CN104388146A - Control method for reducing fire coal power plant flue gas mercury discharge - Google Patents
Control method for reducing fire coal power plant flue gas mercury discharge Download PDFInfo
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- CN104388146A CN104388146A CN201410529219.0A CN201410529219A CN104388146A CN 104388146 A CN104388146 A CN 104388146A CN 201410529219 A CN201410529219 A CN 201410529219A CN 104388146 A CN104388146 A CN 104388146A
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Abstract
The invention discloses a control method for reducing fire coal power plant flue gas mercury discharge. The control method comprises jetting a halide salt aqueous solution into a fire coal boiler from an as-fired coal part by a solution jetting device, wherein a mass ratio of halogen in the halide salt aqueous solution to coal is controlled in a range of 20-100ppm, before flue gas enters into a deduster, and jetting adsorbent solid powder into a pipe in front of the deduster by a powder jetting device so that oxidation state mercury is adsorbed by the adsorbent solid powder and the solid powder and fly ash are captured together by the deduster, wherein a weight ratio of the adsorbent solid powder to mercury in coal is 1000-10000: 1. The control method has the advantages of simple processes, wide raw material source and high mercury removal efficiency.
Description
Technical field
The present invention relates to a kind of control method reducing coal-fired plant flue gas mercury emissions.
Background technology
Thermal power generation is China's present stage main energy sources, and coal-burning power plant is while coal combustion provides energy, and the pollutant emission of generation but brings serious harm to the living environment of people.In multiple coal burning pollution thing, heavy metal Hg is exactly the pollutent that wherein a kind of toxicity is serious.Mercury has sizable toxicity to the mankind and animals and plants, can cause fetation deformity and nervous system abnormality, the growth of serious harm fetus and infant and the health of adult.Therefore, mercury pollution problem is paid attention to day by day widely.According to the statistic data of EPA (EPA), the annual of the current U.S. artificially discharges mercury 135t, and wherein 48t is from coal-burning power plant.The annual emissions of China's coal-fired plant flue gas mercury is higher than the U.S.; along with the development of economic society and the enhancing of environmental consciousness; the heavy metal contamination comprising mercury aggravates further; State Council pays much attention to this; writing instructions and transfer seven ministries and commissions' " instruction about strengthening Heavy Metal Pollution work " (Office of the State Council are sent out (2009) No. 61) of jointly formulating such as Environmental Protection Department, State Development and Reform Commission, mercury chemical industry Product Process will have been related to and be classified as one of emphasis prevention and control object.At the beginning of 2011, State Council has given an written reply again " heavy metal contamination integrated control " 12 " planning " (No. (2011) 13, state's letter), this object of planning set up fairly perfect Heavy Metal Pollution system, accident emergency system and the environment and health risk evaluation system that comprise mercury pollution, key area emphasis heavy metal contaminants quantity discharged reduced 15% than 2007, and non-key area emphasis heavy metal contaminants quantity discharged is no more than level in 2007.
For discharge and the control of heavy metal Hg, cause the concern of domestic and international each side scholar, and conducted extensive research.The control of Mercury Emissions from Coal-Fired Boilers is by the washing of the front coal that burns or realize the removal of mercury of flue gas after burning.Mercury in flue gas is mainly with particle mercury (Hg
p), gaseous state bivalent mercury (Hg
2+) and gaseous elemental mercury (Hg
0) three kinds of forms exist, the oxidative components such as the ratio shared by the mercury of these three kinds of forms and the halogens in coal have substantial connection.Because in the coal of China, content of Cl element is lower, therefore most mercury in flue gas is with Hg more rambunctious
0form exists.Present stage, more general a kind of approach realizing heavy metal Hg emission control was only utilize the pollutant catabolic gene devices such as existing desulphurization and denitration and dedusting to carry out Collaborative Control, and most coal-burning power plant does not also have independent Mercury vacancy device.
Independent Mercury vacancy Research progress is mainly started with from two aspects, is the catalytic oxidation technologies of mercury, on the other hand Novel adsorption technology on the one hand.Chinese patent CN101480555A discloses a kind ofly has the carbon residue of favourable absorption effect to mercury and deep bed filter acts synergistically to remove mercury in flue gas and fine particulates.Chinese patent CN102553522A provides a kind of preparation method and application conditions thereof of the oxidisability sorbent material for removing Mercury In Coal Combustion Flue Gas, sorbent material using method is sprayed the flue gas of injection 60 DEG C to 340 DEG C, the manufacture of this sorbent material and use cost lower than acticarbon, and can reach the gas mercury clearance of more than 85%.Chinese patent CN102580493 discloses a kind of flue gas mercury removal system based on discharge activation halogen family material and method, described halogen family material activating apparatus injects halogen family material in flue gas, and the halogen family material described in being activated by electrion, after changing elemental mercury in flue gas into oxidation state mercury and particle mercury, carry out dedusting and absorbing and removing oxidation state mercury and particle mercury.Chinese patent CN102078757 discloses a kind of halogen for flue gas demercuration spray feeder apparatus and spray adding method, utilize a small amount of heated drying air, prepare rich halogen-containing gas by the halogen bed of heat or the mode of bubbling, pass in the flue before electric dust collector.Current prior art is only started with from being oxidized or adsorbing single aspect, and mercury removal efficiency is not high.
Summary of the invention
The object of this invention is to provide the control method of the high reduction coal-fired plant flue gas mercury emissions of a kind of mercury removal efficiency.
The present invention is by spraying the halide salt solution with oxidative components at as-fired coal place, to make in fire coal mercury through burning to denitrification apparatus process greatly to oxidation state, then the pressed powder of high adsorption capacity is spurted in fly-ash separator front, oxidation state mercury is caught by pressed powder, pressed powder is caught by fly-ash separator thus the mercury in fire coal is caught by fly-ash separator, decrease mercury to the discharge in air, reduce the impact of coal-fired mercury contaminants on atmospheric environment.
Its principle is halide-ions O in combustion processes and air
2reaction generates the halogen simple substance of strong oxidizing property, and halogen simple substance and Elemental Mercury react production oxidation state mercury.For NaBr, the chemical equation of generation is as follows:
4NaBr+O
2→2Na
2O+2Br
2
Br
2+Hg→HgBr
2
In order to realize above object, control method of the present invention comprises the steps:
(1) prepare halide salt solution, halide salt is mixed with the aqueous solution that mass percent is 5%-15% concentration;
(2) prepare adsorbent solids powder, adsorbent solids fragmentation is become particle diameter and be less than 300 object powder;
(3) the halide salt aqueous solution is used solution jet apparatus, spurt in coal firing boiler at as-fired coal place, wherein emitted dose is controlled by the content of halogen in solution and the ratio of coal, and in halide salt solution, the mass ratio of halogen and coal controls at 20-100ppm.
(4) use Powderjet device, before flue gas enters fly-ash separator, adsorbent solids powder spray injected in the pipeline before fly-ash separator, make oxidation state mercury by adsorbent solids powder adsorption, pressed powder is caught together with fly-ash separator with flyash; Wherein absorbent powder emitted dose is absorbent powder: in coal, mercury weight ratio is 1000-10000:1.
Described halide salt comprises the halide salts of basic metal or alkaline-earth metal, comprises CaCl
2, NaBr, CaBr
2or KI.
Described solid adsorbent comprises commercial activated carbons, activated coke or zeolite molecular sieve material.Wherein the specific surface area of gac class sorbent material is 800-1200m
2/ g, pore diameter range 2-10nm; The specific surface area of activated coke class sorbent material is 600-1000m
2/ g, pore diameter range 2-10nm; The specific surface area of zeolitic materials is 200-800m
2/ g, pore diameter range 0.5-5nm.
Described solution jet apparatus comprises container for storing liquid, constant current infusion pump, a nozzle and a transport pipe thereof, and its emitted dose is controlled by constant current infusion pump, and nozzle is that corrosion-resistant ceramic liner makes, and has the nozzle of uniform atomizing effect.
Described nozzle can comprise: the DMZJX type atomizing nozzle that Shandong thumb spraying equipment company limited produces; Dongguan City Fu Ruide sprays and purifies the FN-1 type atomizing nozzle of company limited's production; The YSPJ type atomizing nozzle that Jining Ya Temei Trade Co., Ltd. produces.
Described solid adsorbent Powderjet device comprises feed bin, screw feeder, roots blower, venturi-type eductors and transport pipe thereof, and its solid phase emitted dose is controlled by screw feeder and roots blower gas velocity thereof.The screw feeder used realizes uniform feeding speed by electronically controlled.The roots blower used can by transmission speed and the jet velocity regulating air velocity to control powder.The venturi-type eductors used makes for mechanically resistant material, can slow down the injector of wearing and tearing and high speed injection air-flow prevention fouling.
Described venturi-type eductors can comprise the LZS type injector that Hebei Huaqiang Technology Development Co., Ltd produces; Wuxi City become famous anticorrosion equipment factory produce WGP series injector; The DLPS type injector that Nanjing De Like Chemical Equipment Co., Ltd. produces.
The present invention has following features:
1) processing method is convenient: coal-fired flue-gas mercury control method provided by the invention technological operation is simple, and safe and reliable to operation, obvious environment benefit, plant area area is little, and process costs is cheap, is easy to transform field device.
2) raw material sources are extensive: the equal wide material sources of solids liq material needed for injection, and preparation method is simple, equipment non-corrosiveness, and with low cost.
3) demercuration efficiency is high: the present invention has successful to removing of mercury in coal-fired plant flue gas, and has the low advantage of removal of mercury cost, is a kind of very promising mercury contaminants control method.
The present invention can be used for outside coal-fired plant flue gas demercuration, also may be used for the coal firing boiler equipment demercuration of the industries such as the metallurgy of outfit cleaning apparatus.
Accompanying drawing explanation
Fig. 1 is schema of the present invention;
Fig. 2 is solution jet apparatus figure of the present invention;
Fig. 3 is solid adsorbent Powderjet device figure of the present invention;
As shown in the figure, 1 is coal firing boiler, and 2 is denitrification apparatus, and 3 is cleaning apparatuss, and 4 is desulfurizers, and 5 is chimneys.Liquid and solid eject position mark on Fig. 1.6 is container for storing liquids, and 7 is constant current infusion pumps, and 8 is nozzles, and 9 is feed bins, and 10 is screw feeders, and 11 is roots blowers, and 12 is transfer lines, and 13 is venturi-type eductors.
Embodiment
Below, by reference to the accompanying drawings embodiments of the present invention are further elaborated.Should be understood that this embodiment is only not limited to scope of the present invention for illustration of the present invention.
Embodiment 1
As shown in drawings, this invention needs be equipped with the coal-burning power plant of denitrification apparatus and cleaning apparatus to implement, by means of existing denitrification apparatus and cleaning apparatus cooperative achievement removal efficiency of mercury.Wherein the effect of denitrification apparatus realizes solution oxide agent to Hg by means of the katalysis of denitrating catalyst in device
0oxygenizement; The effect of cleaning apparatus is caught by the absorbent powder of absorption Hg.
Carry out spraying and mercury emissions test experiments in the coal-burning power plant of certain 300MW unit coal-powder boiler.First do and spray opening, transfer line connection, and the preparation work of mercury emissions Concentration Testing.Stove place opening is entered, position as shown in Figure 1 at coal, by liquid injection apparatus according to after connecting shown in accompanying drawing 2, nozzle 8 insertion opening.Opening between denitrification apparatus and cleaning apparatus, by feed bin 9, screw feeder 10, after roots blower 11 and pressed powder transfer line 12 connect according to accompanying drawing 3, Venturi spray tube 13 insertion opening.The continuous analyser of mercury concentration is arranged in desulfurizer 4 exit.
Configuration CaBr
2solution, according to CaBr
2with deionized water quality than the proportional arrangement solution for 1:10, by mechanical stirring, after colourless transparent solution to be formed, be transferred in container for storing liquid stand-by.The business bituminous coal activated carbon product bought, specific surface area is 960m
2/ g, mean pore size 3.8nm.Pulverize with pulverizer, mistake 300 mesh sieve obtain particle diameter and are less than 300 object pressed powders, powder transfer are entered in feed bin stand-by.
The coal consumption of coal unit is 100t/h, and recording coal-fired mercury content is 56ppb, calculates required liquid and solid emitted dose with this.Until coal firing boiler unit stable after, maintain load more than 90%, denitration, dedusting and desulfurizer are all stable, carry out mercury emissions base measurement.By the mercury concentration that flue gas continuous mercury analyzer measurement desulfurizer exports out, after within continuous one hour, stablizing, gas mercury concentration is 11.1 μ g/m
3, can be used as the mercury emissions concentration baseline do not carried out before spraying fire.
After obtaining mercury concentration baseline results, open liquid and solid splashing device simultaneously.Spouting of liquid amount is according to CaBr
2in solution, the mass ratio 100ppm of Br and coal sprays.Solid emitted dose is with absorbent powder: in coal, mercury weight ratio is that 10000:1 sprays.After starting injection, the continuous mercury analyzer exported by desulfurizer detects mercury emissions concentration, and when ejected when 30 minutes, can monitor outlet mercury concentration and start to decline, after 1 hour, mercury emissions concentration tends towards stability.When implementing according to above-mentioned embodiment, the outlet mercury concentration that monitoring obtains is outlet mercury concentration is 1.8 μ g/m
3, can 85% be reduced compared to baseline outlet mercury concentration.
Embodiment 2
Carry out spraying and mercury emissions test experiments in the coal-burning power plant of certain 200MW unit coal-powder boiler, the coal consumption of coal unit is 60t/h, and recording coal-fired mercury content is 145ppb, calculates required liquid and solid emitted dose with this.Configuration CaCl
2solution, according to CaCl
2with deionized water quality than the proportional arrangement solution for 1:10, by mechanical stirring, after colourless transparent solution to be formed, be transferred in container for storing liquid stand-by.Buy lignite semi-coke product, specific surface area 730m
2/ g, mean pore size 4.5nm.Pulverize with pulverizer, mistake 300 mesh sieve obtain particle diameter and are less than 300 object pressed powders, powder transfer are entered in feed bin stand-by.Spouting of liquid amount is according to CaCl
2in solution, the mass ratio 60ppm of Cl and coal sprays, and solid emitted dose is with absorbent powder: in coal, mercury weight ratio is that 5000:1 sprays, and all the other are with embodiment 1.When ejected when 30 minutes, can monitor outlet mercury concentration and start to decline, after 1 hour, mercury emissions concentration tends towards stability, from 15.6 initial μ g/m
3drop to 5.1 μ g/m
3.When implementing according to above-mentioned embodiment, outlet mercury concentration can reduce by 68% compared to baseline outlet mercury concentration.
Embodiment 3
Carry out spraying and mercury emissions test experiments in the coal-burning power plant of certain 200MW unit coal-powder boiler, the coal consumption of coal unit is 60t/h, and recording coal-fired mercury content is 145ppb, calculates required liquid and solid emitted dose with this.Configuration CaCl
2solution, according to CaCl
2with deionized water quality than the proportional arrangement solution for 1:10, by mechanical stirring, after colourless transparent solution to be formed, be transferred in container for storing liquid stand-by.The business bituminous coal activated carbon product bought, specific surface area 960m
2/ g, mean pore size 3.8nm.Pulverize with pulverizer, mistake 300 mesh sieve obtain particle diameter and are less than 300 object pressed powders, powder transfer are entered in feed bin stand-by.Spouting of liquid amount is according to CaCl
2in solution, the mass ratio 30ppm of Cl and coal sprays, and solid emitted dose is with absorbent powder: in coal, mercury weight ratio is that 1000:1 sprays, and all the other are with embodiment 1.When ejected when 30 minutes, can monitor outlet mercury concentration and start to decline, after 1 hour, mercury emissions concentration tends towards stability, from 14.8 initial μ g/m
3drop to 3.6 μ g/m
3.When implementing according to above-mentioned embodiment, outlet mercury concentration can reduce by 76% compared to baseline outlet mercury concentration.
Embodiment 4
Carry out spraying and mercury emissions test experiments in the coal-burning power plant of certain 200MW unit coal-powder boiler, the coal consumption of coal unit is 60t/h, and recording coal-fired mercury content is 145ppb, calculates required liquid and solid emitted dose with this.Configuration CaCl
2solution, according to CaCl
2with deionized water quality than the proportional arrangement solution for 1:10, by mechanical stirring, after colourless transparent solution to be formed, be transferred in container for storing liquid stand-by.The business bituminous coal activated carbon product bought, specific surface area 960m
2/ g, mean pore size 3.8nm.Pulverize with pulverizer, mistake 300 mesh sieve obtain particle diameter and are less than 300 object pressed powders, powder transfer are entered in feed bin stand-by.Spouting of liquid amount is according to CaCl
2in solution, the mass ratio 30ppm of Cl and coal sprays, and solid emitted dose is with absorbent powder: in coal, mercury weight ratio is that 3000:1 sprays, and all the other are with embodiment 1.When ejected when 30 minutes, can monitor outlet mercury concentration and start to decline, after 1 hour, mercury emissions concentration tends towards stability, from 14.5 initial μ g/m
3drop to 2.6 μ g/m
3.When implementing according to above-mentioned embodiment, outlet mercury concentration can reduce by 82% compared to baseline outlet mercury concentration.
Claims (11)
1. reduce a control method for coal-fired plant flue gas mercury emissions, it is characterized in that comprising the steps:
(1) prepare halide salt solution, halide salt is mixed with the aqueous solution that mass percent is 5%-15% concentration;
(2) prepare adsorbent solids powder, adsorbent solids fragmentation is become particle diameter and be less than 300 object powder;
(3) the halide salt aqueous solution is used solution jet apparatus, spurt in coal firing boiler at as-fired coal place, wherein emitted dose is controlled by the content of halogen in solution and the ratio of coal, and in halide salt solution, the mass ratio of halogen and coal controls at 20-100ppm;
(4) use Powderjet device, before flue gas enters fly-ash separator, adsorbent solids powder spray injected in the pipeline before fly-ash separator, make oxidation state mercury by adsorbent solids powder adsorption, pressed powder is caught together with fly-ash separator with flyash; Wherein absorbent powder emitted dose is absorbent powder: in coal, mercury weight ratio is 1000-10000:1.
2. a kind of control method reducing coal-fired plant flue gas mercury emissions as claimed in claim 1, is characterized in that described halide salt comprises the halide salts of basic metal or alkaline-earth metal.
3. a kind of control method reducing coal-fired plant flue gas mercury emissions as claimed in claim 2, is characterized in that described alkali halide salts is NaBr or KI; Alkaline earth metal halide salt CaCl
2or CaBr
2.
4. a kind of control method reducing coal-fired plant flue gas mercury emissions as claimed in claim 1, is characterized in that described solid adsorbent comprises commercial activated carbons, activated coke or zeolite molecular sieve material.
5. a kind of control method reducing coal-fired plant flue gas mercury emissions as claimed in claim 4, is characterized in that the specific surface area of described commercial activated carbons is 800-1200m
2/ g, pore diameter range 2-10nm.
6. a kind of control method reducing coal-fired plant flue gas mercury emissions as claimed in claim 4, is characterized in that the specific surface area of described activated coke is 600-1000 m
2/ g, pore diameter range 2-10nm.
7. a kind of control method reducing coal-fired plant flue gas mercury emissions as claimed in claim 4, is characterized in that the specific surface area of described zeolite molecular sieve is 200-800m
2/ g, pore diameter range 0.5-5nm.
8. a kind of control method reducing coal-fired plant flue gas mercury emissions as claimed in claim 1, it is characterized in that described solution jet apparatus comprises container for storing liquid (6), constant current infusion pump (7), a nozzle (8) and a transport pipe thereof, its emitted dose is controlled by constant current infusion pump, nozzle is that corrosion-resistant ceramic liner makes, and has the nozzle of uniform atomizing effect.
9. a kind of control method reducing coal-fired plant flue gas mercury emissions as claimed in claim 8, is characterized in that described nozzle comprises the DMZJX type atomizing nozzle of Shandong thumb spraying equipment company limited production; The FN-1 type atomizing nozzle that Dongguan City Fu Ruide spraying purification company limited produces or the YSPJ type atomizing nozzle that Jining Ya Temei Trade Co., Ltd. produces.
10. a kind of control method reducing coal-fired plant flue gas mercury emissions as claimed in claim 1, it is characterized in that described solid adsorbent Powderjet device comprises feed bin (9), screw feeder (10), roots blower (11), venturi-type eductors (13) and transport pipe (12) thereof, its solid phase emitted dose is controlled by screw feeder (10) and roots blower (11) gas velocity thereof, and the screw feeder (10) used realizes uniform feeding speed by electronically controlled; The roots blower (11) used can control transmission speed and the jet velocity of powder by regulating air velocity, and the venturi-type eductors used (13) makes for mechanically resistant material.
11. a kind of control methods reducing coal-fired plant flue gas mercury emissions as claimed in claim 10, is characterized in that described venturi-type eductors (13) comprises the LZS type injector of Hebei Huaqiang Technology Development Co., Ltd's production; Wuxi City become famous anticorrosion equipment factory produce WGP series injector or Nanjing De Like Chemical Equipment Co., Ltd. produce DLPS type injector.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105126561A (en) * | 2015-08-04 | 2015-12-09 | 东南大学 | Coal-fired flue gas PM2.5/SO3/Hg combined removing method based on desulfurization wastewater evaporation treatment |
| CN106823773A (en) * | 2017-01-21 | 2017-06-13 | 北京清新环境技术股份有限公司 | A kind of coal-fired flue gas mercury removal method of use additive and adsorbent |
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