resource consumption of the present invention is few, operating cost is low, has flow process simple, and floor space is little, and cost of investment is low, denitrification efficiency advantages of higher.
Brief description of the drawings
Below in conjunction with the drawings and specific embodiments, the present invention is described in further detail:
Fig. 1 is the schematic diagram of a kind of embodiment of the flue gas purification system of a kind of integrated desulfurizing denitration of the present invention.
Drawing reference numeral explanation:
1, flue gas; 2, air-introduced machine; 3, washing absorption tower; 4, circulating pump; 5, spraying layer; 6, nozzle; 7, demist layer; 8, fresh water (FW); 9, purify rear flue gas; 10, chimney; 11, ozone generating-device; 12, gaseous oxidation valve; 13, liquid phase oxidation valve; 14, two-fluid mixing duct; 15, flow control valve; 16, absorption liquid replenishment valve; 17, acid solution excavationg pump.
Detailed description of the invention
In order to be illustrated more clearly in the embodiment of the present invention or technical scheme of the prior art, to the accompanying drawing of required use in embodiment or description of the Prior Art be briefly described below, apparently, accompanying drawing in the following describes is only some embodiments of the present invention, for those of ordinary skill in the art, do not paying under the prerequisite of creative work, can also obtain according to these accompanying drawings other accompanying drawing.
In the smoke gas treatment technical fields such as smelting, sintering machine, coal-burning boiler, chemical industry, the pollutant in flue gas is mainly NO and SO
2, in the present invention, utilize ozone gas phase liquid phase oxidation NO and SO
2reaction mechanism as follows:
NO+O
3→NO
2+O
2
NO
2+O
3→NO
3+O
2
SO
2·H
2O(aq)+O
3→H
2SO
4+O
2
In embodiments of the invention one, a kind of flue gas purification system of integrated desulfurizing denitration comprises: ozone generating-device, washing absorption tower, chimney, wherein, described washing absorption tower comprises the demist layer, spraying layer and the tower reactor that set gradually from top to bottom, outer setting one circulating pump of described tower reactor; Described ozone generating-device is communicated with the gas approach of described washing absorption tower by the first pipeline, and flue gas was mixed with ozone before entering described washing absorption tower; Described ozone generating-device is communicated with described spraying layer by second pipe, and imports ozone in described spray piping, ozone is mixed with absorption liquid after from the ejection of described spraying layer; Described tower reactor is communicated with described spraying layer by described circulating pump; The clean exhanst gas outlet of described washing absorption tower is communicated with described chimney.The present invention takes full advantage of gaseous oxidation and the liquid phase oxidation characteristic of ozone, and on the one hand, ozone mixes with the flue gas before entering washing absorption tower, realizes the abundant oxidation (direct oxidation is high valence state) to nitrogen oxide by the gaseous oxidation of ozone; On the other hand, ozone mixes with the spray-absorption liquid of washing absorption tower inside, can be converted into high valence state to the oxysulfide in flue gas by liquid phase oxidation, and oxidation fully, effectively avoids being oxidized halfway situation.The nitrogen oxide of high valence state and oxysulfide more easily remove and are extracted and recycle.
Ozone generating-device is by the first pipeline (pipeline one, with reference to Fig. 1, the first pipeline place is provided with gaseous oxidation valve 12) be communicated to the flue that the gas approach of washing absorption tower or this gas approach are communicated with, object is to make flue gas to mix with ozone before entering washing absorption tower, nitrogen oxide in flue gas is fully oxidized, is oxidizing to high valence state; Ozone generating-device is by second pipe (pipeline two, with reference to Fig. 1, second pipe place is provided with liquid phase oxidation valve 13) be communicated with the spraying layer in absorption tower, so that ozone is imported in spraying layer and to be mixed with spray liquid, due to ozone pair and the mixed SO of water
2have stronger oxidation, thereby the ozone mixing with spray liquid can be directly by SO
2be oxidizing to high valence state.Spray liquid adsorbs the nitrogen oxide of high valence state and oxysulfide simultaneously, and falls into tower reactor, the nitrogen in solution in tower reactor and sulphur is recycled afterwards again, has completed the abundant oxidation removal of the pollutant to flue gas.Clean flue gas is discharged from the top of washing absorption tower enters chimney, meets the discharge standard of national regulation.The inside of washing absorption tower sets gradually demister, spraying layer and tower reactor from top to bottom, because absorption tower is in running, easily producing particle diameter is " mist " of 10--60 micron, " mist " not only contains moisture, it is also dissolved with sulfuric acid, sulfate, sulfur dioxide etc., also easily causes staining and heavy corrosion of blower fan, heat exchanger and flue, therefore simultaneously, absorption equipment is proposed to the requirement of demist, complete by demister.In tower reactor, there is absorption liquid, and by being located at outside circulating pump, absorption liquid is imported to the spraying layer in tower, flue gas is sprayed to absorption.
Above-described embodiment one is a basic embodiment of the present invention, also can be optimized it, obtains more preferred embodiment.
Preferably, the present invention also can introduce air-introduced machine on the basis of embodiment mono-, the first device for cleaning pipeline is crossed air-introduced machine and is communicated with the gas approach of washing absorption tower, and the entrance of air-introduced machine is communicated with a flue simultaneously, so that the flue gas in ozone and the flue of the first pipeline mixed before entering air-introduced machine.Particularly, the entrance of air-introduced machine is communicated with a flue, and extremely described flue of the first pipeline communication, and the outlet of described air-introduced machine is communicated to the gas approach of described washing absorption tower.Can be with reference to Fig. 1, in the flue that flue gas 1 is communicated with at the entrance of air-introduced machine 2, mix with ozone, after the eddy current effect of air-introduced machine, can further strengthen the oxidation effectiveness of ozone to nitrogen oxides in effluent.More preferably, the flue place before air-introduced machine entrance arranges uniform device, can make flue gas be uniformly distributed, and ozone is mixed with flue gas fully, also can strengthen the oxidation effectiveness of ozone to nitrogen oxides in effluent.
Preferably, the gas approach of washing absorption tower is positioned at the top of described tower reactor.
Preferably, the spraying layer in tower reactor comprises shower, nozzle, and shower is multilayer, for example, be 3-5 layer, and spray flux is larger, can improve adsorption efficiency; And nozzle has hollow cone tangent type structure, and simple in structure, atomization is even, easy to use.
Preferably, in basic embodiment for the circulating pump that is communicated with tower reactor and spraying layer by the spray flux of spraying layer described in a flow control valve control, adjusting time easy to use, for example, can regulate according to exhaust gas volumn.
Preferably, the outside of tower reactor is also provided with an acid solution excavationg pump, and the interface position of described acid solution excavationg pump and described tower reactor is higher than the interface position of described circulating pump and described tower reactor.Because the absorption liquid of tower reactor inside circulates between tower reactor and spraying layer, and nitrogen oxide and the oxysulfide of absorption liquid from spraying layer spray and in flue gas carries out adsorption reaction, after operation a period of time, in tower reactor, the pH value of absorption liquid can change, need in the present invention to monitor this pH value and be greater than 5, otherwise adsorption reaction efficiency will reduce greatly.The pH value sensor of pH in one monitoring tower reactor preferably, is set in tower reactor; After monitoring the pH value of absorption liquid in tower reactor and being less than or equal to 5, by the acid solution excavationg pump being connected with tower reactor, the part solution in tower reactor is discharged.Meanwhile, be communicated with one at tower reactor place for supplement the absorption liquid pipeline of absorption liquid to this tower reactor, after absorption liquid is discharged by acid solution excavationg pump, in tower reactor, supplement new absorption liquid by absorption liquid pipeline; And an absorption liquid replenishment valve is set in absorption liquid pipeline, for controlling the magnitude of recruitment of absorption liquid in tower reactor.
Preferably, the demist layer in tower reactor comprises demist filter screen and washer jet, and described washer jet has hollow-core construction, and the cleaning solution at demist layer place is fresh water (FW) (process water).
In the present invention, ozone generating-device belongs to ozone application technical field, can be discharge type generating means or electrolytic water generator.Discharge type generating means, by electrolysis air or pure oxygen, generates ozone, but wherein the content of foreign gas is higher.The water-soluble formation function water of ozone that electrolytic water generator produces, its ozoniferous purity is higher, is widely used in the fields such as beverage, precise part cleaning, surface treatment.The present invention mainly adopts discharge type generating means.Preferably, ozone generating-device of the present invention comprises liquid oxygen storage tank, vaporizer and ozone generator, and wherein, liquid oxygen storage tank is the low-temperature storage tank for storing liquid oxygen, can replace the repeatedly round transport of gas cylinder, saves manpower and cost, is the first-selection of central gas supply; Vaporizer is a kind of industry and civilian energy-saving equipment, and effect is the gas that liquid gas is converted into gaseous state; Ozone generator is for producing ozone gas (O
3) device.Ozone is easy to decompose and cannot stores, and needs scene to produce on-the-spot use (in special situation, can carry out the storage of short time), and the place that can use ozone so every all needs to use ozone generator.In use, the liquid oxygen in liquid oxygen storage tank becomes gaseous oxygen by vaporizer, is produced and is obtained ozone more afterwards by ozone generator.
In use of the present invention, preferably, described second pipe is communicated with described spraying layer by a pair of fluid line, and this two-fluid pipeline is bushing type pipeline, it comprises inner tube and is placed on the outer tube outside this inner tube, and offers uniform aperture on the tube wall of described inner tube.The inner tube of described bushing type pipeline passes into gas (ozone), outer tube passes into liquid (spray-absorption liquid), on the tube wall of inner tube, have uniform aperture, can make ozone and spray-absorption liquid can realize mixing in sleeve pipe, and be mixed to get comparatively even.Wherein, preferably, the small aperture of offering on inner pipe wall is 3～5cm, and percent opening is 50～60%.With reference to Fig. 1, the liquid phase oxidation valve 13 on second pipe is with check function, prevents liquid backflow.
In a full implementation example of the present invention, with reference to Fig. 1, the flue gas purification system of integrated desulfurizing denitration of the present invention comprises air-introduced machine 2, washing absorption tower 3, chimney 10, ozone generating-device 11, washing absorption tower 3 comprises from top to bottom demist layer 7, spraying layer 5 and is positioned at the tower reactor of washing absorption tower 3 bottoms.Flue gas 1 after dedusting enters air-introduced machine 2 from flue, and ozone generating-device is communicated with this flue by the first pipeline (the first pipeline place is provided with gaseous oxidation valve 12), ozone and flue gas are mixed entering before air-introduced machine, and be provided with uniform device in this flue, the mixture of flue gas and ozone is entered in washing absorption tower 3 by the eddy current effect of uniform device and air-introduced machine, and mixing and oxidation effectiveness are all more abundant.Simultaneously the second pipe (second pipe place is provided with liquid phase oxidation valve 13) of ozone generating-device 11 by a telescopic two-fluid mixing duct 14 be communicated with spraying layer 5, the inner tube of two-fluid mixing duct 14 is ozone, it in outer tube, is spray liquid, on inner tubal wall, be evenly equipped with aperture, ozone is fully mixed with spray liquid, obtain ozone-water blend absorbent, and from nozzle 6 ejections.Solution in tower reactor is communicated to spraying layer place by circulating pump 4, is spray liquid, and mixes with ozone, and spray flux is controlled by flow control valve 15.In the time that the pH in tower reactor is less than or equal to 5, by acid solution excavationg pump 17, part solution is discharged, and in tower reactor, supplement new solution by absorption liquid pipeline; And an absorption liquid replenishment valve 16 is set in absorption liquid pipeline, for controlling the magnitude of recruitment of absorption liquid in tower reactor.And the interface position of acid solution excavationg pump 17 and tower reactor is the interface position with tower reactor higher than circulating pump 4.On the top of washing absorption tower 3, demist layer 7 operation water 8 carry out demist to flue gas, and after the purification obtaining, flue gas 9 is discharged from chimney 10.
In a specific embodiment, flue gas condition to be clean is as follows: C (SO
2)=1200mg/m
3, C (NO)=450mg/m
3, 120 DEG C of flue-gas temperatures, enter after dedusting in flue gas purification system of the present invention, and in the ozone straying quatity of ozone generating-device and flue gas, nitric oxide production mol ratio is 1.0, and tower reactor pH value is controlled at 6.0 left and right, and washing absorption tower liquid-gas ratio is controlled at 8L/m
3, absorbing through the liquid phase oxidation of ozone gas phase, smoke desulfurization efficiency is 95%, denitration efficiency is 80%.
The present invention also provides a kind of flue gas purifying method of integrated desulfurizing denitration, and it has adopted the flue gas purification system of above-mentioned integrated desulfurizing denitration.In an embodiment of flue gas purifying method of the present invention, comprise the following steps:
Ozone and flue gas mix entering before the gas approach of described washing absorption tower, and ozone carries out gaseous oxidation to flue gas; (step 1)
Ozone mixes with the liquid of described circulating-pump outlet, forms ozone-water blend absorbent; (step 2)
Enter described washing absorption tower with the mixed flue gas of ozone, described ozone-water blend absorbent carries out further liquid phase oxidation through spraying layer spray to flue gas, simultaneously to flue gas desulfurization and denitrification; (step 3)
Flue gas after desulphurization denitration carries out after demist is dried entering described smoke stack emission through described demister.(step 4)
In the embodiment of above-mentioned flue gas purifying method, do not limit the enforcement order of each step, for example step 1 and step 2 just can be carried out simultaneously.This embodiment is the basic embodiment of flue gas purifying method of the present invention, also can make improvements, and obtains more preferably embodiment.
Preferably, after ozone mixes with flue gas, be introduced into described washing absorption tower by air-introduced machine, can utilize like this eddy current effect of air-introduced machine, strengthen the oxidation effectiveness of ozone to the nitrogen oxide in flue gas.
Preferably, ozone mixes with flue gas, and enters described washing absorption tower after uniform in pipeline.Can by arranging in flue, uniform device be realized ozone and flue gas is mixed uniform, ozone is mixed with flue gas, and then can improve the gaseous oxidation efficiency of ozone.
Preferably, described ozone-water blend absorbent flue gas is oxidized and desulphurization denitration after, falling to the solution in described tower reactor is being discharged to the extraction recovery of carrying out nitrogen and sulphur after tower reactor, so not only can effectively avoid secondary pollution, also can recycle nitrogen sulphur simultaneously, turn waste into wealth.In the time extracting recovery, can make elemental sulfur or nitrogen by technique, or other modes are extracted.
Preferably, in order to ensure the adsorption efficiency of washing absorption tower to pollutant in flue gas, need the pH value that ensures the absorption liquid in tower reactor to be greater than 5, after being less than or equal to 5, adsorption efficiency just has decline by a relatively large margin.Whether one pH value monitor can be set monitors the pH value of absorption liquid in tower reactor and meets the demands.In the time that the pH of absorption liquid in tower reactor value is less than or equal to 5, the absorption liquid in tower reactor is discharged.And can supplement absorption liquid to tower reactor by absorption liquid pipeline, and by the liquid level of an absorption liquid replenishment valve control absorption liquid in tower reactor, control the absorption liquid measure in tower reactor.
Preferably, in the step of mixing before ozone is entering the gas approach of washing absorption tower with flue gas, the mol ratio of NO in ozone and the flue gas passing into is 0.8-1.2, can effectively ensure that like this ozone is more abundant to the nitrogen oxide oxidation in flue gas, and be unlikely to pass into more ozone amount, cause the waste of ozone.In this step, the ozone amount passing into also can be adjusted according to the content of the nitrogen oxide in flue gas, and it is more convenient to use.
Preferably, in the step of mixing with the absorption liquid at spraying layer place at ozone, the SO in ozone and the flue gas passing into
2mol ratio be 0.8-1.2, can effectively ensure that like this ozone is more abundant to the oxidation of oxysulfide, and be unlikely to cause the waste of ozone.In this step, the ozone amount passing into also can be adjusted according to the content of the oxysulfide in flue gas, and it is more convenient to use.
Preferably, the liquid-gas ratio in described washing absorption tower is 7～10L/m
3, can effectively ensure that washing absorption tower operation is safer, and ensure to flue gas internal contamination thing compared with high adsorption rate.
In concrete application of the present invention, former flue gas after dedusting fully mixes entering before air-introduced machine with from ozone generating-device Yi road ozone gas, NO gas in flue gas is oxidized to high valence state nitrogen oxide, and enter into washing absorption tower, with the ozone-water blend absorbent counter current contacting from spraying layer, NOx and SO
2after the oxidation of absorbent absorption and ozone, be converted into certain density nitric acid and sulfuric acid, and fall after rise in tower reactor.And that flue gas enters the demist of demist layer after desulphurization denitration is dry, finally enter smoke stack emission.Solution in tower reactor is squeezed into spraying layer as absorbent through circulating pump, and mixes with the other road ozone gas from ozone generating-device before entering spraying layer, and the absorption liquid that is dissolved with ozone is to the absorption that circulates of the pollutant in flue gas.In the time that the pH of the solution in tower reactor value is less than 5, part acid solution is discharged through acid solution excavationg pump, and the absorbent in tower reactor is crossed absorption liquid replenishment valve by absorption liquid device for cleaning pipeline and supplemented, and stops supplementing absorption liquid in the time that liquid level reaches requirement.And the acid solution of discharging in tower reactor adopts, and conventional method is concentrated, separation obtains sulfuric acid and nitric acid product.Fresh water (FW) is delivered to demist layer through pressurization and is rinsed, and prevents fouling.
The present invention is by two kinds of mode combinations of ozone gas phase liquid phase oxidation, strengthening assimilation effect, and the liquid phase oxidation of ozone is directly by paramount oxidize sulfur oxides valence state compound, and without increasing extra oxidation unit, and the certain density tower reactor acid solution obtaining also can be sold through being further processed into finished product.It is simple that whole system has flow process, and floor space is little, and cost of investment is low, denitrification efficiency advantages of higher, and resource consumption is few, operating cost is low.
It should be noted that all independent assortments as required of above-described embodiment.The above is only the preferred embodiment of the present invention; it should be pointed out that for those skilled in the art, under the premise without departing from the principles of the invention; can also make some improvements and modifications, these improvements and modifications also should be considered as protection scope of the present invention.
Claims (10)
1. a flue gas purification system for integrated desulfurizing denitration, is characterized in that, comprising:
Ozone generating-device, washing absorption tower, chimney,
Wherein, described washing absorption tower comprises the demist layer, spraying layer and the tower reactor that set gradually from top to bottom, outer setting one circulating pump of described tower reactor;
Described ozone generating-device is communicated with the gas approach of described washing absorption tower by the first pipeline, and flue gas was mixed with ozone before entering described washing absorption tower; Described ozone generating-device is communicated with described spraying layer by second pipe, and imports ozone in described spray piping, ozone is mixed with absorption liquid after from the ejection of described spraying layer;
Described tower reactor is communicated with described spraying layer by described circulating pump;
The clean exhanst gas outlet of described washing absorption tower is communicated with described chimney.
2. the flue gas purification system of integrated desulfurizing denitration according to claim 1, is characterized in that, further comprises:
Air-introduced machine, described the first device for cleaning pipeline is crossed described air-introduced machine and is communicated with the gas approach of described washing absorption tower, and the entrance of described air-introduced machine is communicated with a flue simultaneously, so that the flue gas in the ozone of described the first pipeline and described flue mixed before entering described air-introduced machine.
3. the flue gas purification system of integrated desulfurizing denitration according to claim 2, is characterized in that:
In described flue, be provided with uniform device;
And/or;
The gas approach of described washing absorption tower is positioned at the top of described tower reactor;
And/or;
Described spraying layer comprises shower, nozzle, and described shower is multilayer; Described nozzle has hollow cone tangent type structure;
And/or;
Described circulating pump is by the spray flux of spraying layer described in a flow control valve control;
And/or;
The outside of described tower reactor is also provided with an acid solution excavationg pump, and the interface position of described acid solution excavationg pump and described tower reactor is higher than the interface position of described circulating pump and described tower reactor.
4. the flue gas purification system of integrated desulfurizing denitration according to claim 1, is characterized in that:
In described tower reactor, be provided with the pH value sensor for monitoring pH in described tower reactor;
Described tower reactor place is communicated with one for supplement the absorption liquid pipeline of absorption liquid to described tower reactor, and an absorption liquid replenishment valve is set in described absorption liquid pipeline.
5. the flue gas purification system of integrated desulfurizing denitration according to claim 1, is characterized in that:
Described demist layer comprises demist filter screen and washer jet, and described washer jet has hollow-core construction.
6. according to the flue gas purification system of the integrated desulfurizing denitration described in claim 1-5 any one, it is characterized in that:
Described ozone generating-device comprises liquid oxygen storage tank, vaporizer and ozone generator;
And/or;
Described second pipe is communicated with described spraying layer by a pair of fluid line, and described two-fluid pipeline is bushing type pipeline, and it comprises inner tube and be placed on the outer tube outside this inner tube, and offers uniform aperture on the tube wall of described inner tube.
7. a flue gas purifying method for integrated desulfurizing denitration, is characterized in that:
The flue gas purification system of the integrated desulfurizing denitration described in employing claim 1-6 any one, it comprises the following steps:
Ozone and flue gas mix entering before the gas approach of described washing absorption tower, and ozone carries out gaseous oxidation to flue gas;
Ozone mixes with the liquid of described circulating-pump outlet, forms ozone-water blend absorbent;
Enter described washing absorption tower with the mixed flue gas of ozone, described ozone-water blend absorbent carries out further liquid phase oxidation through spraying layer spray to flue gas, simultaneously to flue gas desulfurization and denitrification;
Flue gas after desulphurization denitration carries out after demist is dried entering described smoke stack emission through described demister.
8. the flue gas purifying method of integrated desulfurizing denitration according to claim 7, is characterized in that,
After ozone mixes with flue gas, be introduced into described washing absorption tower by air-introduced machine;
And/or;
Ozone mixes with flue gas, and enters described washing absorption tower after uniform in pipeline;
And/or;
Described ozone-water blend absorbent flue gas is oxidized and desulphurization denitration after, reclaim discharging the extraction of carrying out nitrogen and sulphur after tower reactor falling after rise to the solution in described tower reactor.
9. the flue gas purifying method of integrated desulfurizing denitration according to claim 7, is characterized in that,
Monitor the pH value of the absorption liquid in described tower reactor, in the time of its pH≤5, the absorption liquid in described tower reactor is discharged;
And/or;
By described absorption liquid pipeline to described tower reactor supplement absorption liquid, and by described absorption liquid replenishment valve control absorption liquid the liquid level in described tower reactor.
10. the flue gas purifying method of integrated desulfurizing denitration according to claim 7, is characterized in that:
In mixing before described ozone and flue gas are entering the gas approach of described washing absorption tower, the mol ratio of the NO in ozone and the flue gas passing into is 0.8-1.2;
And/or;
In described ozone mixes with the absorption liquid at described spraying layer place, the SO in ozone and the flue gas passing into
2mol ratio be 0.8-1.2;
And/or;
Liquid-gas ratio in described washing absorption tower is 7～10L/m
3.
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