CN101485957B - Device and method of simultaneous desulfuration and denitration for flue gas using ozone oxygenation combined with double-tower washing - Google Patents
Device and method of simultaneous desulfuration and denitration for flue gas using ozone oxygenation combined with double-tower washing Download PDFInfo
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Abstract
The invention relates to a technique for processing flue gas of a coal burning boiler, and aims to provide a device and a method for desulfurizing and denitrating the flue gas of the coal burning boiler by using ozone oxidation and double tower washing. The device comprises a flue which is connected with a heat exchanger, an alkali liquor washing tower A, and an alkali liquor washing tower B in sequence, wherein the insides of the alkali liquor washing tower A and the alkali liquor washing tower B are provided with a circular spraying device A and a circular spraying device B respectively; and an ozone generator is connected with a lower liquid phase area of the alkali liquor washing tower A and a pipeline in front of the circular spraying device B respectively. The novel method for desulfurizing and denitrating the flue gas of the coal burning boiler by using ozone oxidation and double tower washing can achieve the denitration efficiency of more than 80 percent and desulfurization efficiency of more than 95 percent, and realize the reclaiming and reusing denitrated and desulfurized products in different devices respectively.
Description
Technical field
The present invention relates to the fire coal boiler fume treatment technology, relate in particular to the device and method of a kind of using ozone oxygenation combined with double-tower washing the flue gas and desulfurizing and denitrifying of coal-burning boiler.
Background technology
The oxysulfide that produces in the combustion of fossil fuel process, nitrogen oxide have caused serious day by day harm to the atmospheric environment of China.Desulfur technology at combustion system can be divided three classes at present: dry method, semidry method and wet method.Wherein, dry method, semidry method investment operating cost is low, but often desulfuration efficiency is not high, if use the discharging etc. of the oxygen sulfur compound of dry method and semi-dry desulphurization technology large-sized boiler combustion apparatus such as station boiler often can not reach environmental requirement.The high-efficiency desulfurization device that station boiler extensively adopts is a limestone/gypsum wet process of FGD technology (WFGD), this method desulfuration efficiency height, stable, but this sulfur method exists the fouling on absorption tower to stop up, the recovery system complex process of desulfurizing byproduct, investment is high, and quality of desulphurization gypsum is low, most of desulfurization product causes the shortcoming of secondary pollution easily for abandoning processing.
The control technology of nitrogen oxide mainly contains two classes: denitration of stove internal combustion and denitrating flue gas.The former mainly contains the low-NOx combustor technology, OFA (Over fire air) technology, and the low oxygen combustion technology, combustion technology etc. is controlled NO by the combustion process adjustment again
xDischarging, can be with NO
xBe controlled at medium emission level, general denitration efficiency is about 30～50%.But these denitration technologies cause combustion stability to descend easily, and burner region forms local reduction atmosphere easily, cause ash fusion point to descend, and cause the pickup slagging scorification phenomenon of water-cooling wall, influence the normal safe operation of boiler.Along with the further raising of environmental requirement, very difficult realization is NO more efficiently simultaneously
xEmission control.For a kind of denitration technology in back, developed countries such as American-European Japan extensively adopt SCR technology (SCR).SCR technology denitration efficiency height, stable, the problem that exists is, the inactivation of catalyst, reducing substances (as ammoniacal liquor etc.) are revealed the secondary pollution that causes, under the high grey deployment scenarios in the flue gas higher dust granules cause that easily problem, operation and the investment costs such as wearing and tearing, obstruction of catalyst are very expensive.Environmental Protection in China work is started late, if the thinking that adopts developed country to administer item by item, adopt the desulfurization of wet process of FGD WFGD device, the method of selectivity catalysis SCR denitration certainly will increase investment, operating cost, and therefore some old units even have problem such as difficult arrangement need developing low-cost, high efficiency while desulphurization denitration and can realize the technology of product recycling.
Flue gas and desulfurizing and denitrifying technology in research has dry method while desulphurization denitration technology in the stove, electro-catalysis while desulphurization denitration technology etc. at present.Electro-catalysis desulphurization denitration technology removal efficiency height simultaneously wherein, operating cost is low, is becoming the focus of people's research.Present electro-catalysis technology comprises electron beam technology, pulsed discharge plasma technology, technology such as steam ammonia corona discharge activation.Mainly utilize the neutral molecule (N in high energy electron and the flue gas
2, O
2, H
2O etc.) collision produces some living radicals (O, OH, O
3, HO
2Deng), the SO in these free radicals and the flue gas
2And NO
xMolecular reaction generates SO
3, high valence state nitrogen oxide, nitric acid, sulfuric acid etc. are at NH
3Generate byproducts such as ammonium sulfate, ammonium nitrate under the condition that exists.Advantage is a dry removal, does not produce waste water and dregs, and energy is desulphurization denitration simultaneously, and accessory substance can recycling.But because the free radical time-to-live is very short, the generation and the smoke reaction device of free radical need be united two into one, discharge at whole flue, and contain a large amount of N in the boiler smoke
2, CO
2, H
2Material such as O, dust, discharging condition is abominable, simultaneously N
2, CO
2Consume a large amount of input energy, cause capacity usage ratio low, overall operation expense costliness, the desulphurization denitration product is the impurity of sulphur nitrogen in addition, and is not easily separated, is worth lower.
Summary of the invention
The objective of the invention is characteristics single at present various flue gas desulfurization and denitrification technical functionalitys, that investment is big, operating cost is high, accessory substance value is low, the device of a kind of using ozone oxygenation combined with double-tower washing to the flue gas and desulfurizing and denitrifying of coal-burning boiler is provided, and further object of the present invention provides a kind of method based on this device.
Using ozone oxygenation combined with double-tower washing among the present invention comprises flue to the device of flue gas and desulfurizing and denitrifying, and flue is connected with heat exchanger, alkali liquid washing tower A, alkali liquid washing tower B successively; In alkali liquid washing tower A and the alkali liquid washing tower B circulating sprayer A and circulating sprayer B are set respectively, ozone generator respectively with alkali liquid washing tower A bottom liquid phase region with enter alkali liquid washing tower B before pipeline link to each other.
As a kind of improvement, the bottom of alkali liquid washing tower A, alkali lye surge tank A, NaOH solution circulating pump A, alkali lye spray vacuum tank A, circulating sprayer A connect successively by pipeline.
As a kind of improvement, the bottom of alkali liquid washing tower B, alkali lye surge tank B, NaOH solution circulating pump B, alkali lye spray vacuum tank B, circulating sprayer B connect successively by pipeline.
As a kind of improvement, alkali lye surge tank A, alkali lye surge tank B are connected to the alkali storage tank by pipeline respectively.
As a kind of improvement, alkali lye surge tank A, alkali lye surge tank B are connected to crystallization apparatus A, crystallization apparatus B by pipeline respectively.
As a kind of improvement, alkali lye surge tank A, alkali lye surge tank B are connected to the fresh water (FW) supply line by pipeline respectively.
Using ozone oxygenation combined with double-tower washing among the present invention may further comprise the steps flue gas and desulfurizing and denitrifying:
1) boiler smoke enters first alkali liquid washing tower A after heat exchanger is cooled to 90 ℃, and the sulfur dioxide of Yi Rong is absorbed into liquid phase; The ozone that ozone generator produces feeds the liquid phase region of alkali liquid washing tower A bottom, and the sexavalence sulphur that under 40～60 ℃ temperature the sulphur of tetravalence is oxidized to generates stable sulfate, and the mol ratio of feeding ozone amount and liquid phase tetravalence sulphur is 0.8～1.0;
2) ozone is sneaked into the flue that enters before the alkali liquid washing tower B, ozone amount that sprays into and the nitrogen oxide molar ratio in the boiler smoke are 0.5～1.5, water-fast oxidation of nitric oxide in the boiler smoke is become high price nitrogen oxide such as nitrogen dioxide soluble in water, nitrogen peroxide, in alkali liquid washing tower B, absorbed by alkali lye.
3) through behind the alkali liquid washing tower B, flue gas is sent flue back to after being heated through heat exchanger again.
As a kind of improvement, described alkali lye is the wherein at least a aqueous solution of NaOH, potassium hydroxide, calcium hydroxide, calcium oxide or calcium carbonate.
As a kind of improvement, described alkali lye is ammoniacal liquor.
Device among the present invention has the flue that is connected successively, heat exchanger, two alkali liquid washing towers, scrubbing tower bottoms and the alkali lye surge tank is set respectively with circulating sprayer, alkali lye surge tank the PH meter is set and links to each other with crystallization apparatus with liquid level emasuring device, surge tank, circulating sprayer has circulating pump, vacuum tank and nozzle, and vacuum tank is provided with device for pressure measurement.Ozone generator and first scrubbing tower bottom liquid phase region with enter second pipeline before the scrubbing tower and link to each other.Through returning flue after the heating of two scrubbing tower flue gas after being purified heater via again.
Fire coal boiler fume may further comprise the steps with the method for strong oxidizer using ozone oxygenation combined with double-tower washing while desulphurization denitration:
1) boiler smoke (1) is cooled to about 90 ℃ behind heat exchanger (2), enter first alkali liquid washing tower (3), easily molten sulfur dioxide is absorbed into liquid phase, the part ozone that ozone generator produces feeds scrubbing tower bottom liquid phase region, the sexavalence sulphur that under 40-60 ℃ temperature the sulphur of tetravalence is oxidized to feeds that tetravalence sulphion mol ratio is about 0.8～1.0 in ozone amount and the liquid phase.
2) by pH value and liquid level in the monitoring surge tank, to realize automatic Jia Shui, add alkali and product discharging, the high concentration product of discharge prepares sulfate, nitrate behind condensing crystallizing.
3) spray equipment realizes that by vacuum tank is set nozzle exit pressure is stable, guarantees atomizing effect.
4) part ozone is sprayed into enter the preceding flue of second alkali liquid washing tower (11), the nitric oxide molar ratio that sprays in ozone amount and the boiler smoke is 0.5～1.5, water-fast oxidation of nitric oxide in the boiler smoke is become high price nitrogen oxide such as nitrogen dioxide soluble in water, nitrogen peroxide, in second scrubbing tower (11), absorbed by alkali lye.
5) described alkali lye is that NaOH, potassium hydroxide, calcium hydroxide, calcium oxide, calcium carbonate, ammoniacal liquor are wherein at least a.
The invention has the beneficial effects as follows: flue gas by ozone oxidation combined with double-tower washing provided by the invention is the desulphurization denitration new method simultaneously, can reach denitration efficiency and 95% above desulfuration efficiency more than 80%, realize the recycling respectively in different devices of desulphurization denitration product.
Description of drawings
Fig. 1 is a fire coal boiler fume strong oxidizer using ozone oxygenation combined with double-tower washing desulfuring and denitrifying apparatus structural representation simultaneously;
Among the figure: boiler flue 1, heat exchanger 2, alkali liquid washing tower A3, ozone generator 4, alkali lye surge tank A5, NaOH solution circulating pump A6, alkali lye spray vacuum tank A7, fresh water (FW) 8, alkali storage tank A9, crystallization apparatus A10, alkali liquid washing tower B11, alkali lye surge tank B12, NaOH solution circulating pump B13, alkali lye spray vacuum tank B14, crystallization apparatus B15.
The specific embodiment
The present invention is directed to and spray into the liquid phase region of first scrubbing tower respectively and enter the preceding flue of second scrubbing tower after local air or oxygen discharge produce ozone, realization is to nitric oxide production oxidation respectively in tetravalence sulphion and the gas phase in the liquid phase, in two wet scrubbing towers, carry out desulphurization denitration respectively then, if wet desulphurization device being installed then can effectively transform, realize desulphurization denitration simultaneously.
O
3Extensively exist in electron beam, pulsed plasma discharge as a kind of of free radical, and O
3Life cycle is longer relatively, therefore can with little air or oxygen at first ionization generate O
3, send into then and remove device, just can reduce the power consumption of system greatly, through estimation O
3Only need gas to total exhaust gas volumn about 6% discharge just can to satisfy oxidation requirement to the pollutant in the flue gas.
Below in conjunction with the drawings and specific embodiments the present invention is described in further detail.
A kind of fire coal boiler fume has flue 1, heat exchanger 2, alkali liquid washing tower A3, the alkali liquid washing tower B11 that is connected successively with the device of strong oxidizer using ozone oxygenation combined with double-tower washing while desulphurization denitration.In alkali liquid washing tower A3 and the alkali liquid washing tower B11 circulating sprayer A and circulating sprayer B are set respectively.Alkali lye surge tank A5, alkali lye surge tank B12 all are provided with PH meter and liquid level emasuring device.Alkali lye surge tank A5, alkali lye surge tank B12 are connected to crystallization apparatus A10, crystallization apparatus B15 by pipeline respectively.Spray equipment has circulating pump, vacuum tank and nozzle, and vacuum tank is provided with device for pressure measurement.Ozone generator 4 and alkali liquid washing tower A3 bottom liquid phase region with enter alkali liquid washing tower B11 before pipeline link to each other.Through returning flue 1 after 2 heating of two scrubbing tower flue gas after being purified heater via again.
Fire coal boiler fume may further comprise the steps with the method for strong oxidizer using ozone oxygenation combined with double-tower washing while desulphurization denitration:
1) boiler smoke enters first alkali liquid washing tower A3 easily molten sulfur dioxide is absorbed into liquid phase after heat exchanger 2 is cooled to 90 ℃.The part ozone that ozone generator 4 produces feeds scrubbing tower bottom liquid phase region, and the sexavalence sulphur that under 40～60 ℃ temperature the sulphur of tetravalence is oxidized to generates stable sulfate, and the mol ratio of feeding ozone amount and liquid phase tetravalence sulphur is 0.8～1.0.
2) part ozone is sneaked into the flue that enters before the alkali liquid washing tower B 11, the nitrogen oxide molar ratio that sprays in ozone amount and the boiler smoke is 0.5～1.5, water-fast oxidation of nitric oxide in the boiler smoke is become high price nitrogen oxide such as nitrogen dioxide soluble in water, nitrogen peroxide, in scrubbing tower 11, absorbed, generate and stablize nitrate by alkali lye.
3) through behind the alkali liquid washing tower B11, flue gas is sent flue 1 back to after being heated through heat exchanger 2 again.
In the oxysulfide of boiler smoke discharging mainly is sulfur dioxide, is dissolved in the sulphur of the tetravalence of liquid phase, can is sexavalence sulphur by ozone oxidation, generates and stablizes sulfate.Nitric oxide accounts for more than 95% in the nitrogen oxide in the flue gas, other is nitrogen dioxide, nitrous oxide etc., and nitric oxide is water insoluble, it is one of gaseous contamination material that is difficult to handle, and the nitrogen dioxide of high valence state, nitrogen peroxide can generate nitrous acid, nitric acid with the water reaction, are very easily removed by the wet scrubbing device.By spraying into ozone, O
3/ NO molar ratio gets 0.5～1.5, can be high valence state material soluble in water with oxidation of nitric oxide, removes by the wet scrubbing tower.Utilize ozone oxidation just can realize the sulphur nitrogen recycling of efficient desulphurization denitration simultaneously and product in conjunction with afterbody wet method double-tower washing.If be equipped with limestone/gypsum wet process of FGD equipment, perhaps water dust scrubber then can carry out integrating the cost of reducing investment outlay with this method after the appropriate reconstruction to it.
Detailed process is: flue gas at first is cooled to 90 ℃ through heat exchanger 2, enters alkali liquid washing tower A3 then easily molten sulfur dioxide is removed, and part ozone feeds liquid phase region tetravalence sulphur is oxidized to sexavalence sulphur; Flue before entering alkali liquid washing tower B 11 sprays into part ozone, nitrogen oxide after the oxidation removes by alkali liquid washing tower B11, absorption liquid is an alkali lye, and absorption liquid is recycling, and the sulfate of enrichment, nitrate are handled the back respectively and sold or further handle in two concentration and crystallization devices.Further specify below in conjunction with accompanying drawing:
Fire coal boiler fume strong oxidizer using ozone oxygenation combined with double-tower washing desulphurization denitration arrangement simultaneously, as shown in Figure 1.Fire coal boiler fume successively through two alkali liquid washing towers, returns and sends flue 1 again back to after heat exchanger 2 heats after heat exchanger 2 coolings.Air or oxygen is sent into ozone generator 4 preparation high-concentrated ozones, ozone one tunnel is sent into the liquid phase region of alkali liquid washing tower A3, oxidation tetravalence sulphion in liquid phase, the feeding amount is adjusted in real time according to tetravalence sulphion concentration in the liquid phase, guarantee that mol ratio is about 0.8～1.0, another road sprays into and enters the preceding flue of alkali liquid washing tower B11, according to nitric oxide concentration in the flue gas, press ozone and nitric oxide mol ratio 0.5～1.5 and adjust in real time, sulfur dioxide and nitrogen oxide absorb in two each and every one scrubbing towers respectively.The absorption liquid of two towers is recycling, and the sulfate of absorption and nitrate carry out condensing crystallizing to be handled.Scrubbing tower adopts alkali lye as absorbent, and scrubbing tower is a spray column.Alkali lye as absorbent is NaOH, also can be water, the perhaps aqueous solution of potassium hydroxide, calcium hydroxide, calcium oxide, these materials of calcium carbonate, or in the ammoniacal liquor one or more.
At last, it is also to be noted that what more than enumerate only is specific embodiments of the invention.Obviously, the invention is not restricted to above embodiment, many distortion can also be arranged.
The present invention can summarize with other the concrete form without prejudice to spirit of the present invention and principal character.Therefore, no matter from which point, above-mentioned embodiment of the present invention all can only be thought can not limit the present invention to explanation of the present invention, claims have been pointed out scope of the present invention, and scope of the present invention is not pointed out in above-mentioned explanation, therefore, in implication suitable and any change in the scope, all should think to be included in the scope of claims with claims of the present invention.
Claims (9)
1. a using ozone oxygenation combined with double-tower washing comprises flue to the device of flue gas and desulfurizing and denitrifying, it is characterized in that flue is connected with heat exchanger, alkali liquid washing tower A, alkali liquid washing tower B successively; In alkali liquid washing tower A and the alkali liquid washing tower B circulating sprayer A and circulating sprayer B are set respectively, ozone generating-device respectively with alkali liquid washing tower A bottom liquid phase region with enter alkali liquid washing tower B before pipeline link to each other.
2. using ozone oxygenation combined with double-tower washing according to claim 1 is to the device of flue gas and desulfurizing and denitrifying, it is characterized in that the bottom of alkali liquid washing tower A, alkali lye surge tank A, NaOH solution circulating pump A, alkali lye spray vacuum tank A, circulating sprayer A connect successively by pipeline.
3. using ozone oxygenation combined with double-tower washing according to claim 1 is to the device of flue gas and desulfurizing and denitrifying, it is characterized in that the bottom of alkali liquid washing tower B, alkali lye surge tank B, NaOH solution circulating pump B, alkali lye spray vacuum tank B, circulating sprayer B connect successively by pipeline.
According to claim 2 or 3 described any one using ozone oxygenation combined with double-tower washing to the device of flue gas and desulfurizing and denitrifying, it is characterized in that alkali lye surge tank A, alkali lye surge tank B are connected to the alkali storage tank by pipeline respectively.
According to claim 2 or 3 described any one using ozone oxygenation combined with double-tower washing to the device of flue gas and desulfurizing and denitrifying, it is characterized in that alkali lye surge tank A, alkali lye surge tank B are connected to crystallization apparatus A, crystallization apparatus B by pipeline respectively.
According to claim 2 or 3 described any one using ozone oxygenation combined with double-tower washing to the device of flue gas and desulfurizing and denitrifying, it is characterized in that alkali lye surge tank A, alkali lye surge tank B are connected to the fresh water (FW) supply line by pipeline respectively.
7. one kind based on the using ozone oxygenation combined with double-tower washing of the described device of claim 1 method to flue gas and desulfurizing and denitrifying, it is characterized in that, may further comprise the steps:
1) boiler smoke enters first alkali liquid washing tower A after heat exchanger is cooled to 90 ℃, and the sulfur dioxide of Yi Rong is absorbed into liquid phase; The ozone that ozone generator produces feeds the liquid phase region of alkali liquid washing tower A bottom, and the sexavalence sulphur that under 40～60 ℃ temperature the sulphur of tetravalence is oxidized to generates stable sulfate, and the mol ratio of feeding ozone amount and liquid phase tetravalence sulphur is 0.8～1.0;
2) ozone is sneaked into the flue that enters before the alkali liquid washing tower B, ozone amount that sprays into and the nitrogen oxide molar ratio in the boiler smoke are 0.5～1.5, water-fast oxidation of nitric oxide in the boiler smoke is become higher nitrogen oxides nitrogen dioxide, nitrogen peroxide soluble in water, in alkali liquid washing tower B, absorbed by alkali lye;
3) through behind the alkali liquid washing tower B, flue gas is sent flue back to after being heated through heat exchanger again.
8. using ozone oxygenation combined with double-tower washing according to claim 7 is characterized in that to the method for flue gas and desulfurizing and denitrifying described alkali lye is the wherein at least a aqueous solution of NaOH, potassium hydroxide, calcium hydroxide, calcium oxide or calcium carbonate.
9. using ozone oxygenation combined with double-tower washing according to claim 7 is characterized in that to the method for flue gas and desulfurizing and denitrifying described alkali lye is ammoniacal liquor.
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