CN103933838B - In coal, chlorine element circular utilizes the device and method realizing pollutant combined removal - Google Patents

In coal, chlorine element circular utilizes the device and method realizing pollutant combined removal Download PDF

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CN103933838B
CN103933838B CN201310020027.2A CN201310020027A CN103933838B CN 103933838 B CN103933838 B CN 103933838B CN 201310020027 A CN201310020027 A CN 201310020027A CN 103933838 B CN103933838 B CN 103933838B
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waste water
modified
coal
flue gas
desulfurization wastewater
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CN201310020027.2A
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CN103933838A (en
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董勇
李玉忠
崔琳
张梦泽
雎辉
王鹏
张立强
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山东大学
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Abstract

The invention discloses chlorine element circular in a kind of coal and utilize the device and method realizing pollutant combined removal, including boiler, SCR denitration device, air preheater, cleaner unit, desulfurizing tower, chimney, serosity pump II, described boiler is connected with SCR denitration device, it is connected by air preheater between SCR denitration device with cleaner unit, cleaner unit is connected with desulfurizing tower, desulfurizing tower is connected with chimney, also include desulfurization wastewater storage tank, atomizer, the modified tank of waste water, air compressor machine, atomizer is located on the connection pipeline between CR denitrification apparatus and air preheater, atomizer is connected with the modified tank of waste water by serosity pump II, air compressor machine is connected with atomizer, desulfurization wastewater storage tank is connected with desulfurizing tower, desulfurization wastewater storage tank is connected with the modified tank of waste water, it is provided with highly basic in the modified tank of waste water. promote the elimination of mercury in flue gas, simultaneously by regulating the pH value of rich chlorine desulfurization wastewater, it is achieved effectively the utilizing and improve SO in flue gas of desulfurization wastewater3The method of removal efficiency.

Description

In coal, chlorine element circular utilizes the device and method realizing pollutant combined removal

Technical field

The present invention relates to elemental mercury oxidation, elimination and the degree of depth in Gypsum Wet fire coal boiler fume to fix, and the pollutant removing technical field such as sulfur trioxide, dust, particularly relate to chlorine element circular in a kind of coal and utilize the device and method realizing pollutant combined removal.

Background technology

Hydrargyrum is the first kinds of pollution matter that air toxic is very strong, it is possible to the nervous system of the mankind is damaged. Coal-fired boiler in power plant fume emission is the main source of hydrargyrum in air. Hydrargyrum is main with elemental mercury (Hg in flue gas0), oxidation state hydrargyrum (Hg2+) and particle mercury (HgP) three kinds of forms exist, wherein oxidation state hydrargyrum and particle mercury are easily controlled equipment by Conventional pollution and remove, and not oxidized elemental mercury is discharged in air pollutes owing to its stronger stability and slightly solubility hardly result in effectively control.

Research finds, in coal, the chlorine element of trace is conducive to the gaseous elemental mercury conversion to oxidation state hydrargyrum and flying dust to the absorption of hydrargyrum and fixation. In flue gas, the hydrargyrum of oxidation state is mainly with mercuric chloride (HgCl2) form exist, utilize thermodynamical model[1]To under oxidizing atmosphere, the analog result that in coal, mercury shape variation with temperature carries out under 2ppmCl, 20ppmCl, 200ppmCl difference content of Cl element, as shown in Figure 1. Result shows that hydrargyrum exists in a chloride-form under low temperature (less than 650K), exists with elemental mercury under high temperature (more than 650K); In flue gas, content of Cl element is more big, and mercuric chloride is more wide as the temperature range of stable phase. China's chlorine content in coal is relatively low, limits the oxidation of elemental mercury in flue gas. Therefore, improve the content of chlorine element in flue gas in suitable temperature province and be conducive to improving the removal efficiency of mercury in flue gas.

Oxidation state hydrargyrum may reside in gas phase, it is also possible to is adsorbed onto ash surface and forms particle mercury. Chlorine element and calcium constituent are conducive to oxidation state hydrargyrum in the absorption of ash surface.The particle mercury being adsorbed on ash surface has higher stability, is difficult to desorption out at normal temperatures, and under heating at 200 DEG C, desorption rate also only has about 20%. Therefore it is adsorbed on the particle mercury that ash surface obtains elimination with cleaner to obtain the degree of depth and fix, does not result in secondary pollution.

Wet desulfurization of flue gas by limestone-gypsum method technique (WFGD) is the means of flue gas desulfurization of power plant technology being most widely used at present, in wet method fume desulfurizing system running, chloride ion has enrichment phenomenon in desulphurization circulating serosity, when chlorine ion concentration is enriched to and is about 20g/L in its desulfurization wastewater, extraction desulphurization system must be discharged continuously. Waste water contains substantial amounts of calcium ion, sulfate ion and chloride ion. It addition, desulfurization wastewater has acid big, heavy metal ion and suspension content high, it is necessary to could discharge through complicated chemical treatment. Current desulfurization wastewater processes has processing cost height, and discharge causes secondary pollution problems.

Human health is caused high risks by the discharge of PM2.5, is the difficult problem in coal-burning power plant's pollutant catabolic gene. The PM2.5 of coal-burning power plant's discharge is divided into and may filter that granule (PM) and condensable granule (secondary PM) two classes, wherein may filter that the ratio of granule and condensable granule is 1:3. And the main source of condensable granule is SO in flue gas2The SO that partial oxidation is formed3With the sulfuric acid aerosol that moisture in flue gas is formed, additionally study discovery, the introducing of SCR denitration also can SO in catalysis flue gas2It is oxidized to SO3. Electrostatic precipitation and bag-type dust can not remove this part of sulfuric acid aerosol particle, and WFGD is to SO3Removal efficiency is relatively low, causes PM2.5 elimination difficulty, it usually needs adds wet static dedusting (WESP) after WFGD and removes sulfuric acid aerosol granule. SO3Downstream flue and equipment are caused corrosion by acid mist, have increased the weight of the discharge of PM2.5 condensable granule simultaneously. Research finds that dry flue gas desulphurization device can effectively remove SO3, realize SO except adding WESP after WFGD3Elimination outside, WFGD upstream add dry method FGD also be realize elimination flue gas in SO3Effective ways.

Summary of the invention

The present invention is to solve prior art above shortcomings, it is provided that in a kind of coal, chlorine element circular utilizes the device realizing pollutant combined removal; Promote the elimination of mercury in flue gas, simultaneously by regulating the pH value of rich chlorine desulfurization wastewater, it is achieved effectively the utilizing and improve SO in flue gas of desulfurization wastewater3The method of removal efficiency.

The present invention also provides for chlorine element circular utilization in a kind of coal and realizes pollutant combined removal method.

It is an object of the invention to adopt following technical proposals to realize:

In a kind of coal, chlorine element circular utilizes the device realizing pollutant combined removal, including boiler, SCR(SelectiveCatalyticReducation, i.e. selective catalytic reduction) denitrification apparatus, air preheater, cleaner unit, desulfurizing tower, chimney, serosity pump II, described boiler is connected with SCR denitration device, it is connected by air preheater between SCR denitration device with cleaner unit, cleaner unit is connected with desulfurizing tower, desulfurizing tower is connected with chimney, also include desulfurization wastewater storage tank, atomizer, the modified tank of waste water, air compressor machine, atomizer is located on the connection pipeline between CR denitrification apparatus and air preheater, atomizer is connected with the modified tank of waste water by serosity pump II, air compressor machine is connected with atomizer, desulfurization wastewater storage tank is connected with desulfurizing tower, desulfurization wastewater storage tank is connected with the modified tank of waste water, it is provided with highly basic in the modified tank of waste water. desulfurization slurry in desulfurizing tower obtains desulfurated plaster by separating measure and is stored in the desulfurization wastewater in desulfurization wastewater storage tank.

Desulfurizing tower adopts Limestone-gypsum Wet Flue Gas Desulfurization Process tower.Highly basic adopts slaked lime.

Pipeline between desulfurization wastewater storage tank and the modified tank of waste water is provided with serosity pump I.

Shown in modified in the modified tank of waste water after waste water pH value >=8.

In a kind of coal, chlorine element circular utilizes the method realizing pollutant combined removal, comprises the following steps:

1) in the modified tank of waste water, slaked lime is added modified, waste water pH value >=8 after modified;

2) waste water after modified is ejected into the position between flue SCR denitration device and air preheater by atomizer, regulates compression air and wastewater flow, control atomization droplets diameter, it is ensured that atomized drop moisture is evaporated within the setting time.

Beneficial effects of the present invention:

1. achieve recycling of chlorine element in coal, given full play to the effect in improving Mercury In Coal Combustion Flue Gas elimination performance of the chlorine element, solved content of Cl element in China's subbituminous coal and brown coal on the low side, the problem of elemental mercury emission control difficulty in flue gas;

2. improve content of Cl element in back-end ductwork flue gas without the content of Cl element increased in burner hearth flue gas, it is to avoid the corrosion to furnace heating surface of the chlorine element;

3. improve SO3Removal efficiency, solves coal-burning power plant and installs SO after SCR denitration device3The problem that discharge is increased;

4. equipment investment is few, takes up room little;

5. promote the cleaner unit removal efficiency to particulate matter, reduce the water consumption of WFGD;

6. this method realizes changing waste into resources utilization, and the treatment of wastes with processes of wastes against one another has preferably economical and environmentally friendly benefit.

Accompanying drawing explanation

Fig. 1 is the chlorinity schematic diagram on mercury shape and the impact of distribution;

Fig. 2 is the process chart of the present invention;

In figure: 1. boiler, 2.SCR denitrification apparatus, 3. atomizer, 4. air preheater, 5. cleaner unit, 6. desulfurizing tower, 7. chimney, 8. desulfurization wastewater storage tank, 9. desulfurated plaster, 10. serosity pump I, the 11. modified tanks of waste water, 12. serosity pumps II, 13. air compressor machines.

Detailed description of the invention

Below in conjunction with drawings and Examples, the present invention will be further described.

In a kind of coal, chlorine element circular utilizes the device realizing pollutant combined removal, in conjunction with Fig. 2, including boiler 1, SCR denitration device 2, air preheater 4, cleaner unit 5, desulfurizing tower 6, chimney 7, serosity pump II 12, described boiler 1 is connected with SCR denitration device 2, it is connected by air preheater 4 between SCR denitration device 2 with cleaner unit 5, cleaner unit 5 is connected with desulfurizing tower 6, desulfurizing tower 6 is connected with chimney 7, also include desulfurization wastewater storage tank 8, atomizer 3, the modified tank 11 of waste water, air compressor machine 13, atomizer 3 is located on the connection pipeline between CR denitrification apparatus 2 and air preheater 4, atomizer 3 is connected with the modified tank 11 of waste water by serosity pump II 12, air compressor machine 13 is connected with atomizer 3, desulfurization wastewater storage tank 8 is connected with desulfurizing tower 6, desulfurization wastewater storage tank 8 is connected with the modified tank 11 of waste water, it is provided with highly basic in the modified tank 11 of waste water, desulfurizing tower 6 adopts Limestone-gypsum Wet Flue Gas Desulfurization Process tower. highly basic adopts slaked lime. desulfurization slurry in desulfurizing tower 6 obtains desulfurated plaster 9 by separating measure and is stored in the desulfurization wastewater in desulfurization wastewater storage tank 8. pipeline between desulfurization wastewater storage tank 8 and the modified tank 11 of waste water is provided with serosity pump I 10. waste water pH value >=8 in the modified tank 11 of waste water.

In a kind of coal, chlorine element circular utilizes the method realizing pollutant combined removal, comprises the following steps:

1) in the modified tank of waste water 11, slaked lime is added modified, waste water pH value >=8 after modified;

2) waste water after modified is ejected into the position between flue SCR denitration device and air preheater by atomizer, regulates compression air and wastewater flow, control atomization droplets diameter, it is ensured that atomized drop moisture is evaporated within the setting time.

Coal dust is injected in boiler 1 through burner, at high temperature burns, and mercury element in coal and chlorine Element release are in flue gas. At high temperature major part hydrargyrum precipitates out with elemental mercury form, and along with boiler heating surface absorbs heat, flue-gas temperature is gradually lowered, and the effect of SCR denitration device 2 catalyst, and Partial Elements state hydrargyrum is oxidized to oxidation state hydrargyrum. Before air preheater 4, flue-gas temperature probably drops between 600K-700K. In this position, the modified serosity of desulfurization wastewater wet desulfurization of flue gas by limestone-gypsum method technique produced is ejected in flue by the atomizer 3 being arranged in flue, the drop that waste water is small dissolves the partial oxidation state hydrargyrum in flue gas, simultaneously, moisture evaporates rapidly, major part oxidation state hydrargyrum under calcium ion and chloride ion effect, condenses on the fine particle that waste water evaporation precipitates out or is adsorbed onto on burned-coal fly ash with fine particle simultaneously in waste water. Meanwhile, it is adsorbed on the chloride on flying dust and the elemental mercury in flue gas is had important catalysed oxidn, promote that the elemental mercury in flue gas is converted into oxidation state hydrargyrum. What these oxidation state hydrargyrum had is adsorbed on burned-coal fly ash, together removing with flying dust in cleaner unit 5 together with passing through to dissolve the oxidation state hydrargyrum that evaporation and condensation process catches, small part stops in the desulfurization wastewater or Gypsum Fibrosum 9 entering in desulfurization wastewater storage tank 8 in the gas phase under the cleaning function of wet desulfurization of flue gas by limestone-gypsum method device 6. Part does not have oxidized elemental mercury and few partly staying in flue gas not over the oxidation state hydrargyrum of wet desulphurization device 6 elimination to be discharged in air through chimney 7.

SO in flue gas2Catalytic oxidation partial oxidation through SCR denitration device 2 catalyst becomes SO3, at desulfurization wastewater modified serosity spraying place, major part SO3With part SO less2It is adsorbed onto in serosity, along with the evaporation of serosity is with the elimination that is fixed on flying dust removing dust device of the form of calcium sulfate.

The chlorine element that coal combustion evaporate in flue gas after producing hydrogen chloride and desulfurization wastewater spraying enters in wet desulfurization of flue gas by limestone-gypsum method device 6 with flue gas, the sour gas SO in flue gas2, HCl etc. enters in desulfurization wastewater in washing process, SO2Constantly precipitating out formation Gypsum Fibrosum by reaction generation calcium sulfate to be removed, chloride ion is then constantly enriched with in waste water. In waste water, desulfurizing tower is caused corrosion to affect the quality of desulfurated plaster by the too high meeting of content of Cl element simultaneously, about technical specification all using content of Cl element in desulfurization wastewater more than the 20000mg/L criterion discharged as desulfurization wastewater. This partial desulfurization waste water is transported in the modified tank 11 of waste water through serosity pump 10, adjusts waste water pH value to 8.0 by adding slaked lime in waste water. Be transported to the atomizer 3 being arranged in flue through serosity pump 12 through modified waste water, air compressor machine 13 produce compressed-air actuated effect mist chemical conversion drop be ejected in flue gas. The particle diameter of atomized drop is controlled, it is ensured that drop can be evaporated rapidly in flue gas by the compression air of air compressor machine 13 and serosity pump 12 control entrance atomizer 3 and waste water slurry hydraulic coupling.

From burner hearth 1 up to SCR denitration device 2 in whole technique, content of Cl element in flue gas does not change, only atomizer 3 improves to the chlorine concentration of element in the flue gas of one section, limestone-gypsum desulphurization system 5 porch, and this partial fume temperature is exactly the optimum temperature of the absorption of mercury in flue gas element and catalytic oxidation, in flue gas, the raising of chlorine element is greatly promoted mercury in flue gas pollutant at the absorption of ash surface and catalytic oxidation, improves coal-burning power plant's Conventional pollution and controls the control of device 5 and 6 pairs of mercury contaminants.The chlorine element that coal combustion precipitate in flue gas is continuously replenished and forms one dynamic equilibrium in cyclic process with the chlorine element being adsorbed on flying dust to obtain elimination. Chlorine element a small amount of in coal has played the effect of elimination mercury in flue gas pollutant to the utmost when equipment not being impacted.

The detailed description of the invention of invention is described in conjunction with accompanying drawing although above-mentioned; but not limiting the scope of the invention; one of ordinary skill in the art should be understood that; on the basis of technical scheme, those skilled in the art need not pay various amendments or deformation that creative work can make still within protection scope of the present invention.

Claims (5)

1. in a coal, chlorine element circular utilizes the device realizing pollutant combined removal, including boiler, SCR denitration device, air preheater, cleaner unit, desulfurizing tower, chimney, serosity pump II, described boiler is connected with SCR denitration device, it is connected by air preheater between SCR denitration device with cleaner unit, cleaner unit is connected with desulfurizing tower, desulfurizing tower is connected with chimney, it is characterized in that, also include desulfurization wastewater storage tank, atomizer, the modified tank of waste water, air compressor machine, atomizer is located on the connection pipeline between SCR denitration device and air preheater, atomizer is connected with the modified tank of waste water by serosity pump II, air compressor machine is connected with atomizer, desulfurization wastewater storage tank is connected with desulfurizing tower, desulfurization wastewater storage tank is connected with the modified tank of waste water, it is provided with highly basic in the modified tank of waste water, in the modified tank of waste water modified after waste water pH value >=8,
Before air preheater, flue-gas temperature drops between 600K-700K, in this position, the modified serosity of desulfurization wastewater wet desulfurization of flue gas by limestone-gypsum method technique produced is ejected in flue by the atomizer being arranged in flue, the drop that waste water is small dissolves the partial oxidation state hydrargyrum in flue gas, simultaneously, moisture evaporates rapidly, major part oxidation state hydrargyrum is in waste water under calcium ion and chloride ion effect, condense on the fine particle that waste water evaporation precipitates out or be adsorbed onto on burned-coal fly ash with fine particle simultaneously, simultaneously, it is adsorbed on the chloride on flying dust to the elemental mercury in flue gas, promote that the elemental mercury in flue gas is converted into oxidation state hydrargyrum, what these oxidation state hydrargyrum had is adsorbed on burned-coal fly ash, together remove with flying dust in cleaner unit together with passing through to dissolve the oxidation state hydrargyrum that evaporation and condensation process catches, small part stops in the desulfurization wastewater or Gypsum Fibrosum entering in desulfurization wastewater storage tank in the gas phase under the cleaning function of wet desulfurization of flue gas by limestone-gypsum method device.
2. in coal as claimed in claim 1, chlorine element circular utilizes the device realizing pollutant combined removal, it is characterized in that, described desulfurizing tower adopts Limestone-gypsum Wet Flue Gas Desulfurization Process tower.
3. in coal as claimed in claim 1, chlorine element circular utilizes the device realizing pollutant combined removal, it is characterized in that, described highly basic adopts slaked lime.
4. in coal as claimed in claim 1, chlorine element circular utilizes the device realizing pollutant combined removal, it is characterized in that, the pipeline between described desulfurization wastewater storage tank and the modified tank of waste water is provided with serosity pump I.
5. adopt the method that in a kind of coal as claimed in claim 1, chlorine element circular utilizes the device realizing pollutant combined removal, it is characterized in that, comprise the following steps:
1) in the modified tank of waste water, slaked lime is added modified, waste water pH value >=8 after modified;
2) waste water after modified is ejected into the position between flue SCR denitration device and air preheater by atomizer, regulates compression air and wastewater flow, control atomization droplets diameter, it is ensured that atomized drop moisture is evaporated within the setting time.
CN201310020027.2A 2013-01-21 2013-01-21 In coal, chlorine element circular utilizes the device and method realizing pollutant combined removal CN103933838B (en)

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