CN110420548A - The device and method of flue gas ammonia process collaboration denitration desulfuration demercuration minimum discharge - Google Patents
The device and method of flue gas ammonia process collaboration denitration desulfuration demercuration minimum discharge Download PDFInfo
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- CN110420548A CN110420548A CN201910828883.8A CN201910828883A CN110420548A CN 110420548 A CN110420548 A CN 110420548A CN 201910828883 A CN201910828883 A CN 201910828883A CN 110420548 A CN110420548 A CN 110420548A
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- flue gas
- demercuration
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- mercury
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- 239000003546 flue gas Substances 0.000 title claims abstract description 107
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 title claims abstract description 103
- 238000006477 desulfuration reaction Methods 0.000 title claims abstract description 52
- 238000000034 method Methods 0.000 title claims abstract description 40
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 title claims abstract description 32
- 230000008569 process Effects 0.000 title claims abstract description 16
- 229910021529 ammonia Inorganic materials 0.000 title claims abstract description 15
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 claims abstract description 106
- 229910052753 mercury Inorganic materials 0.000 claims abstract description 103
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 44
- 230000003647 oxidation Effects 0.000 claims abstract description 43
- 238000010521 absorption reaction Methods 0.000 claims abstract description 33
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 claims abstract description 25
- 229910052921 ammonium sulfate Inorganic materials 0.000 claims abstract description 25
- 235000011130 ammonium sulphate Nutrition 0.000 claims abstract description 24
- 239000012716 precipitator Substances 0.000 claims abstract description 16
- 239000000126 substance Substances 0.000 claims description 29
- 239000007788 liquid Substances 0.000 claims description 27
- 238000006243 chemical reaction Methods 0.000 claims description 20
- 239000006096 absorbing agent Substances 0.000 claims description 12
- 239000007921 spray Substances 0.000 claims description 12
- 239000013049 sediment Substances 0.000 claims description 11
- 239000003054 catalyst Substances 0.000 claims description 10
- 239000000706 filtrate Substances 0.000 claims description 9
- 238000005192 partition Methods 0.000 claims description 6
- DPLVEEXVKBWGHE-UHFFFAOYSA-N potassium sulfide Chemical compound [S-2].[K+].[K+] DPLVEEXVKBWGHE-UHFFFAOYSA-N 0.000 claims description 6
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 4
- 239000000908 ammonium hydroxide Substances 0.000 claims description 4
- 238000005507 spraying Methods 0.000 claims description 2
- 229920002472 Starch Polymers 0.000 claims 1
- 235000019698 starch Nutrition 0.000 claims 1
- 239000008107 starch Substances 0.000 claims 1
- 238000004064 recycling Methods 0.000 abstract description 5
- 239000003337 fertilizer Substances 0.000 abstract description 3
- 239000002351 wastewater Substances 0.000 abstract description 3
- 230000008901 benefit Effects 0.000 abstract description 2
- 238000000926 separation method Methods 0.000 abstract description 2
- 239000003245 coal Substances 0.000 description 22
- 239000000243 solution Substances 0.000 description 20
- 239000000460 chlorine Substances 0.000 description 10
- 229910052801 chlorine Inorganic materials 0.000 description 9
- 238000005516 engineering process Methods 0.000 description 9
- 239000007789 gas Substances 0.000 description 8
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 7
- 229910052731 fluorine Inorganic materials 0.000 description 7
- 238000006722 reduction reaction Methods 0.000 description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 239000002245 particle Substances 0.000 description 6
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 5
- 238000002485 combustion reaction Methods 0.000 description 5
- 238000001914 filtration Methods 0.000 description 5
- 239000011737 fluorine Substances 0.000 description 5
- 239000003463 adsorbent Substances 0.000 description 4
- 239000000428 dust Substances 0.000 description 4
- 239000004744 fabric Substances 0.000 description 4
- 229910052602 gypsum Inorganic materials 0.000 description 4
- 239000010440 gypsum Substances 0.000 description 4
- 238000006213 oxygenation reaction Methods 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 230000009467 reduction Effects 0.000 description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 4
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 3
- 239000011575 calcium Substances 0.000 description 3
- 229910052791 calcium Inorganic materials 0.000 description 3
- 239000003344 environmental pollutant Substances 0.000 description 3
- 229910052736 halogen Inorganic materials 0.000 description 3
- 150000002367 halogens Chemical class 0.000 description 3
- 229910000474 mercury oxide Inorganic materials 0.000 description 3
- UKWHYYKOEPRTIC-UHFFFAOYSA-N mercury(ii) oxide Chemical compound [Hg]=O UKWHYYKOEPRTIC-UHFFFAOYSA-N 0.000 description 3
- 231100000719 pollutant Toxicity 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 238000011069 regeneration method Methods 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 2
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 235000011941 Tilia x europaea Nutrition 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 239000012065 filter cake Substances 0.000 description 2
- 229910001385 heavy metal Inorganic materials 0.000 description 2
- 239000004571 lime Substances 0.000 description 2
- LWJROJCJINYWOX-UHFFFAOYSA-L mercury dichloride Chemical compound Cl[Hg]Cl LWJROJCJINYWOX-UHFFFAOYSA-L 0.000 description 2
- 238000005065 mining Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 238000010248 power generation Methods 0.000 description 2
- 230000008929 regeneration Effects 0.000 description 2
- 239000002893 slag Substances 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 229910052785 arsenic Inorganic materials 0.000 description 1
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000004568 cement Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000003486 chemical etching Methods 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 235000019504 cigarettes Nutrition 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 238000004939 coking Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 230000023556 desulfurization Effects 0.000 description 1
- 230000003009 desulfurizing effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- FMSYTQMJOCCCQS-UHFFFAOYSA-L difluoromercury Chemical compound F[Hg]F FMSYTQMJOCCCQS-UHFFFAOYSA-L 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 239000003500 flue dust Substances 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910000069 nitrogen hydride Inorganic materials 0.000 description 1
- 238000009856 non-ferrous metallurgy Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- 239000011573 trace mineral Substances 0.000 description 1
- 235000013619 trace mineral Nutrition 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
- 238000004065 wastewater treatment Methods 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
- B01D53/48—Sulfur compounds
- B01D53/50—Sulfur oxides
- B01D53/501—Sulfur oxides by treating the gases with a solution or a suspension of an alkali or earth-alkali or ammonium compound
-
- 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
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/77—Liquid phase processes
- B01D53/78—Liquid phase processes with gas-liquid contact
-
- 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
- B01D53/86—Catalytic processes
- B01D53/8621—Removing nitrogen compounds
- B01D53/8625—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
- B01D53/96—Regeneration, reactivation or recycling of reactants
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2251/00—Reactants
- B01D2251/20—Reductants
- B01D2251/206—Ammonium compounds
- B01D2251/2062—Ammonia
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2255/00—Catalysts
- B01D2255/20—Metals or compounds thereof
- B01D2255/207—Transition metals
- B01D2255/20707—Titanium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2255/00—Catalysts
- B01D2255/20—Metals or compounds thereof
- B01D2255/207—Transition metals
- B01D2255/20723—Vanadium
-
- 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
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- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- Health & Medical Sciences (AREA)
- Biomedical Technology (AREA)
- Analytical Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Life Sciences & Earth Sciences (AREA)
- Sustainable Development (AREA)
- Treating Waste Gases (AREA)
Abstract
The invention discloses a kind of devices of flue gas ammonia process collaboration denitration desulfuration demercuration minimum discharge, including denitration and mercury oxidation reactor, electric precipitator, desulfuration demercuration absorption tower and demercuration reactive tank；The electric precipitator is connected to the denitration with mercury oxidation reactor and desulfuration demercuration absorption tower respectively by pipeline, and the desulfuration demercuration absorption tower is connected to demercuration reactive tank by pipeline.The invention has the advantages that the ammonium sulfate fertilizer of no mercury pollution can be obtained, the mercury in flue gas can be effectively removed, mercury separation, enrichment are come out, recycling and non-wastewater discharge are conducive to.
Description
Technical field
The invention belongs to chemical technology field, a kind of flue gas ammonia process collaboration denitration desulfuration demercuration minimum discharge is particularly related to
Device and method.
Background technique
The energy is the basis of economic development, and China's energy resource structure determines that coal fired power generation is the main body of energy supply, coal combustion
Burn discharge SO2、NOx, the pollutant that endangers ecological environment, seriously jeopardize human health such as heavy metal Hg.Whole world mercury emission at present
Continue to increase mainly mankind's activity caused by, various man-made pollution sources every year to atmosphere discharge mercury amount be 1900~
2200t, wherein the mercury discharged every year into atmosphere using coal as the thermal power generation of fuel and burning away the refuse up to 1500t, account for the mankind to
Atmosphere discharges the 70% of mercury, and Asia discharge 860t is global highest.It is about according to statistics China's fire coal atmosphere annual emissions
200t or so, other there are also nonferrous metallurgy, iron and steel industry, cement, coking industries to discharge mercury.
For strict control coal-fired flue-gas pollutant emission, China's strict regulations discharge standard of power-plant flue gas, it is desirable that
Reach minimum discharge limit value, i.e., under conditions of benchmark oxygen content 6%, flue dust, SO2、NOxConcentration of emission is respectively no higher than 10,
35、50mg/m3.Due to the hypertoxicity of mercury, China's " fossil-fuel power plant atmospheric pollutant emission standard " promulgated in 2011
(GB13223-2011) increases the discharge standard of mercury, it is desirable that coal-burning boiler mercury and mercuric compounds emission limit is 0.03mg/
Nm3(30μg/Nm3).The first international convention " the Minamata pact about mercury " for control and the global mercury emissions of reduction of in August, 2017
Formally effective, China is one of discharge big country of mercury, and administering mercury is urgent task.
Different control intensity and control measures, different regions, difference are needed for different coal-fired, different operating conditions
The coal mercury content of coal mine is different, differs greatly, and mercury content is 0.01~1mg/kg in the coal of China overwhelming majority mining area, and statistics is put down
Mean value is about 0.22mg/kg, and also having individual local mining area mercury is up to 100mg/kg.
Mercury Emissions from Coal-Fired Boilers control technology is controlled before being divided into burning, is controlled after control and burning in burning, and preceding control of burning is
Processed by washing and moulded coal, in burning control be by burner hearth by the modes such as injection adsorbent realize mercury conversion and
Removing, only transfer mercury pollution then needs to be further processed these two kinds of methods.Mercury is discharged into flue gas after coal combustion, flue gas collection
Middle processing demercuration is more complete, and most of Mercury Emissions from Coal-Fired Boilers are combustion product gases control technology, but domestic not yet realize is answered on a large scale
With.
The control method of coal-fired flue-gas mercury is that have 3 kinds of existing forms mainly to have Elemental Mercury Hg based on the mercury in flue gas0, divalent
Mercury Hg2+With particle mercury Hgp, wherein Elemental Mercury Hg0Accounting example it is maximum, can be using at different methods for These characteristics
Manage gas mercury: 1. adsorbent demercuration technology utilizes the modified removing cigarette of the non-carbon-supported catalysts such as active carbon, calcium base, clay material
Mercury in gas, but the regeneration of adsorbent is there are problem, thus at high cost, adsorbent, which is abandoned, causes secondary pollution；2. using inhaling
Receiving method first has to solve simple substance Hg0Insoluble problem, utilize the existing denitration desulfurizer of coal burning plant, developmental research Hg0Oxygen
Turn to bivalent mercury Hg2+Technology, then can pass through subsequent wet desulphurization system remove bivalent mercury Hg2+, this is in device setting, skill
Art is economically more reasonable.
Simple substance Hg0Method for oxidation it is very much, pass through existing denitrification apparatus, under certain control condition, denitrating catalyst
Simple substance Hg can be improved0Oxidisability so that original denitrating flue gas desulfuration demercuration Collaborative Control become Technological Economy it is feasible
Technology.Using this technique in addition to solving simple substance Hg0Problem of oxidation, the Hg after being absorbed0It is transferred to solution or product, it is such as right
It is transferred in gypsum in lime stone-gypsum Hg, either calcium method or ammonia process has flue gas and enter Hg after absorbing liquid2+Quilt
SO3 2-、HSO3 2-It is reduced to simple substance Hg0To reduce Hg0Removal efficiency, the problems such as further relating to wastewater treatment.
Summary of the invention
The technical problem to be solved in the present invention is to provide a kind of dresses of flue gas ammonia process collaboration denitration desulfuration demercuration minimum discharge
It sets.
In order to solve the above-mentioned technical problem, the technical solution of the present invention is as follows:
A kind of device of flue gas ammonia process collaboration denitration desulfuration demercuration minimum discharge, including denitration and mercury oxidation reactor, electricity
Deduster, desulfuration demercuration absorption tower and demercuration reactive tank；
The electric precipitator is connected to the denitration with mercury oxidation reactor and desulfuration demercuration absorption tower respectively by pipeline,
The desulfuration demercuration absorption tower is connected to demercuration reactive tank by pipeline.
Preferably, according to be disposed in denitration described in flow of flue gas direction and mercury oxidation reactor I section of reactor,
II section and III section of reactor of reactor；According to being disposed with flue gas demercuration in desulfuration demercuration absorption tower described in flow of flue gas direction
Section, SO2Absorber portion and super demister；The flue gas demercuration section is pumped by first circulation and is set in the flue gas demercuration section
Spray thrower pipeline connection.
Preferably, further including absorbing liquid circulating slot；The sub-salt is divided by apertured partition in the absorbing liquid circulating slot
Oxidation trough and SO2Absorbing liquid circulating slot；
The The sub-salt oxidation trough is connected to the flue gas demercuration segment pipe；The SO2Absorbing liquid circulating slot is followed by second
Ring pumps and is set to the SO2Spray thrower connection in absorber portion；The SO2Absorbing liquid circulating slot passes through pipeline and the SO2It inhales
Receive the reservoir of section and external supply ammonium hydroxide.
Preferably, further including boiler system；The boiler system is connected to for I section by pipeline with the reactor.
Preferably, further including filter aid adding trough and filter；The filter aid adding trough and the demercuration reactive tank
Pipeline connection, is connected to by filtrate delivery pump with the filter pipes.
The present invention also provides a kind of method for carrying out the minimum discharge of denitration desulfuration demercuration to flue gas using described device, packets
Include following steps:
Flue gas to be processed successively passes through denitration and mercury oxidation reactor, electric precipitator and desulfuration demercuration absorption tower, then arranges
It puts.
Pollution components are in addition to there is SO in coal combustion flue gas2Outside NOx, there are also Trace Element Fluorine, chlorine, mercury, arsenic, lead, cadmium, chromium
Deng wherein the volatile elements such as fluorine, chlorine, mercury are mainly present in boiler emission flue gas with gaseous state, according to the reality of coal-fired flue-gas
Border situation makes full use of each association component interreaction feature to achieve the effect that comprehensive treatment.Fluorine-containing 0.005 in most coals~
0.1% (50~1000mg/kg), coal (500mg/kg) containing chlorine≤0.05%, a small number of chlorine content in coal are 0.05~0.15%
(500~1500mg/kg) containing chlorine up to 0.47% (4700mg/kg), F, Cl is all active halogen family member in individual high ash fine coal
Element, fluorine, chlorine are mainly with HF, HCl, Cl in the state of high-temp combustion2Etc. forms exist, halogen has to pass mercury in flue gas
Important oxidability, the reaction temperature of catalysis oxidation are most of between 150~300 DEG C.This patent is average according to mercury in coal
Value is 0.22mg/kg, and fluorine-containing, chlorine average content is 0.015% (150mg/kg), then (F—+Cl—): Hg=1364:1, by F—
+Cl—Average content is 0.025% (250mg/kg) in coal, then (F—+Cl—): Hg=2272:1.
Denitration mercury oxide device is respectively I section of reactor, II section of reactor and reaction by 2+1 subsection setup in this invention
III section of device, the catalyst of denitration mercury oxide is conventional V2O5/TiO2Catalyst, main function are avoided because of catalyst part
Obstruction is so that gas is unevenly distributed, and improves the oxidability of mercury.
Flue gas enters I section and II section of reactor of the reactor, this two sections are pressed normal denitrating technique conditional operation, is reacting
NH is added in the entrance that I section of device3NOx catalysis is reduced to N2, the reduction reaction temperature of denitration is in 450 → 300 DEG C, this two sections
Since flue-gas temperature is low to nonvalent mercury oxygenation efficiency higher than 300 DEG C, and wherein contain reducing agent NH3To oxidation Hg0There is inhibition to make
With the main reduction reaction in I section and II section of reactor of reactor: 4NH3+4NO+O2→4N2+6H2O, 4NH3+2NO2+O2→
3N2+6H2O。
Increase residence time 0.5s with upper two sections of clearance spaces at III section of the reactor, reaction temperature is 250 → 200
DEG C, the O using the catalytic action of SCR denitration, in flue gas2, F, Cl be Hg0It is oxidized to HgCl2、HgF2, oxygenation efficiency >
90%.It enhances the ability of mercury oxidation with the increase of halogen content, I section of reactor and II section of denitration of reactor
Substantially NH is run out of in journey3, the NH in III section of reactor3Inhibiting effect it is smaller, increase the residence time, reduction reaction temperature
Be conducive to improve the oxygenation efficiency of nonvalent mercury, the oxidation reaction of nonvalent mercury in III section of reactor: Hg with lesser inhibiting effect0+e2 +→Hg2+。
Flue gas after denitration, mercury oxide enters electric precipitator and removes chalk dust removing, in dust suction-operated taken away=about 5%~
10% HgT, HgT=Hg0+Hg2++Hgp, total mercury=nonvalent mercury+bivalent mercury+particle mercury.
It preferably, flue gas enters the ammonium sulfate spray section on the desulfuration demercuration absorption tower, while being also to absorb two
Valence Hg2+Demercuration section, using from oxidation trough ammonium sulfate spray flue gas, flue-gas temperature by 150 DEG C~200 DEG C reduce
To 45 DEG C~50 DEG C, temperature reduction is conducive to absorb Hg2+, the Hg in flue gas is absorbed with ammonium sulfate2+It will not then be reduced to
Hg0, the density of the ammonium sulfate is 1.12~1.14g/mL, and the sprinkle density of solution is 10~18m3/(m2H), after demercuration
Flue gas by flow partition enter SO2Absorber portion absorbs SO using The sub-salt2, by spray washing section and SO2Absorber portion takes off respectively
Except the divalent Hg in flue gas2+And SO2, achieve the effect that desulfuration demercuration.
Absorb SO2The sub-salt absorbing liquid afterwards enters external absorbing liquid circulating slot, absorbing liquid circulating slot and Asia by pipeline
Salt oxidation trough is combination settings, setting up-flow partition between two parts, and lower part is absorbing liquid circulating slot, top is The sub-salt oxidation
Slot；Make NH in absorbing liquid circulating slot supplement ammonium hydroxide4HSO3It is converted into (NH4)2SO3Regeneration of absorption solution, the The sub-salt after regeneration absorb
Liquid is divided into two-way, squeezes into combined type desulfuration demercuration tower absorber portion as spray liquid through pump all the way and absorbs SO2, another way The sub-salt solution
Enter oxidation trough by flowing up partition, is passed through air for The sub-salt and is oxidized to ammonium sulfate, the oxygenation efficiency of The sub-salt is greater than 99.5%, The sub-salt
The ammonium sulfate of oxidation trough overflow overflows to the demercuration section on combined type desulfuration demercuration absorption tower as de- Hg2+The benefit of absorbing liquid
It fills.
Preferably, spraying the resulting demercuration solution of flue gas through the ammonium sulfate, it is placed in the demercuration reactive tank,
Potassium sulfide is added into the demercuration reactive tank, generates insoluble HgS sediment；Into the solution containing the HgS sediment
Filter aid is added, filtering obtains filtrate and the enriched substance containing HgS respectively；The enriched substance containing HgS is received by mercury enriched substance
Acquisition means are collected.
Ammonium sulfate after the resulting demercuration of ammonium sulfate spray section, has dissolved HgCl2、HgF2Sulphur
Acid ammonium solution flows into external ammonium sulfate demercuration Hg2+In reactor, potassium sulfide is added in Xiang Suoshu demercuration reactive tank, adds
Ratio Hg2+: K2S=1:1.2~1.8 (molar ratio) generate insoluble HgS sediment；Add into the solution containing HgS sediment
Add filter aid diatomite, then enter filter device, isolates ammonium sulfate (containing micro KCl, KF, NH4Cl、NH4) and HgS F
Filter residue solids enrichment object.Hg solution S suspended solid is micron order, submicron particles, there was only several grams in every cubic metre of solution
HgS, since quantity is few, can send recycling mercury metal outside after more batches of enrichments.
HgS wears filter since partial size is too small in the ammonium sulfate, therefore needs to add super-cell and form filter cake,
The HgS solids in ammonium sulfate is separated by the absorption of filter cake and interception function, filter aid is extremely fine for filtering
Particle solution wears the additive that filter uses, main function:
(1) by atomic thin granular absorption in the surface and micropore of filter aid；
(2) filter medium filter cloth has certain aperture, and subparticle is easy to wear filter, and filter aid can form frame on filter cloth
Bridge effect, it is thus possible to the little particle of micronic dust, sub-micron be stopped to pass through filter cloth；
(3) present apparatus utilizes super-cell, chemical composition SiO2, heatproof is resistant to chemical etching, when mercurous filter residue
SiO when recycling mercury2It is the stable quality for not influencing mercury；
(4) when starting filtering, every cubic metre of solution adds 1~2kg super-cell particle, when on filter medium filter cloth
Cake layer is formed, no longer filter aid can be added and continuously filter, until filtration resistance reaches predetermined value, after slag dumping (when slag dumping
Between it is short) again another batch start solution in add filter aid.
By adopting the above technical scheme, flue gas by denitration, mercury oxidation, electric precipitator, combined type desulfuration demercuration absorption tower and
Super demister, the final mass concentration for discharging mercury in flue gas are much smaller than national emission standard limit value 0.03mg/m3(30μg/m3)。
The present invention realizes NOx, SO2, Hg collaboration administer, obtained chemical fertilizer products ammonium sulfate (containing minimal amount of KCl and KF), kept away
Exempt from mercuric reduction, improved the removal efficiency of total mercury in flue gas, while making the oxidation efficiency of mercury, removal efficiency
It is more stable, the mercury in ammonium sulfate is removed by enrichment, is conducive to recycling and is used, non-wastewater discharge and processing problem.
To other flue gas ammonia method desulfurizings, flue gas enters removing of the combined type desulfuration demercuration absorption tower to total mercury, and this patent is same
Sample is applicable in.
Under certain control condition, by existing denitration, dedusting, desulfurizer, denitrating catalyst can improve simple substance Hg0
Oxidisability so that original denitrating flue gas desulfuration demercuration Collaborative Control become the feasible technology of Technological Economy, utilize this
One technique is in addition to solving simple substance Hg0Problem of oxidation, while also can solve mercuric absorption problem.Hg after being absorbed0Turn
Enter solution or product, such as lime stone-gypsum Hg be transferred in gypsum, either calcium method or ammonia process exist flue gas into
Enter Hg after absorbing liquid2+By SO3 2-、HSO3 2-It is reduced to simple substance Hg0To reduce HgTRemoval efficiency, this patent from technology original
Mercuric reduction is solved the problems, such as in reason, control reaction condition and device setting, so that the oxidation efficiency of mercury, removal efficiency are more
Stablize.
Detailed description of the invention
Fig. 1 is the structural diagram of the present invention.
In figure, 1- boiler system；2- denitration and mercury oxidation reactor；I section of 21- reactor；II section of 22- reactor；23- is anti-
Answer III section of device；3- electric precipitator；4- desulfuration demercuration absorption tower；41- flue gas demercuration section；42-SO2Absorber portion；The super demisting of 43-
Device；44- first circulation pump；5- absorbing liquid circulating slot；51- The sub-salt oxidation trough；52-SO2Absorbing liquid circulating slot；53- second circulation
Pump；6- demercuration reactive tank；7- filter aid adding trough；8- filtrate delivery pump；9- filter；10- mercury enriched substance collection device.
Specific embodiment
Specific embodiments of the present invention will be further explained with reference to the accompanying drawing.It should be noted that for
The explanation of these embodiments is used to help understand the present invention, but and does not constitute a limitation of the invention.In addition, disclosed below
The each embodiment of the present invention involved in technical characteristic can be combined with each other as long as they do not conflict with each other.
Embodiment 1
As shown in Figure 1, a kind of device of flue gas ammonia process collaboration denitration desulfuration demercuration minimum discharge, including denitration and mercury oxidation
Reactor 2, electric precipitator 3, desulfuration demercuration absorption tower 4 and demercuration reactive tank 6；Electric precipitator 3 by pipeline respectively with denitration with
Mercury oxidation reactor 2 is connected to desulfuration demercuration absorption tower 4, and desulfuration demercuration absorption tower 4 is connected to demercuration reactive tank 6 by pipeline.
Wherein, according to being disposed with I section 21 of reactor in the denitration of flow of flue gas direction and mercury oxidation reactor 2, react
II section 22 of device and III section 23 of reactor；According to being disposed with flue gas demercuration section in flow of flue gas direction desulfuration demercuration absorption tower 4
41、SO2Absorber portion 42 and super demister 43；Flue gas demercuration section 41 is by first circulation pump 44 and is set to flue gas demercuration section 41
Interior spray thrower pipeline connection.
It wherein, further include absorbing liquid circulating slot 5；The sub-salt oxidation trough is divided by apertured partition in absorbing liquid circulating slot 5
51 and SO2Absorbing liquid circulating slot 52；
The sub-salt oxidation trough 51 is connected to 41 pipeline of flue gas demercuration section；SO2Absorbing liquid circulating slot 52 passes through second circulation pump 53
Be set to the SO2Spray thrower connection in absorber portion 42；SO2Absorbing liquid circulating slot 52 passes through pipeline and SO242 He of absorber portion
The reservoir of outside supply ammonium hydroxide.
It wherein, further include boiler system 1；Boiler system 1 is connected to by pipeline with I section 21 of reactor.
It wherein, further include filter aid adding trough 7 and filter 9；Filter aid adding trough 7 is connected to 6 pipeline of demercuration reactive tank,
It is connected to by filtrate delivery pump 8 with 9 pipeline of filter.By the filter residue that filter 9 is obtained by filtration, i.e., containing the enriched substance of HgS
It is collected by mercury enriched substance collection device 10, the producer to processing heavy metal can be sent to be recycled.
Embodiment 2
A method of using device described in embodiment 1 to flue gas progress denitration desulfuration demercuration minimum discharge, including with
Lower step:
Flue gas to be processed successively passes through denitration and mercury oxidation reactor 2, electric precipitator 3 and desulfuration demercuration absorption tower 4, then
Discharge.
Wherein, enter denitration and II section 22 of I section 21 of reactor, reactor in mercury oxidation reactor 2 in flue gas and react
At III section 23 of device, it is separately added into V2O5/TiO2Denitrating catalyst is reacted；It is reacted in I section 21 of reactor and II section 22 of reactor
When reaction temperature be 380 DEG C, III section 23 of reactor reaction when reaction temperature be 220 DEG C.When reaction, at I section of reactor
NH is added in 21 entrance3。
The flue gas demercuration section 41 in desulfuration demercuration absorption tower 4 is entered in flue gas, flue gas is sprayed by ammonium sulfate, until
Flue-gas temperature is reduced to 45 DEG C~50 DEG C.
The resulting demercuration solution of flue gas is sprayed through the ammonium sulfate, is placed in demercuration reactive tank 6, to demercuration reactive tank
Potassium sulfide is added in 6, generates insoluble HgS sediment；Diatomite is added into the solution containing HgS sediment, is filtered, respectively
Obtain filtrate and the enriched substance containing HgS；Enriched substance containing HgS is collected by mercury enriched substance collection device 10.
Embodiment 3
A method of using device described in embodiment 1 to flue gas progress denitration desulfuration demercuration minimum discharge, including with
Lower step:
Flue gas to be processed successively passes through denitration and mercury oxidation reactor 2, electric precipitator 3 and desulfuration demercuration absorption tower 4, then
Discharge.
Wherein, enter denitration and II section 22 of I section 21 of reactor, reactor in mercury oxidation reactor 2 in flue gas and react
At III section 23 of device, it is separately added into V2O5/TiO2Denitrating catalyst is reacted；It is reacted in I section 21 of reactor and II section 22 of reactor
When reaction temperature be 450 DEG C, III section 23 of reactor reaction when reaction temperature be 250 DEG C.When reaction, at I section of reactor
NH is added in 21 entrance3。
The flue gas demercuration section 41 in desulfuration demercuration absorption tower 4 is entered in flue gas, flue gas is sprayed by ammonium sulfate, until
Flue-gas temperature is reduced to 45 DEG C~50 DEG C.
The resulting demercuration solution of flue gas is sprayed through the ammonium sulfate, is placed in demercuration reactive tank 6, to demercuration reactive tank
Potassium sulfide is added in 6, generates insoluble HgS sediment；Diatomite is added into the solution containing HgS sediment, is filtered, respectively
Obtain filtrate and the enriched substance containing HgS；Enriched substance containing HgS is collected by mercury enriched substance collection device 10.
Embodiment 4
A method of using device described in embodiment 1 to flue gas progress denitration desulfuration demercuration minimum discharge, including with
Lower step:
Flue gas to be processed successively passes through denitration and mercury oxidation reactor 2, electric precipitator 3 and desulfuration demercuration absorption tower 4, then
Discharge.
Wherein, enter denitration and II section 22 of I section 21 of reactor, reactor in mercury oxidation reactor 2 in flue gas and react
At III section 23 of device, it is separately added into V2O5/TiO2Denitrating catalyst is reacted；It is reacted in I section 21 of reactor and II section 22 of reactor
When reaction temperature be 300 DEG C, III section 23 of reactor reaction when reaction temperature be 200 DEG C.When reaction, at I section of reactor
NH is added in 21 entrance3。
The flue gas demercuration section 41 in desulfuration demercuration absorption tower 4 is entered in flue gas, flue gas is sprayed by ammonium sulfate, until
Flue-gas temperature is reduced to 45 DEG C~50 DEG C.
The resulting demercuration solution of flue gas is sprayed through the ammonium sulfate, is placed in demercuration reactive tank 6, to demercuration reactive tank
Potassium sulfide is added in 6, generates insoluble HgS sediment；Diatomite is added into the solution containing HgS sediment, is filtered, respectively
Obtain filtrate and the enriched substance containing HgS；Enriched substance containing HgS is collected by mercury enriched substance collection device 10.
The flue gas handled through above-described embodiment 2-4 can obtain the ammonium sulfate fertilizer of no mercury pollution, can effectively remove in flue gas
Mercury, by mercury separation, enrichment come out, be conducive to recycling and non-wastewater discharge.
Commonly using coal-fired calorific value is 15000KJ/kg~20000KJ/kg, and mercury content also has big difference, and mercury content is more
For 0.2~0.5mg/kg, average content 0.22mg/kg, due to different calorific values, air capacity dosage, exhaust gas volumn, thus it is different
Mercury concentration in coal-fired flue-gas also has bigger difference, the dust in usual clinker and electric precipitator can actually remove mercury 20~
30%, effect of the coal-fired flue-gas after patent device demercuration is as follows:
1, when the coal using calorific value 15000KJ/kg, mercury content 0.5mg/kg, flue gas enters wet desulphurization mercury removal device
Mercury concentration is 56~64 μ g/Nm3, by efficiency >=90% of wet process demercuration, then discharging the mercury content in flue gas is 5.6~6.4 μ
g/Nm3。
The coal of same calorific value, when mercury content is calculated by 0.22mg/kg, mercury that flue gas discharges after wet desulphurization demercuration
Concentration is 2.82~2.42 μ g/Nm3。
2, when the coal that calorific value is 20000KJ/kg, mercurous 0.5mg/kg, by oxidation deduster above-mentioned, into wet process
The gas mercury concentration of desulfuration demercuration is 41.86~59.8 μ g/Nm3, after smoke-gas wet desulfurization demercuration, discharge mercury in flue gas is dense
Degree is 4.18~5.98 μ g/Nm3。
The coal of same calorific value, when mercury content is calculated by 0.22mg/kg, the gas mercury concentration into wet desulphurization demercuration is
18.42~26.31 μ g/Nm3, the mercury concentration that flue gas discharges after wet desulphurization demercuration is 1.84~2.63 μ g/Nm3。
It is above-mentioned statistics indicate that, using this item patented technology, the fire coal different for calorific value, when mercury content be 0.2~
0.5mg/kg, the discharge mercury in flue gas content after wet desulphurization demercuration is less than 7 μ g/Nm3.When mercury content presses 0.22mg/kg in coal
When calculating, the discharge mercury in flue gas content after wet desulphurization demercuration is less than 3 μ g/Nm3.It is below " thermal power plant's atmosphere pollution row
Put standard " the discharge standard 0.03mg/Nm of (GB13223-2011) mercury3(30μg/Nm3)。
In conjunction with attached drawing, the embodiments of the present invention are described in detail above, but the present invention is not limited to described implementations
Mode.For a person skilled in the art, in the case where not departing from the principle of the invention and spirit, to these embodiments
A variety of change, modification, replacement and modification are carried out, are still fallen in protection scope of the present invention.
Claims (10)
1. a kind of device of flue gas ammonia process collaboration denitration desulfuration demercuration minimum discharge, which is characterized in that including denitration and mercury oxidation
Reactor (2), electric precipitator (3), desulfuration demercuration absorption tower (4) and demercuration reactive tank (6)；
The electric precipitator (3) by pipeline respectively with the denitration and mercury oxidation reactor (2) and desulfuration demercuration absorption tower (4)
Connection, the desulfuration demercuration absorption tower (4) are connected to demercuration reactive tank (6) by pipeline.
2. the device of flue gas ammonia process collaboration denitration desulfuration demercuration minimum discharge according to claim 1, which is characterized in that press
I section of reactor (21), II section of reactor is disposed with according to denitration described in flow of flue gas direction and mercury oxidation reactor (2) are interior
(22) and III section of reactor (23)；It is de- according to flue gas is disposed in desulfuration demercuration absorption tower (4) described in flow of flue gas direction
Mercury section (41), SO2Absorber portion (42) and super demister (43)；The flue gas demercuration section (41) by first circulation pump (44) with
The spray thrower pipeline connection being set in the flue gas demercuration section (41).
3. the device of flue gas ammonia process collaboration denitration desulfuration demercuration minimum discharge according to claim 2, which is characterized in that also
Including absorbing liquid circulating slot (5)；In the absorbing liquid circulating slot (5) by apertured partition be divided into The sub-salt oxidation trough (51) and
SO2Absorbing liquid circulating slot (52)；
The The sub-salt oxidation trough (51) is connected to flue gas demercuration section (41) pipeline；The SO2Absorbing liquid circulating slot (52) passes through
Second circulation pumps (53) and is set to the SO2Spray thrower connection in absorber portion (42)；The SO2Absorbing liquid circulating slot (52)
Pass through pipeline and the SO2The reservoir of absorber portion (42) and external supply ammonium hydroxide.
4. the device of flue gas ammonia process collaboration denitration desulfuration demercuration minimum discharge according to claim 2, which is characterized in that also
Including boiler system (1)；The boiler system (1) is connected to by pipeline with I section of the reactor (21).
5. the device of flue gas ammonia process collaboration denitration desulfuration demercuration minimum discharge according to claim 1, which is characterized in that also
Including filter aid adding trough (7) and filter (9)；The filter aid adding trough (7) and demercuration reactive tank (6) pipeline connect
It is logical, it is connected to by filtrate delivery pump (8) with the filter (9) pipeline.
6. a kind of method that the minimum discharge of denitration desulfuration demercuration is carried out to flue gas using any one of claim 1-5 described device,
It is characterized by comprising following steps: flue gas to be processed successively pass through denitration and mercury oxidation reactor (2), electric precipitator (3) and
Desulfuration demercuration absorption tower (4), is then discharged.
7. according to the method described in claim 6, it is characterized by: entering the denitration and mercury oxidation reactor (2) in flue gas
Interior I section of reactor (21), II section of reactor (22) and when reactor III section (23), be separately added into denitrating catalyst carry out it is anti-
It answers；Reaction temperature when the reactor I section (21) and II section of reactor (22) react is 300 DEG C~450 DEG C, described anti-
Answering reaction temperature when III section of device (23) reaction is 200 DEG C~250 DEG C.
8. according to the method described in claim 7, it is characterized by: NH is added in the entrance in I section of the reactor (21)3。
9. according to the method described in claim 6, it is characterized by: being entered in the desulfuration demercuration absorption tower (4) in flue gas
Flue gas demercuration section (41), by ammonium sulfate spray flue gas, until flue-gas temperature is reduced to 45 DEG C~50 DEG C.
10. according to the method described in claim 9, it is characterized by: spraying the resulting demercuration of flue gas through the ammonium sulfate
Solution is placed in the demercuration reactive tank (6), and potassium sulfide is added in Xiang Suoshu demercuration reactive tank (6), and it is heavy to generate insoluble HgS
Starch；Filter aid is added into the solution containing the HgS sediment, is filtered, obtains filtrate and the enriched substance containing HgS respectively；
The enriched substance containing HgS is collected by mercury enriched substance collection device (10).
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