CN107930359A - The apparatus and method that elemental mercury in coal-fired flue-gas is removed using desulfurization wastewater - Google Patents
The apparatus and method that elemental mercury in coal-fired flue-gas is removed using desulfurization wastewater Download PDFInfo
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- CN107930359A CN107930359A CN201711398764.0A CN201711398764A CN107930359A CN 107930359 A CN107930359 A CN 107930359A CN 201711398764 A CN201711398764 A CN 201711398764A CN 107930359 A CN107930359 A CN 107930359A
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- desulfurization
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- 238000006477 desulfuration reaction Methods 0.000 title claims abstract description 186
- 230000023556 desulfurization Effects 0.000 title claims abstract description 186
- 239000002351 wastewater Substances 0.000 title claims abstract description 128
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 title claims abstract description 122
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 title claims abstract description 86
- 239000003546 flue gas Substances 0.000 title claims abstract description 86
- 238000000034 method Methods 0.000 title claims abstract description 37
- 229910052602 gypsum Inorganic materials 0.000 claims abstract description 102
- 239000010440 gypsum Substances 0.000 claims abstract description 102
- 229910052753 mercury Inorganic materials 0.000 claims abstract description 100
- 235000019738 Limestone Nutrition 0.000 claims abstract description 36
- 239000006028 limestone Substances 0.000 claims abstract description 36
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 27
- 238000000889 atomisation Methods 0.000 claims abstract description 24
- 238000000605 extraction Methods 0.000 claims abstract description 17
- 239000007921 spray Substances 0.000 claims abstract description 10
- 239000007788 liquid Substances 0.000 claims description 35
- 239000011505 plaster Substances 0.000 claims description 26
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 23
- 229910052791 calcium Inorganic materials 0.000 claims description 23
- 239000011575 calcium Substances 0.000 claims description 23
- 239000007789 gas Substances 0.000 claims description 23
- 239000002002 slurry Substances 0.000 claims description 20
- 239000000203 mixture Substances 0.000 claims description 14
- 229910000372 mercury(II) sulfate Inorganic materials 0.000 claims description 13
- 239000000779 smoke Substances 0.000 claims description 13
- DOBUSJIVSSJEDA-UHFFFAOYSA-L 1,3-dioxa-2$l^{6}-thia-4-mercuracyclobutane 2,2-dioxide Chemical group [Hg+2].[O-]S([O-])(=O)=O DOBUSJIVSSJEDA-UHFFFAOYSA-L 0.000 claims description 12
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 12
- 229940074994 mercuric sulfate Drugs 0.000 claims description 12
- 239000006228 supernatant Substances 0.000 claims description 12
- 239000005864 Sulphur Substances 0.000 claims description 10
- 239000013078 crystal Substances 0.000 claims description 10
- 239000013049 sediment Substances 0.000 claims description 9
- 125000001741 organic sulfur group Chemical group 0.000 claims description 8
- 230000018044 dehydration Effects 0.000 claims description 5
- 238000006297 dehydration reaction Methods 0.000 claims description 5
- 238000006243 chemical reaction Methods 0.000 claims description 4
- 239000012467 final product Substances 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims description 2
- 239000003595 mist Substances 0.000 claims 1
- 239000000428 dust Substances 0.000 abstract description 18
- 230000000149 penetrating effect Effects 0.000 abstract 1
- 238000012360 testing method Methods 0.000 description 15
- 239000012717 electrostatic precipitator Substances 0.000 description 9
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 6
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 6
- 230000007797 corrosion Effects 0.000 description 5
- 238000005260 corrosion Methods 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 4
- 229910052736 halogen Inorganic materials 0.000 description 4
- 150000002367 halogens Chemical class 0.000 description 4
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 3
- 239000003344 environmental pollutant Substances 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 231100000719 pollutant Toxicity 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 229910052717 sulfur Inorganic materials 0.000 description 3
- 239000011593 sulfur Substances 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000003463 adsorbent Substances 0.000 description 2
- 239000003245 coal Substances 0.000 description 2
- 239000006071 cream Substances 0.000 description 2
- 230000006378 damage Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000003628 erosive effect Effects 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 229910001385 heavy metal Inorganic materials 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- 238000004065 wastewater treatment Methods 0.000 description 2
- 229920002472 Starch Polymers 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 229910052925 anhydrite Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000004173 biogeochemical cycle Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 235000019504 cigarettes Nutrition 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000013618 particulate matter Substances 0.000 description 1
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 1
- 210000002966 serum Anatomy 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/46—Removing components of defined structure
- B01D53/64—Heavy metals or compounds thereof, e.g. mercury
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/46—Removing components of defined structure
- B01D53/48—Sulfur compounds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/46—Removing components of defined structure
- B01D53/54—Nitrogen compounds
- B01D53/56—Nitrogen oxides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/75—Multi-step processes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/77—Liquid phase processes
- B01D53/79—Injecting reactants
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F11/00—Compounds of calcium, strontium, or barium
- C01F11/46—Sulfates
- C01F11/464—Sulfates of Ca from gases containing sulfur oxides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2251/00—Reactants
- B01D2251/40—Alkaline earth metal or magnesium compounds
- B01D2251/404—Alkaline earth metal or magnesium compounds of calcium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2251/00—Reactants
- B01D2251/60—Inorganic bases or salts
- B01D2251/606—Carbonates
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2251/00—Reactants
- B01D2251/60—Inorganic bases or salts
- B01D2251/608—Sulfates
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/60—Heavy metals or heavy metal compounds
- B01D2257/602—Mercury or mercury compounds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2258/00—Sources of waste gases
- B01D2258/02—Other waste gases
- B01D2258/0283—Flue gases
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/10—Process efficiency
- Y02P20/129—Energy recovery, e.g. by cogeneration, H2recovery or pressure recovery turbines
Abstract
The present invention provides a kind of apparatus and method that element mercury in coal-fired flue-gas is removed using desulfurization wastewater, described device includes denitrification apparatus and dust-extraction unit, further include air preheater and lime stone desulfurization of gypsum device, the denitrification apparatus, air preheater, dust-extraction unit and lime stone desulfurization of gypsum device are sequentially connected by pipeline, the lime stone desulfurization of gypsum device is connected by desulfurization water pump with the denitrification apparatus, atomization flue is additionally provided between the denitrification apparatus and the air preheater, one end of the atomization flue is connected with the desulfurization water pump, the other end of the atomization flue is connected with the air preheater；The method removes the element mercury in flue gas by the device.The present invention is by the way that before the position of the spray site of desulfurization wastewater is arranged on air preheater, the temperature range of penetrating reduces the ratio resistance of flying dust at 260~400 DEG C, be conducive to the trapping of flying dust, desulfurization wastewater demercuration is used merely, secondary pollution is avoided, reduces cost.
Description
Technical field
The invention belongs to environmental protection technical field, is related to the device of elemental mercury and side in a kind of removing coal-fired flue-gas
A kind of method, and in particular to apparatus and method that element mercury in coal-fired flue-gas is removed using desulfurization wastewater.
Background technology
With the continuous improvement of industrialized level, various industrial pollution events take place frequently, and cause the extensive concern of people, especially
It is the trace heavy metals of industrial discharge.Mercury, is listed in the pollutant most poisoned in trace heavy metal pollutant.Data
It has been shown that, mankind's activity is mercury emissions main source in air, and 85% comes from burning of coal in artificial mercury emissions source.
The main method of coal-fired flue gas mercury removal is divided into two aspects at present, that is, adsorbs spraying technique method and with existing air
Demercuration technology is cooperateed with based on pollution control device.It is efficient to adsorb spraying technique method, but coal fired power plant flue gas to be treated
Amount is big, therefore need to consume a large amount of activated carbon adsorbents, and adsorbent subsequent treatment is difficult, and secondary pollution is easily caused if dealing with improperly；
Method using existing pollution control device collaboration demercuration has relatively large advantage.The oxidation state mercury formed in coal-fired process
(Hg2+) and particulate form mercury (Hgp) can be taken off respectively by wet desulphurization device (WFGD) and dust processing equipment (such as ESP)
Remove.And elemental mercury (the Hg formed0), stability is extremely strong, not soluble in water, often exists with gaseous form, can stop for a long time after discharge
Stay in an atmosphere, global mercury pollution is easily caused by biogeochemical cycle diffusion.Therefore, how thermal power plant is controlled
Hg in pollutant0Discharge, become effectively control mercury pollution key.
During desulfurization wastewater is mainly coal-burning power plant's limestone/gypsum method smoke-gas wet desulfurization, in order to maintain desulfurization to fill
The balance of serum recycle system material is put, a certain amount of waste water is discharged from system.The pH of desulfurization wastewater is 4.5-6.5, wherein
Contain a large amount of Cl-、F-, suspended matter etc., this high salinity it is outer get rid of sulphur wastewater in waters direct harm it is extremely serious, must
Must qualified discharge after treatment.Conventional to use three header technical finesse desulfurization wastewaters, system configuration is complicated, cost for wastewater treatment
It is high.Patent 201310424364.8, a kind of desulfurization wastewater using coal-burning power plant is carried out in the method and system of flue gas demercuration, public
A kind of method by the desulfurization wastewater removal of mercury is opened, but it needs to add demercuration catalyst and halogen in the desulfurization wastewater used
Element, which not only adds demercuration cost, and brings secondary pollution, increases subsequent wastewater treatment expense, and its removal of mercury is imitated
Rate is relatively low.In addition, the current relevant method using desulfurization wastewater demercuration carries out demercuration, it is impossible to effectively reduces flying dust
Ratio resistance, the efficiency of electrostatic precipitator are low.
The content of the invention
It is therefore an object of the present invention to for the problem of presently, there are, there is provided one kind removes coal-fired cigarette using desulfurization wastewater
The apparatus and method of element mercury in gas, without adding extra demercuration catalyst and halogen, use desulfurization wastewater demercuration merely, keep away
Exempt from secondary pollution, reduced cost, and expeditiously remove the element mercury in flue gas.
The technical solution of provider of the present invention is as follows：
On the one hand, the present invention provides a kind of device that element mercury in coal-fired flue-gas is removed using desulfurization wastewater, including denitration
Device and dust-extraction unit, further include air preheater and lime stone desulfurization of gypsum device, the denitrification apparatus, air preheater,
Dust-extraction unit and lime stone desulfurization of gypsum device are sequentially connected by pipeline, and the lime stone desulfurization of gypsum device passes through desulfurization water
Pump is connected with the denitrification apparatus, and atomization flue, the atomization are additionally provided between the denitrification apparatus and the air preheater
One end of flue is connected with the desulfurization water pump, and the other end of the atomization flue is connected with the air preheater.
Preferably, source of the gas is also associated with the atomising device, the source of the gas is pumped into atomising device by air pump, passes through
Air pump pump air into atomization flue nozzle, under high-speed flow, by desulfurization wastewater atomization be tiny drop, add and
The contact surface of element mercury, further improves demercuration efficiency in flue gas.Preferably, the lime stone desulfurization of gypsum device takes off with described
Desulfurization wastewater case is additionally provided between sulphur water pump, organic sulfur is placed in the desulfurization wastewater case, desulfurization slurry is captured by organic sulfur
In Hg2+, form sediment and separated from desulfurization wastewater, so as to improve removal efficiency of mercury.
Preferably, gypsum rotational flow station group is additionally provided between the desulfurization wastewater case and the lime stone desulfurization of gypsum device
Part, one end of the gypsum rotational flow station component is also associated with calcium plaster liquid case, and the supernatant in the calcium plaster liquid case is back to
In the gypsum rotational flow station component, the suspended matter in desulfurization wastewater is on the one hand reduced by the device, avoids atomizer from grinding
Damage corrosion, is on the other hand conducive to the comprehensive utilization of desulfurated plaster.
Preferably, the side of the calcium plaster liquid case is also connected with vacuum belt dewaterer, and opposite side is connected to the stone
The other end of cream rotational flow station component, its supernatant is back in the gypsum rotational flow station component.
Preferably, the gypsum rotational flow station component includes one or more gypsum rotational flow stations.
Preferably, when the gypsum rotational flow station component includes multiple gypsum rotational flow stations, the multiple gypsum rotational flow station according to
Secondary connection, first gypsum rotational flow station in the multiple gypsum rotational flow station are connected with the lime stone desulfurization of gypsum device, institute
Last the gypsum rotational flow station stated in multiple gypsum rotational flow stations is connected with the calcium plaster liquid case, first gypsum eddy flow
The desulfurization slurry stood is back in last gypsum rotational flow station, and the supernatant in the calcium plaster liquid case is back to last
In gypsum rotational flow station.By way of multiple gypsum rotational flow stations, the moisture content of desulfurated plaster can be further reduced, is conducive to take off
The integrated application of sulphur gypsum
Preferably, gas gas exchanger is also associated with the lime stone desulfurization of gypsum device, it is possible to increase chimney emission temperature
Degree, avoids polluting surrounding environment.Preferably, the gas gas heat exchange is equipped with first interface and second interface, described
First interface is located between the dust-extraction unit and the lime stone desulfurization of gypsum device, the side of the second interface with it is described
Lime stone desulfurization of gypsum device connects, and opposite side is connected with chimney.On the other hand, the present invention also provides a kind of according to above-mentioned profit
The demercuration method of the device of element mercury in coal-fired flue-gas is removed with desulfurization wastewater, is comprised the following steps：
1) desulfurization wastewater is formed by atomized drop by desulfurization water pump, then at 260~400 DEG C, by the atomized liquid
Drop sprays into atomization flue and is reacted by the element mercury in the flue gas after denitrification apparatus denitrogenation, and flue gas mixes after obtaining waste water demercuration
Thing, the existence form of mercury includes the bivalent mercury in flue gas and is attached to ash surface in smoke mixture after the waste water demercuration
Mercuric sulfate crystal；
2) smoke mixture after the waste water demercuration is first passed through into air preheater again, then be passed through in dust-extraction unit, removed
The mercuric sulfate crystal of ash surface is attached to, and the bivalent mercury in flue gas is trapped by lime stone desulfurization of gypsum device,
Make to flow out containing mercuric desulfurization slurry, and the flue gas discharge after demercuration, to obtain the final product.
Preferably, in step 1), at 350~400 DEG C, the atomized drop is sprayed into atomization flue and by de-
Element mercury reaction in flue gas after nitre device denitration, mercury removal efficiency is more preferable in this temperature range.
Preferably, in step 1), the straying quatity that the atomized drop sprays into atomization flue is 0.012~0.025L/m3
(liquid-gas ratio), is preferably 0.018L/m3, under the straying quatity of the scope, the removal efficiency of element mercury remains in flue gas
More than 90%.
Preferably, the pH of the desulfurization wastewater is 5~8, is preferably 5.5, under the pH of the scope, element mercury in flue gas
Removal efficiency remains at more than 90%.
Preferably, it is further comprising the steps of after the outflow containing mercuric desulfurization slurry in step 2)：
It is passed through described containing mercuric desulfurization slurry in desulfurization wastewater case, in soluble bivalent mercury and desulfurization wastewater case
Organic sulfur combine to form sediment export, the step can by organic sulfur capture sweetening process in trap under Hg2+, it is heavy to be formed
Starch is separated from desulfurization wastewater, so as to improve removal efficiency of mercury.
Preferably, it is described be passed through desulfurization wastewater case containing mercuric desulfurization slurry before, it is further comprising the steps of：
By it is described containing mercuric desulfurization slurry be passed through gypsum hang stream station component after, split into two parts, a part of shape
Enter calcium plaster liquid case into denseer gypsum liquid, supernatant is formed in the calcium plaster liquid case and hangs stream station group back to gypsum
Part, lower floor's muddiness gypsum liquid are sent into vacuum belt dewaterer, and gypsum is formed after dehydration and is utilized；Another part eddy flow obtains clear
Night is desulfurization wastewater, after being sent to desulfurization wastewater case removing bivalent mercury, is passed through the utilization of desulfurization water pump, passes through one side of the device
Face reduces the suspended matter in desulfurization wastewater, avoids atomizer erosion corrosion, improves demercuration efficiency, is on the other hand conducive to take off
The comprehensive utilization of sulphur gypsum.
The apparatus and method that element mercury in coal-fired flue-gas is removed using desulfurization wastewater of the present invention, by by desulfurization wastewater
The position of spray site is arranged between denitrification apparatus and air preheater, and the temperature range sprayed into is sprayed at 260~400 DEG C
Enter desulfurization wastewater, reduce the ratio resistance of flying dust, be conducive to the trapping of flying dust；It is and substantial amounts of due to being enriched in desulfurization wastewater
Cl-Ion, therefore a large amount of Cl in desulfurization wastewater can be utilized-Ion, achievees the purpose that to remove element mercury in flue gas, saves at the same time
The processing cost of power plant desulfurization wastewater；In addition, the present invention is no additionally to add demercuration catalyst and halogen, merely using desulfurization
Waste water demercuration, avoids secondary pollution, reduces cost；Spray into desulfurization wastewater straying quatity it is small, flue-gas temperature for acid dew point on,
Smaller to the corrosion impact of follow-up equipment, demercuration efficiency is high；In addition, by adding desulfurization wastewater case, and in desulfurization wastewater case
Middle placement organic sulfur, can capture the Hg under being trapped in sweetening process by organic sulfur2+, sediment is formed from desulfurization wastewater
Separate, so as to improve removal efficiency of mercury, the removal efficiency for making elemental mercury is more than 90%；And it can effectively reduce flying dust
Ratio resistance, electrostatic precipitator it is efficient.
Brief description of the drawings
Hereinafter, the embodiment that the present invention will be described in detail is carried out with reference to attached drawing, wherein：
Fig. 1 is the structure diagram that the device of element mercury in coal-fired flue-gas is removed using desulfurization wastewater of the present invention；
Fig. 2 is the XRD diffracting spectrums in the deposit obtained in the embodiment of the present invention 1；
Fig. 3 is that the method for removing element mercury in coal-fired flue-gas in the test example 1 of the present invention using desulfurization wastewater passes through waste water
The experimental result picture of the element mercury in flue gas is removed with pure water；
Fig. 4 is to utilize desulfurization wastewater to remove the method for element mercury in coal-fired flue-gas in not equality of temperature in the test example 2 of the present invention
The experimental result picture of element mercury in the lower removing flue gas of degree；
Fig. 5 is that the method for utilizing desulfurization wastewater to remove element mercury in coal-fired flue-gas in the test example 3 of the present invention is useless in difference
Experimental result picture under water straying quatity；
Fig. 6 is to utilize desulfurization wastewater to remove the method for element mercury in coal-fired flue-gas in different pH in the test example 4 of the present invention
Under experimental result picture；
Fig. 7 is the part-structure schematic diagram that the device of element mercury in coal-fired flue-gas is removed using desulfurization wastewater of the present invention；
Wherein：
1. denitrification apparatus, 2. dust-extraction units, 3. air preheaters, 4. lime stone desulfurization of gypsum devices, 5. desulfurization water pumps, 6.
Atomization flue, 7. sources of the gas, 8. desulfurization wastewater casees, 9. gypsum rotational flow stations, 10. calcium plaster liquid cases, 11. vacuum belt dewaterers, 12.
First interface, 13. second interfaces, 14. chimneys, 15. air pumps, 16. economizers, 17. boilers.
Embodiment
Unless specifically stated otherwise, reagent used in following embodiments can be commercially available from regular channel.
As shown in Figure 1, the present invention provides a kind of device that element mercury in coal-fired flue-gas is removed using desulfurization wastewater, including it is de-
Nitre device 1 and dust-extraction unit 2, further include air preheater 3 and lime stone desulfurization of gypsum device 4, denitrification apparatus 1, air preheat
Device 3, dust-extraction unit 2 and lime stone desulfurization of gypsum device 4 are sequentially connected by pipeline, and lime stone desulfurization of gypsum device 4 passes through de-
Sulphur water pump 5 is connected with denitrification apparatus 1, and atomization flue 6 is additionally provided between denitrification apparatus 1 and air preheater 3, atomization flue 6
One end is connected with desulfurization water pump 5, and the other end of atomization flue 6 is connected with air preheater 3.When it is implemented, denitration fills
Economizer 16 and boiler 17 can be also connected with turn by putting 1 side.
In the above-described embodiments, source of the gas 7 is also associated with atomising device 6, source of the gas 7 is pumped into atomising device by air pump 15
6, atomization flue nozzle is pumped air into by air pump, under high-speed flow, is tiny drop by desulfurization wastewater atomization, increases
Add the contact surface with element mercury in flue gas, further improve demercuration efficiency.
In the above-described embodiments, desulfurization wastewater case 8 is additionally provided between lime stone desulfurization of gypsum device 4 and desulfurization water pump 5, is taken off
Organic sulfur is placed with sulphur waste water tank 8, the Hg in desulfurization slurry is captured by organic sulfur2+, sediment is formed from desulfurization wastewater
Separate, so as to improve removal efficiency of mercury.
In the above-described embodiments, gypsum rotational flow station group is additionally provided between desulfurization wastewater case 8 and lime stone desulfurization of gypsum device 4
Part, one end of gypsum rotational flow station component is also associated with calcium plaster liquid case 10, and the supernatant in the calcium plaster liquid case is back to institute
Gypsum rotational flow station component is stated, on the one hand reduces the suspended matter in desulfurization wastewater, avoids atomizer erosion corrosion, improves demercuration
Efficiency, is on the other hand conducive to the comprehensive utilization of desulfurated plaster.When it is implemented, side and the vacuum belt of calcium plaster liquid case 10
Dewaterer 11 connects, and opposite side is connected to the other end of gypsum rotational flow station component, its supernatant is back to the gypsum rotational flow station
In component.
In the above-described embodiments, gypsum rotational flow station component includes one or more gypsum rotational flow stations 9.
In the above-described embodiments, when gypsum rotational flow station component includes multiple gypsum rotational flow stations 9, multiple gypsum rotational flow stations 9
It is sequentially connected, first gypsum rotational flow station in multiple gypsum rotational flow stations 9 is connected with lime stone desulfurization of gypsum device 4, Duo Geshi
Last gypsum rotational flow station in cream rotational flow station 9 is connected with calcium plaster liquid case 10, the desulfurization slurry in first gypsum rotational flow station 9
Liquid is back in last gypsum rotational flow station, and the supernatant in calcium plaster liquid case 10 is back in last gypsum rotational flow station 9.
When it is implemented, gypsum rotational flow station component may include two gypsum rotational flow stations 9, as shown in Figure 7.
In the above-described embodiments, gas gas exchanger is also associated with lime stone desulfurization of gypsum device 4, being capable of lifting smoke evacuation temperature
Degree, avoids polluting surrounding environment.
In the above-described embodiments, the heat exchange of gas gas is equipped with first interface 12 and second interface 13, and first interface 12 is located at
Between dust-extraction unit 2 and lime stone desulfurization of gypsum device 4, the side of second interface 13 is connected with lime stone desulfurization of gypsum device 4,
Opposite side is connected with chimney 14.
Embodiment 1
1) desulfurization wastewater that pH is 5.5 is formed by atomized drop by desulfurization water pump, then at 350 DEG C, with 0.018L/
m3Straying quatity, by atomized drop spray into atomization flue in pass through in flue gas after denitrification apparatus elemental mercury react (mercury concentration
For 48.52 μ g/m3), obtain smoke mixture after waste water demercuration；After the waste water demercuration in smoke mixture mercury existence form
Including the bivalent mercury in flue gas and the mercuric sulfate crystal for being attached to ash surface；
2) smoke mixture after the flue gas desulfurization waste-water demercuration after the denitration is passed through in dust-extraction unit again, removes attachment
Trapped, obtained by lime stone desulfurization of gypsum device in the mercuric sulfate crystal of ash surface, and by the bivalent mercury in flue gas
Contain mercuric desulfurization slurry；
3) it is passed through described containing mercuric desulfurization slurry after gypsum hangs stream station, splits into two parts, a part is formed
Denseer gypsum liquid enters calcium plaster liquid case, and supernatant is formed in the calcium plaster liquid case and hangs stream station back to gypsum, under
The muddy gypsum liquid of layer is sent into vacuum belt dewaterer, and gypsum is formed after dehydration and is utilized；The stillness of night that another part eddy flow obtains is i.e.
For desulfurization wastewater, be sent to after desulfurization wastewater case after removing bivalent mercury, soluble bivalent mercury with it is organic in desulfurization wastewater case
Sulphur combines to form sediment export, and desulfurization wastewater is passed through desulfurization water pump and recycles.
Flue gas after being handled by the above method is surveyed by QM201H coal-fired flue-gas mercury vapourmeter (SUZHOUQING(sic) pacifies instrument company)
Fixed remaining elemental mercury.The sulfur dioxide in flue gas, nitric oxide are by J2KN Multifunctional smokes analyzer (German Yikang at the same time
E measurement technology company) measure, the results showed that the concentration of elemental mercury is changed into 2.50 μ g/m in flue gas3, demercuration efficiency can reach
96.84%.The ratio of the lower waste water flying dust of DR-3 type high voltage bug dust specific resistances testing stand measure electrostatic precipitator trapping is utilized at the same time
Resistance is reduced to 8.0 × 108(ratio resistance of former flying dust is up to 1010), the efficiency of electrostatic precipitator adds 0.2%.
The mercuric sulfate crystal (deposit) of the ash surface formed in embodiment 1 is specially marked into XRD analysis according to XRD
Quasi- card, selects calcium sulfate CaSO4(JCPDS 30-0279) mercuric sulfate HgSO4(JCPDS 31-0867) and simple substance elemental mercury
Hg (JCPDS 17-0863) is contrasted, and the results are shown in Figure 2, it can be seen that in the deposit, the diffraction of mercuric sulfate occurs
Peak, shows that gaseous element state state mercury in flue gas has been converted into the mercuric sulfate of solid.At the same time, it is known that deposit on solid particulate matter surface
In elemental mercury, show that the deposit can be with absorbed portion elemental mercury.
Embodiment 2
1) desulfurization wastewater that pH is 5 is formed by atomized drop by desulfurization water pump, then at 260 DEG C, with 0.025L/m3
Straying quatity, atomized drop is sprayed into atomization flue with reacting (mercury concentration by element mercury in flue gas after the denitrification apparatus removal of mercury
For 80.89 μ g/m3), obtain the flue gas desulfurization waste-water mixture after denitrating flue gas after waste water demercuration；Flue gas after the waste water demercuration
The existence form of mercury includes the bivalent mercury in flue gas and is attached to the mercuric sulfate crystal of ash surface in mixture；
2) smoke mixture after the waste water demercuration is passed through in dust-extraction unit again, removes the sulfuric acid for being attached to ash surface
Mercury crystal, and the bivalent mercury in flue gas is trapped by lime stone desulfurization of gypsum device, obtain containing mercuric desulfurization
Slurries；
3) it is passed through described containing mercuric desulfurization slurry after gypsum hangs stream station, splits into two parts, a part is formed
Denseer gypsum liquid enters calcium plaster liquid case, and supernatant is formed in the calcium plaster liquid case and hangs stream station back to gypsum, under
The muddy gypsum liquid of layer is sent into vacuum belt dewaterer, and gypsum is formed after dehydration and is utilized；The stillness of night that another part eddy flow obtains is i.e.
For desulfurization wastewater, be sent to after desulfurization wastewater case after removing bivalent mercury, soluble bivalent mercury with it is organic in desulfurization wastewater case
Sulphur combines to form sediment export, and desulfurization wastewater is passed through desulfurization water pump and recycles.
Flue gas after being handled by the above method is surveyed by QM201H coal-fired flue-gas mercury vapourmeter (SUZHOUQING(sic) pacifies instrument company)
Fixed remaining elemental mercury.The sulfur dioxide in flue gas, nitric oxide are by J2KN Multifunctional smokes analyzer (German Yikang at the same time
E measurement technology company) measure, the results showed that the concentration of elemental mercury is changed into 8 μ g/m in flue gas3, demercuration efficiency can reach 90%.
6.9 are reduced to using the ratio resistance of the lower flying dust of DR-3 type high voltage bug dust specific resistances testing stand measure electrostatic precipitator trapping at the same time ×
108(ratio resistance of former flying dust is up to 1010), the arresting efficiency of electrostatic precipitator adds 0.3%.
Embodiment 3
1) desulfurization wastewater that pH is 8 is sent into form atomized drop by desulfurization water pump, then at 400 DEG C, with
0.012L/m3Straying quatity, atomized drop is sprayed into atomization flue with being reacted by element mercury in the flue gas after denitrification apparatus
(mercury concentration is 40.38 μ g/m3), obtain smoke mixture after waste water demercuration；Mercury in smoke mixture after the waste water demercuration
Existence form includes the bivalent mercury in flue gas and is attached to the mercuric sulfate crystal of ash surface；
2) smoke mixture after the waste water demercuration is passed through in dust-extraction unit again, removes the sulfuric acid for being attached to ash surface
Mercury crystal, and the bivalent mercury in flue gas is trapped by lime stone desulfurization of gypsum device, obtain containing mercuric desulfurization
Slurries；
3) it is passed through described containing mercuric desulfurization slurry after gypsum hangs stream station, splits into two parts, a part is formed
Denseer gypsum liquid enters calcium plaster liquid case, and supernatant is formed in the calcium plaster liquid case and hangs stream station back to gypsum, under
The muddy gypsum liquid of layer is sent into vacuum belt dewaterer, and gypsum is formed after dehydration and is utilized；The stillness of night that another part eddy flow obtains is i.e.
For desulfurization wastewater, be sent to after desulfurization wastewater case after removing bivalent mercury, soluble bivalent mercury with it is organic in desulfurization wastewater case
Sulphur combines to form sediment export, and desulfurization wastewater is passed through the utilization of desulfurization water pump.
Flue gas after being handled by the above method is surveyed by QM201H coal-fired flue-gas mercury vapourmeter (SUZHOUQING(sic) pacifies instrument company)
Fixed remaining elemental mercury.The sulfur dioxide in flue gas, nitric oxide are by J2KN Multifunctional smokes analyzer (German Yikang at the same time
E measurement technology company) measure, the results showed that the concentration of elemental mercury becomes 2 μ g/m in flue gas3, demercuration efficiency can reach 95%.Together
The ratio resistance of the lower flying dust of Shi Liyong DR-3 type high voltage bug dust specific resistances testing stand measure electrostatic precipitator trapping is reduced to 8.7 ×
108(ratio resistance of former flying dust is up to 1010), the efficiency of electrostatic precipitator adds 0.18%.
Test example 1
Two groups of experiments are done in the present inventive method, are specially that battery of tests only only adds pure water in the reactor, in addition one
Group adds desulfurization wastewater and carries out demercuration, every 10 minutes, measures mercury fluorescent value by QM201H coal-fired flue-gas mercury vapourmeter, as a result such as
Shown in Fig. 3, as can be seen from Figure 3 only add its demercuration efficiency of the experiment of pure water demercuration very low, only 0.05%, it can ignore
Disregard；And the mercury fluorescent value of the flue gas after desulfurization wastewater is added in flue gas, and it is rapid to decline, after stablizing, the removing effect of elemental mercury
Rate illustrates to there are the component beneficial to element mercury removal in desulfurization wastewater, can reach element using desulfurization wastewater up to 98%
The purpose of state mercury removal.
Test example 2
Remove the element mercury in flue gas as described in Example 1, it is different be in 100 DEG C of temperature, 120 DEG C, 150 DEG C, 200
DEG C, 230 DEG C, 260 DEG C, 300 DEG C, 355 DEG C, do parallel test respectively at a temperature of 400 DEG C, the results are shown in Figure 4, can from figure
To find out, when temperature is more than 100 DEG C, gradually risen with the rise elemental mercury removal efficiency of reaction temperature, when temperature reaches
During to 260 DEG C, the removal efficiency of elemental mercury can reach 90%, continue to increase reaction temperature, the removal efficiency of elemental mercury can
Up to 98%.
Test example 3
The element mercury in flue gas is removed as described in Example 1, and different is with 0.010L/m3、0.012L/m3、
0.015L/m3、0.018L/m3、0.021L/m3、0.025L/m3、0.028L/m3Different straying quatities spray into flue gas as parallel examination
Test, the results are shown in Figure 5, it can be seen from the figure that when liquid-gas ratio is 0.012~0.025L/m3, the elemental mercury removal efficiency beginning
More than 90% is maintained at eventually, higher than 0.025L/m3When, downward trend is presented in elemental mercury removal efficiency.
Test example 4
The element mercury in flue gas is removed as described in Example 1, it is different to be 5.0,5.5,6.25,7.5 and 8.0 by pH
Flue gas as parallel test, the results are shown in Figure 6, it can be seen from the figure that the mercury in the range of pH5~8 of desulfurization wastewater
Removal efficiency is up to more than 90%.
To sum up, the apparatus and method of the invention that element mercury in coal-fired flue-gas is removed using desulfurization wastewater, by by desulfurization
The position of the spray site of waste water is set between denitrification apparatus and air preheater, and the temperature range sprayed into is 260~400
DEG C, desulfurization wastewater is sprayed into, the ratio resistance of flying dust is reduced, is conducive to the trapping of flying dust；And due to being enriched in desulfurization wastewater
Substantial amounts of Cl-Ion, therefore a large amount of Cl in desulfurization wastewater can be utilized-Ion, achievees the purpose that to remove element mercury in flue gas, together
The Shi Jieyue processing costs of power plant desulfurization wastewater；In addition, the present invention makes merely without demercuration catalyst and halogen is additionally added
With desulfurization wastewater demercuration, secondary pollution is avoided, reduces cost；It is small to spray into desulfurization wastewater straying quatity, flue-gas temperature is revealed for acid
Smaller to the corrosion impact of follow-up equipment on point, demercuration efficiency is high；In addition, by adding desulfurization wastewater case, and in desulfurization
Organic sulfur is placed in waste water tank, the Hg under being trapped in sweetening process can be captured by organic sulfur2+, sediment is formed from desulfurization
Separated in waste water, so as to improve removal efficiency of mercury, the removal efficiency for making elemental mercury is more than 90%；And can effectively it drop
Fly at low altitude ash ratio resistance, electrostatic precipitator it is efficient.
Claims (10)
1. a kind of device that element mercury in coal-fired flue-gas is removed using desulfurization wastewater, including denitrification apparatus and dust-extraction unit, it is special
Sign is, further includes air preheater and lime stone desulfurization of gypsum device, the denitrification apparatus, air preheater, dust-extraction unit
Be sequentially connected with lime stone desulfurization of gypsum device by pipeline, the lime stone desulfurization of gypsum device by desulfurization water pump with it is described
Denitrification apparatus connects, and atomization flue is additionally provided between the denitrification apparatus and the air preheater, described to be atomized the one of flue
End is connected with the desulfurization water pump, and the other end of the atomization flue is connected with the air preheater.
2. the device according to claim 1 that element mercury in coal-fired flue-gas is removed using desulfurization wastewater, it is characterised in that institute
State and source of the gas is also associated with atomising device, the source of the gas is pumped into atomising device by air pump.
3. the device according to claim 2 that element mercury in coal-fired flue-gas is removed using desulfurization wastewater, it is characterised in that institute
State and desulfurization wastewater case is additionally provided between lime stone desulfurization of gypsum device and the desulfurization water pump, be placed with the desulfurization wastewater case
Organic sulfur.
4. the device according to claim 3 that element mercury in coal-fired flue-gas is removed using desulfurization wastewater, it is characterised in that institute
State and gypsum rotational flow station component is additionally provided between desulfurization wastewater case and the lime stone desulfurization of gypsum device, the gypsum rotational flow station group
Calcium plaster liquid case is also associated with part, and the supernatant in the calcium plaster liquid case is back in the gypsum rotational flow station component.
5. the device according to any one of claim 1 to 4 that element mercury in coal-fired flue-gas is removed using desulfurization wastewater, its
It is characterized in that, gas gas exchanger is also associated with the lime stone desulfurization of gypsum device；Preferably, set in the gas gas heat exchange
Have a first interface and second interface, the first interface be located at the dust-extraction unit and the lime stone desulfurization of gypsum device it
Between, the side of the second interface is connected with the lime stone desulfurization of gypsum device, and opposite side is connected with chimney.
6. according to any one of claim 1 to 5 remove the device of element mercury in coal-fired flue-gas using desulfurization wastewater
Demercuration method, comprises the following steps：
1) desulfurization wastewater is formed by atomized drop by desulfurization water pump, then at 260~400 DEG C, atomized drop is sprayed into mist
Change flue and reacted by the element mercury in the flue gas after denitrification apparatus denitration, obtain smoke mixture after waste water demercuration, it is described
The existence form of mercury includes the bivalent mercury in flue gas and is attached to the mercuric sulfate of ash surface in smoke mixture after waste water demercuration
Crystal；
2) smoke mixture after the waste water demercuration is passed through in dust-extraction unit again, removes the mercuric sulfate crystalline substance for being attached to ash surface
Body, and the bivalent mercury in flue gas is trapped by lime stone desulfurization of gypsum device, make containing mercuric desulfurization slurry stream
Go out, and the flue gas discharge after demercuration, to obtain the final product.
7. the demercuration method according to claim 6 that the device of element mercury in coal-fired flue-gas is removed using desulfurization wastewater, its
It is characterized in that, in step 1), at 350~400 DEG C, atomized drop is sprayed into atomization flue with passing through denitrification apparatus denitration
Element mercury reaction in flue gas afterwards.
8. the demercuration method that the device of element mercury in coal-fired flue-gas is removed using desulfurization wastewater according to claim 6 or 7,
It is characterized in that, in step 1), the straying quatity that the atomized drop sprays into atomization flue is 0.012~0.025L/m3, preferably
For 0.018L/m3。
9. the device of element mercury in coal-fired flue-gas is removed using desulfurization wastewater according to any one of claim 6 to 8
Demercuration method, it is characterised in that the pH of the desulfurization wastewater is 5~8, is preferably 5.5.
10. the device of element mercury in coal-fired flue-gas is removed using desulfurization wastewater according to any one of claim 6 to 9
Demercuration method, it is characterised in that further comprising the steps of after the outflow containing mercuric desulfurization slurry in step 2)：
It is passed through described containing mercuric desulfurization slurry in desulfurization wastewater case, soluble bivalent mercury and having in desulfurization wastewater case
Machine sulphur combines to form sediment export；
Preferably, it is described be passed through desulfurization wastewater case containing mercuric desulfurization slurry before, it is further comprising the steps of：
Be passed through described containing mercuric desulfurization slurry after gypsum hangs stream station component, split into two parts, a part formed compared with
Dense gypsum liquid enters calcium plaster liquid case, and supernatant is formed in the calcium plaster liquid case and hangs stream station component back to gypsum,
Lower floor's muddiness gypsum liquid is sent into vacuum belt dewaterer, and gypsum is formed after dehydration and is utilized；The stillness of night that another part eddy flow obtains
As desulfurization wastewater, after being sent to desulfurization wastewater case removing bivalent mercury, is passed through the utilization of desulfurization water pump.
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Cited By (1)
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Application publication date: 20180420 |