CN105879632A - Method and system for removing mercury of circulating fluidized bed coal-fired boiler by utilizing white mud - Google Patents
Method and system for removing mercury of circulating fluidized bed coal-fired boiler by utilizing white mud Download PDFInfo
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- CN105879632A CN105879632A CN201410771419.7A CN201410771419A CN105879632A CN 105879632 A CN105879632 A CN 105879632A CN 201410771419 A CN201410771419 A CN 201410771419A CN 105879632 A CN105879632 A CN 105879632A
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Abstract
The invention discloses a control method and system for removal of a harmful trace element Hg in flue gas of a coal-fired power plant and particularly relates to a method and system for removing mercury of a circulating fluidized bed coal-fired boiler by utilizing water-washing white mud. The white mud transported from a white mud waste residue factory is stored in a white mud cabin 10; the white feeding amount of the white mud in the white mud cabin 10 is controlled through a feeding adjusting valve 9, and then the white mud is conveyed into a solid-liquid separation device 8; a dryer 7 is used for conveying the water-washing white mud into a pulverizer 6 so as to be ground into fine powder with certain fineness, and then the powder is conveyed into high-temperature flue gas through a powder discharging machine 5; the white mud powder which is sprayed into the boiler is decomposed under the action of the high-temperature flue gas (900-1000 DEG C) to generate active adsorbing materials; the white mud is washed to obtain Cl-containing clarified liquid, and the clarified liquid passes through an air compressor 13 and is sprayed in front of a selective catalytic reduction device (SCR) through a nozzle 15; HgO is oxidized under the action of Cl to generate Hg<2+> and the Hg<2+> is easily adsorbed into particles Hg by ash particles, and the added white mud powder increases the collision probability of the element mercury and ash; and the Hg-containing ash particles are finally removed by a dust remover 16 under the action of a draught fan 17 so that the aim of removing the Hg in the coal-fired power plant is realized.
Description
Technical field
The present invention relates to a kind of method and system that pulverized-coal fired boiler is carried out demercuration, particularly relate to a kind of method and system utilizing washing white clay that circulating fluidized bed combustion coal boiler carries out demercuration.
Background technology
China is big coal country, is also simultaneously coal-fired big country, and in the primary energy consumption structure of China, coal proportion is more than 75%, and the pollutant such as the sulfur-bearing that produces in coal-fired process, nitrogen, chlorine have caused extensive concern.The pollution problem of Determination of Trace Volatile metallic element (such as Hg, Pb, As, Se etc.) now is the most causing the attention of people.In coal, the most volatile heavy metal contaminants is hydrargyrum, although in coal, mercury content is relatively low, but consumes huge.Worldwide, the mercury emissions owing to causing during coal utilization accounts for mankind's activity and causes the 45% of mercury emissions, and the Mercury Emissions from Coal-Fired Boilers amount of China accounts for about the 10% of world's mercury emission.Therefore, mercury control should be strengthened.During coal-fired power plant, the hydrargyrum of trace can be discharged in flue gas in coal combustion process, and Mercury In Coal Combustion Flue Gas hosts 3 kinds of forms: gaseous elemental Hg (Hg0), oxidation state Hg (Hg2+) and granule Hg (Hgp).In world wide, the mercury content in coal is usually 0.012-33mg/kg, and its average mercury content is about 0.13mg/kg, but the average mercury content of China's coal is about 0.22mg/kg, far surpasses world average level.Owing to its physicochemical properties of hydrargyrum of different shape are different, therefore its removal methods is the most different.HgpAnd Hg2+Due to its water solublity with easily invest the characteristics such as flying dust and can be removed by the existing pollution control equipment of power plant, but Hg0Highly volatile and be insoluble in water, so removing more difficulty, this part Hg is discharged into the atmosphere and environment is caused serious destruction.In " fossil-fuel power plant atmospheric pollutant emission standard " (GB 13223-2011) that China comes into effect on January 1st, 2012, the clear and definite limit value defining mercury and mercuric compounds concentration is 0.03mg/m3(enforcement on January 1st, 2015), this certainly will control mercury emissions to power plants and bring baptism.Therefore, further investigate hydrargyrum reaction mechanism, continually develop promotion Hg0Oxidation and granular technology will become the needs of development.
White clay is that ammonia-soda process soda plant produces being commonly called as of waste residue, and its composition is mainly by CaCO3, the calcium salt such as CaO, CaCl composition, the most about contain the Cl of 10%.At present, owing to generation amount is relatively big, processing mode is usually treatment in accordance with local conditions: or build a dam and deposit slag, clear liquid overflow；Or marine reclamation land, improve soil；Or fill mine etc..If the demercuration of coal-fired plant boiler can be used it for, then can realize with useless pollution treatment, thus pollutant are carried out Comprehensive Control, it is achieved the recycling economy between enterprise.
Summary of the invention
The present invention proposes a kind of method and system utilizing washing white clay that circulating fluidized bed combustion coal boiler carries out demercuration, and this technology promotes Hg in the clear liquor washing out Cl contained in white clay is sprayed into flue0Aoxidize, the white clay grind into powder after simultaneously washing, in feeding coal dust circulating fluid bed boiler at high temperature center, thus promote gaseous elemental Hg (Hg0) to gaseous oxidation Hg (Hg2+) convert, and improve the absorption to non-mercury oxide of the white clay powder, it is achieved control coal-burning power plant's mercury emissions and realize the purpose of waste residue white clay recycling.
Problem alleged by the present invention is solved by techniques below scheme:
A kind of method and system utilizing washing white clay that circulating fluidized bed combustion coal boiler carries out demercuration, it is characterized in that: described method first washes out containing Cl solution from waste residue white clay, being sprayed before selective catalysis device SCR by air compressor containing Cl clear liquor, thus promote the oxidation of HgO；And the white clay powder after washing is sent into the furnace high-temperature center of coal dust CFBB, promote oxidation and the absorption of Hg in coal dust, the addition of described white clay powder determines according to the following formula: Y=kX, k=(2 in formula, 4), Y is to the addition of to convert mass percent chloride in coal dust after white clay, and X is to be not added with chloride mass percent in the coal dust of white clay.
Waste residue white clay described above is washed, and makes chloride ion contained in white clay soluble in water, and its step is as follows: 1) white clay and coagulator is added one-level equipment for separating liquid from solid and is fully dehydrated；2) clay-slag after dehydration is added in dispersing mixer, be simultaneously introduced water, be configured to the white clay serosity of 10-30% mass concentration, be sufficiently mixed；3) white clay serosity two grades of equipment for separating liquid from solid of feeding are fully dehydrated, clear liquor chloride after obtaining washing.Meanwhile, the white clay after washing grinds to form the powder that particle diameter is 200um.
A kind of method and system utilizing washing white clay that circulating fluidized bed combustion coal boiler carries out demercuration, it is characterized in that: it includes coal dust CFBB, the entrance of the exhanst gas outlet connection cyclone separator of boiler, the upper outlet of cyclone separator is sequentially communicated superheater through flue, economizer, air preheater, cleaner unit, air-introduced machine, the lower part outlet connection coal dust boiler hearth of circulating fluidized bed of cyclone separator, described system is additionally provided with white clay storehouse, centrifugal equipment for separating liquid from solid, dehydrator, white clay storehouse flour mill, high-pressure hydraulic pump, described transfer pipeline is provided with feeding fan, also it is positioned at the jetting device before SCR reactor.
The above-mentioned utilization washing white clay system to circulating fluidized bed combustion coal boiler demercuration, described adsorbent sprays into equipment and is provided with flow control valve.
The present invention is for solving gaseous state Hg discharge and the problem of waste residue white clay recycling in control coal dust firing flue gas.Described method utilizes the waste residue white clay that ammonia-soda process soda plant produces, white clay after washing is ground to certain fineness, spray into high temperature center in the burner hearth of coal dust CFBB, define active adsorptive material and add fly ash content, the clear liquor containing finite concentration Cl is sprayed into after air preheater, spray in the flue of coal dust CFBB, elemental mercury oxidation becomes bivalent mercury to utilize the chlorine containing Cl clear liquor to promote, simultaneously by flue gas being carried out spraying cooling to improve its adsorption efficiency, so that the hydrargyrum that burning produces is more easy to flying dust, absorption occur and form particulate Hg, finally removed by cleaner unit, reach to control the purpose of coal dust firing smoke mercury emission, meanwhile achieve the refuse reclamation of waste white mud, reach the perfect adaptation of economic benefit and environmental emission reduction social benefit.
Test shows, beneficial effects of the present invention can make particulate Hg ratio in ash improve more than 30%.Apparatus of the present invention have simple in construction, with low cost, the feature easily realized.
Accompanying drawing explanation
Fig. 1 is present system schematic diagram；
Fig. 2 is the experimental system schematic diagram of embodiment 1, example 2；
Fig. 3 is the schematic diagram of simulation white clay secondary water-washing process.
nullIn accompanying drawing, label is expressed as follows: 1、Burner，2、Boiler furnace，3、Horizontal flue，4、Extraction valve，5、Mill exhauster，6、Flour mill，7、Baker，8、Solid-liquid separator，9、Regulation valve，10、White clay hopper dredger，11、Superheater，12、Economizer，13、Air compressor，14、Air preheater，15、Shower nozzle，16、Dust arrester，17、Air-introduced machine，18、Cyclone separator，19、SCR reactor，20、Flow control valve，21、Wash front white clay，22、Once washing defecator，23、Secondary washing defecator，24、Clear liquor，25、Wash rear white clay，26、Equipment for separating liquid from solid，27、Washing white clay powder，28、Chloride clear liquor，29、To powder system，30、Auto temperature controlled system，31、Ash sample harvester，32、Mercury analyzer.
Detailed description of the invention
The present invention is to leave in white clay storehouse by the waste residue white clay transported from soda plant, white clay in white clay storehouse is delivered to the white clay after de-Cl to dry in baker by equipment for separating liquid from solid, then the powder of particle diameter 200um it is ground to, it is re-fed in the burner hearth of coal dust CFBB at high temperature center, is promoting Hg0The less shortcoming that cannot adsorb Hg formation granule Hg of ash overcoming coal-burning power plant's burning to produce while oxidation, before being sent to selective catalysis device SCR containing Cl clear liquor by air compressor, owing to clear liquor containing chlorine, increase the overall chlorinity in boiler smoke after being ejected in flue gas, thus promote Hg0Oxidation.In addition will washing after white clay clay into power can avoid white clay directly blend with Pulverized Coal to burn cause disturbance and guarantee that the demercuration effect of white clay reaches best.The addition of white clay powder determines according to the following formula: Y=kX, k=(2,4) in formula, Y be with the addition of washing white clay after convert the chloride mass percent of coal dust, X is the chloride mass percent of coal dust being not added with washing white clay.
White clay after washing is heated by 900 DEG C of-1000 DEG C of high-temperature flue gas come from horizontal flue suction, and sends into baker drying, CaCO3At these elevated temperatures by generation decomposed and generate into CaO and CO2, the CaO of generation and CaO, MgO in white clay and the CaCO not decomposed3It is collectively forming active adsorptive material.The i.e. addition of white clay adds the fly ash content in flue gas, and the absorption for Hg provides advantage.The decomposition mechanism of white clay is: CaCO3→CaO+CO2。
Along with flue gas rearwardly flue flows, flue gas is constantly lowered the temperature to the such as heat release such as economizer, air preheater of each heating surface of boiler.Hg in flue gas will constantly be oxidized into bivalence Hg (Hg2+), part Hg0、Hg2+Become granule Hg by ash particle absorption, and spray can effectively facilitate flue gas Hg containing Cl clear liquor and be oxidized to Hg2+, Hg2+Being more easy to be absorbed by ash particle, Cl can also adsorb to react with the Hg in flue gas on ash particle again to be made flue gas Hg become granule Hg, the granule Hg deposition that is finally captured in cleaner unit with ash particle to get off, thus reaches to control the purpose of coal-burning power plant's mercury emissions.
Cl aoxidizes Hg and oxidation state Hg adsorption mechanism on ash particle is:
2Cl--+H2O→2HCl+O
HCl→Cl+H
Hg0+2Cl→HgCl2
Hg0+2HCl→HgCl2+H2
Hg0(g)→Hg0(ads)
Cl(g)→Cl(ads)
Hg0(g)+2Cl(g)→HgCl2
HgCl2→HgCl2(ads)
Hg0(ads)+2Cl(ads)→HgCl2(ads)
Hg0(g)+2Cl(ads)→HgCl2(ads)
In above reaction equation, (ads) represents that this material is that absorption is on ash particle.
Referring to Fig. 1, the work process of present system is as follows: the white clay shipped from white mud waste residue factory leaves white clay storehouse 10 in, white clay in white clay storehouse 10 is controlled white clay feeding coal by feed regulation valve 9 and is sent in equipment for separating liquid from solid 8, by exsiccator 7, the white clay after washing is dried feeding flour mill 6 and wear into the powder of certain fineness, send in high-temperature flue gas through mill exhauster 5 again, spray into the white clay powder in stove and decompose under high-temperature flue gas (900 DEG C～1000 DEG C) acts on and generate active adsorptive material.Flue gas is through cyclone separator 18, and bed and bulky grain in flue gas are sent back in burner hearth 2, and white clay powder will be with flue gas the most rearwardly flue and moves.Along with the flowing of flue gas, flue gas will contact with superheater 11, economizer 12 and the air preheater 14 of back-end surfaces and heat release cooling successively.Whiten spraying into before selective catalytic reduction device (SCR) 19 containing Cl clear liquor of mud gained, Hg through air compressor 13 logical shower nozzle 150Oxidation will be there is under the effect of Cl and generate Hg2+, Hg2+Easily being become granule Hg by ash particle absorption, the white clay powder of interpolation also increases the collision probability of mercury element and ash.Ash particle containing Hg is removed by cleaner unit 16 the most at last under the effect of air-introduced machine 17, thus the purpose of Hg in reaching removing coal-burning power plant.
Pilot system figure used by experimental example 1 is as shown in Figure 2.
The coal sample Industrial Analysis that experimental example 1 uses is Mad1.84%, Aad34.82%, Vad9.81%, Cad53.52%, elementary analysis composition is Cad53.86%, Had2.41%, Nad0.72, Sad1.37%, Oad3.33%, Clad0.019%, trace element Hg189.9ng/g.The composition of white clay is CaCO380.36%, CaO 4.53%, MgO 5.11%, hydrochloric acid insoluble substance 2.36%, iron-aluminium oxide 3.81%, Cl is 7.26%.Before experiment, in One Dimensional Furnace, center is heated to 1350 DEG C by temperature control system.Experiment is undertaken in two steps, and the first step closes lime mud treatment system, opens to powder system, and powder-feeding amount is 500g/min, and excess air coefficient is 1.2.After coal dust burns in sending into stove, the flying dust produced is by along with flue gas cooling section outside body of heater under the swabbing action of air-introduced machine, cooler will make flue gas be cooled to 200 DEG C-300 DEG C, finally measured the ratio of Elemental Mercury in flue gas by mercury analyzer, ash sample collects the flying dust obtained, and records its particulate Hg ratio.Particulate Hg ratio is defined as: in the ash that unit mass coal dust produces, institute's mercury content accounts for unit mass coal dust and carries the percentage ratio of mercury quantity.Mercury content in ash is 27.35ppb, i.e. particulate Hg ratio is 14.41%, and the ratio of Elemental Mercury is 70.23%, and it is 21.12% that oxidation forms hydrargyrum.Second step, repeat test, carry out for the ease of experiment, open lime mud treatment system, first white clay is washed, the white clay after washing is dried through baker, is then ground to the powder of 200 mesh sieves, and extract the white clay powder after the high-temperature flue gas in the coal dust CFBB of operation adds hot water wash, keep coal dust powder-feeding amount and excess air coefficient constant.Washing white clay powder after heating is sent directly into (700 DEG C～800 DEG C) at body of heater afterbody low temperature.Both feeding coals are determined (feeding coal of white clay is 5g/min) by the chlorine percentage composition not whitened in mud.In embodiment 1 after with the addition of white clay, it is simultaneously to be carried to cooling section by air compressor chloride clear liquor, the flying dust that post-combustion capture obtains, recording the mercury content in ash is 42.12ppb, particulate Hg ratio is 22.18%, and Elemental Mercury ratio is 44.63%, oxidised form hydrargyrum is 41.42%.As can be seen here, after with the addition of white clay powder and chloride clear liquor, particulate Hg ratio improves 8.04%, and Elemental Mercury ratio have dropped 25.60%, and oxidised form hydrargyrum improves 20.30%, has reached the effect of preferable reduction Elemental Mercury ratio.
The test method of experimental example 2 is essentially identical with experimental example 1 with experimentation, the coal sample used is the most identical with white lead composition, except for the difference that the ratio of white clay is added, experimental example 2 coal sample after adding white clay is converted chloride mark and is improved four times, now white clay feeding coal 10g/min, the flying dust that post-combustion capture obtains, recording the mercury content in ash is 57.21ppb, particulate Hg ratio is 30.13%, and Elemental Mercury ratio is 38.33%, and oxidised form hydrargyrum is 32.20%.As can be seen here, after with the addition of white clay powder and chloride clear liquor, particulate Hg ratio improves 16.74%, and Elemental Mercury ratio have dropped 31.90%, and oxidised form hydrargyrum improves 29.52%, has reached the effect of preferable reduction Elemental Mercury ratio.
Claims (6)
1. one kind utilizes the washing white clay system to circulating fluidized bed combustion coal boiler demercuration, it is characterised in that described method is first by water
Wash rear waste residue white clay and grind to form 200um powder, send at coal dust circulating fluidized bed boiler flue high-temperature flue gas through horizontal flue, so
Afterwards washing is obtained in the flue that coal dust CFBB spurted into by the clear liquor containing Cl, reduce flue-gas temperature and promote in coal dust
The oxidation of Hg, the addition of described white clay powder determines according to the following formula: Y=kX, and k=(2,4) in formula, Y is for spraying into clarification
Converting the mass percent that coal dust is chloride after liquid, X is to be not injected into chloride mass percent in the coal dust of clear liquor.
The most according to claim 1 utilization washes the white clay system to circulating fluidized bed combustion coal boiler demercuration, it is characterised in that:
Described waste residue white clay adds coagulator and carries out one-level solid-liquid separation, obtains chloride clear liquor followed by two grades of solid-liquid separation.
The most according to claim 1 utilization washes the white clay system to circulating fluidized bed combustion coal boiler demercuration, it is characterised in that:
It is provided with extraction valve (4) in described boiler horizontal gas pass (3), is connected to dehydrator (7) and is dried white clay powder.
The most according to claim 2 utilization washes the white clay system to circulating fluidized bed combustion coal boiler demercuration, it is characterised in that:
The chloride clear liquor that described washing white clay obtains is injected to air preheater through air compressor (13) by shower nozzle (15)
(14) after, before SCR reactor (19).
The most according to claim 3 utilization washes the white clay system to circulating fluidized bed combustion coal boiler demercuration, it is characterised in that:
After described washing, white clay powder is sent into after point is arranged on horizontal flue (3) high temperature bleed off passage and before superheater (11).
The most according to claim 4 utilization washes the white clay system to circulating fluidized bed combustion coal boiler demercuration, it is characterised in that:
Described injection chloride clear liquor pipeline is provided with flow control valve.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN107366906A (en) * | 2017-07-17 | 2017-11-21 | 清华大学 | The multipaths Horizontal CFB Boiler and operation method of a kind of low mercury emissions |
| CN112973403A (en) * | 2021-03-31 | 2021-06-18 | 华北电力大学（保定） | Method for desulfurizing white mud |
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Patent Citations (5)
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| CN102070287A (en) * | 2010-12-03 | 2011-05-25 | 广州市天益三和能源环保有限公司 | Process for reducing chloride ions in white mud from ammonia soda plants |
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| CN107366906A (en) * | 2017-07-17 | 2017-11-21 | 清华大学 | The multipaths Horizontal CFB Boiler and operation method of a kind of low mercury emissions |
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| CN112973403A (en) * | 2021-03-31 | 2021-06-18 | 华北电力大学（保定） | Method for desulfurizing white mud |
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Application publication date: 20160824 |