CN106975331A - A kind of smoke catalytic absorbing synergic mercury removal device and its method - Google Patents
A kind of smoke catalytic absorbing synergic mercury removal device and its method Download PDFInfo
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- CN106975331A CN106975331A CN201710287011.6A CN201710287011A CN106975331A CN 106975331 A CN106975331 A CN 106975331A CN 201710287011 A CN201710287011 A CN 201710287011A CN 106975331 A CN106975331 A CN 106975331A
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- demercuration
- flue gas
- mercury
- catalyst
- adsorbent
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- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 title claims abstract description 63
- 229910052753 mercury Inorganic materials 0.000 title claims abstract description 63
- 238000000034 method Methods 0.000 title claims abstract description 41
- 230000003197 catalytic effect Effects 0.000 title claims description 33
- 239000000779 smoke Substances 0.000 title claims description 29
- 230000002195 synergetic effect Effects 0.000 title claims description 27
- 239000003054 catalyst Substances 0.000 claims abstract description 75
- 239000003546 flue gas Substances 0.000 claims abstract description 71
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims abstract description 70
- 238000010521 absorption reaction Methods 0.000 claims abstract description 40
- 239000000428 dust Substances 0.000 claims abstract description 31
- 239000003463 adsorbent Substances 0.000 claims abstract description 24
- 238000011144 upstream manufacturing Methods 0.000 claims abstract description 22
- 238000005507 spraying Methods 0.000 claims abstract description 19
- 238000002347 injection Methods 0.000 claims abstract description 17
- 239000007924 injection Substances 0.000 claims abstract description 17
- 239000002594 sorbent Substances 0.000 claims abstract description 17
- 230000003647 oxidation Effects 0.000 claims description 18
- 238000007254 oxidation reaction Methods 0.000 claims description 18
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 17
- 230000001590 oxidative effect Effects 0.000 claims description 14
- 239000007800 oxidant agent Substances 0.000 claims description 12
- 239000003795 chemical substances by application Substances 0.000 claims description 7
- 229910052748 manganese Inorganic materials 0.000 claims description 7
- 239000007789 gas Substances 0.000 claims description 6
- 230000008676 import Effects 0.000 claims description 6
- 238000002485 combustion reaction Methods 0.000 claims description 5
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 5
- 239000003513 alkali Substances 0.000 claims description 4
- 238000006555 catalytic reaction Methods 0.000 claims description 4
- 235000019504 cigarettes Nutrition 0.000 claims description 4
- 239000007921 spray Substances 0.000 claims description 4
- 239000012717 electrostatic precipitator Substances 0.000 claims description 3
- 239000004744 fabric Substances 0.000 claims description 3
- 239000007788 liquid Substances 0.000 claims description 3
- 229910018669 Mn—Co Inorganic materials 0.000 claims description 2
- 239000000446 fuel Substances 0.000 claims description 2
- 239000003517 fume Substances 0.000 claims description 2
- 239000013618 particulate matter Substances 0.000 abstract description 2
- 238000006243 chemical reaction Methods 0.000 description 15
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 9
- 229910052593 corundum Inorganic materials 0.000 description 9
- 238000005516 engineering process Methods 0.000 description 9
- 229910001845 yogo sapphire Inorganic materials 0.000 description 9
- 229910016978 MnOx Inorganic materials 0.000 description 6
- 239000002585 base Substances 0.000 description 6
- 238000001179 sorption measurement Methods 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 4
- 239000000460 chlorine Substances 0.000 description 4
- 229910052801 chlorine Inorganic materials 0.000 description 4
- 238000011049 filling Methods 0.000 description 4
- 238000001802 infusion Methods 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 238000003980 solgel method Methods 0.000 description 4
- 241001062472 Stokellia anisodon Species 0.000 description 3
- 239000004568 cement Substances 0.000 description 3
- 230000003750 conditioning effect Effects 0.000 description 3
- 239000003344 environmental pollutant Substances 0.000 description 3
- 238000005504 petroleum refining Methods 0.000 description 3
- 231100000719 pollutant Toxicity 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 229910002451 CoOx Inorganic materials 0.000 description 2
- 239000003610 charcoal Substances 0.000 description 2
- 239000003245 coal Substances 0.000 description 2
- 230000002860 competitive effect Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
- 230000002745 absorbent Effects 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000031709 bromination Effects 0.000 description 1
- 238000005893 bromination reaction Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- 229910000474 mercury oxide Inorganic materials 0.000 description 1
- UKWHYYKOEPRTIC-UHFFFAOYSA-N mercury(ii) oxide Chemical compound [Hg]=O UKWHYYKOEPRTIC-UHFFFAOYSA-N 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 238000005272 metallurgy Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 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
- B01D53/74—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
- B01D53/86—Catalytic processes
- B01D53/8621—Removing nitrogen compounds
- B01D53/8625—Nitrogen oxides
- B01D53/8631—Processes characterised by a specific device
-
- 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
- B01D53/8665—Removing 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
- B01D53/86—Catalytic processes
- B01D53/90—Injecting reactants
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F23—COMBUSTION APPARATUS; COMBUSTION PROCESSES
- F23J—REMOVAL OR TREATMENT OF COMBUSTION PRODUCTS OR COMBUSTION RESIDUES; FLUES
- F23J15/00—Arrangements of devices for treating smoke or fumes
- F23J15/006—Layout of treatment plant
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F23—COMBUSTION APPARATUS; COMBUSTION PROCESSES
- F23J—REMOVAL OR TREATMENT OF COMBUSTION PRODUCTS OR COMBUSTION RESIDUES; FLUES
- F23J15/00—Arrangements of devices for treating smoke or fumes
- F23J15/02—Arrangements of devices for treating smoke or fumes of purifiers, e.g. for removing noxious material
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2253/00—Adsorbents used in seperation treatment of gases and vapours
- B01D2253/10—Inorganic adsorbents
- B01D2253/102—Carbon
-
- 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
- B01D2255/2073—Manganese
-
- 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
- B01D2255/20746—Cobalt
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2255/00—Catalysts
- B01D2255/20—Metals or compounds thereof
- B01D2255/209—Other metals
- B01D2255/2092—Aluminium
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F23—COMBUSTION APPARATUS; COMBUSTION PROCESSES
- F23J—REMOVAL OR TREATMENT OF COMBUSTION PRODUCTS OR COMBUSTION RESIDUES; FLUES
- F23J2219/00—Treatment devices
- F23J2219/30—Sorption devices using carbon, e.g. coke
Landscapes
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Chemical & Material Sciences (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)
- Mechanical Engineering (AREA)
- General Engineering & Computer Science (AREA)
- Treating Waste Gases (AREA)
Abstract
The present invention provides a kind of flue gas hydrargyrum-removing method and device, and this method carries out high-efficiency mercury removal using demercuration catalyst and in duct sorbent injection adsorbent coordination technique.Wherein demercuration catalyst layer be arranged in denitration ammonia-spraying grid upstream or (and) catalyst for denitrating flue gas layer downstream, adsorbent is in dust arrester upstream in duct sorbent injection.Hg in flue gas0Hg is largely changed into the presence of demercuration catalyst2+, while fully being mixed with being injected into the adsorbent of flue gas, reacting absorption, adsorbed mercury is removed in the lump in cleaner with particulate matter afterwards, and mercury not to be adsorbed is further absorbed in absorption plant, so that the mercury effectively in control discharge flue gas.The flue gas hydrargyrum-removing method technique that the present invention is provided is simple, and easy to operate, demercuration rate can reach 94%.
Description
Art
The present invention relates to a kind of smoke catalytic absorbing synergic mercury removal device and its method, belong to power plant, metal smelt, water
The fields such as mud, chemical industry, petroleum refining.
Background technology
The burning of the energy can produce many atmosphere pollutions such as SOx, NOx, dust, mercury, wherein mercury conduct during utilizing
Environmental and human health impacts are produced significant damage by heavy metal contaminants.Coal-burning power plant, coal-burned industrial boiler, non-ferrous metal metallurgy,
Cement industry is, in the main mercury emissions source of China, to account for more than the 80% of whole industry mercury emissions.
Because the chlorine content in coal of China is low, the mercury overwhelming majority is all with gaseous elementary mercury (Hg in coal combustion process0) shape
Formula enters in flue gas；With the cooling of flue gas, part Hg0With the interaction of other combustion products, a part changes into gaseous oxygen
Change mercury (Hg2+) and particle mercury (HgP).At present, China does not have single Mercury vacancy device also on gas mercury control aspect, greatly
Part carries out pollutant Collaborative Control using existing denitration, dedusting, desulphurization plant, but its overall demercuration efficiency is relatively low.
In recent years, numerous studies had been carried out on gas mercury control aspect both at home and abroad, its main technology can be divided into two kinds,
A kind of is the oxidative absorption technology of mercury, and the technology is by adding all kinds of catalyst or oxidant in flue gas, strengthening Hg0In cigarette
To Hg in gas2+Conversion, recycle absorption plant mercury is removed from flue gas, wherein the mercury oxidation catalyst studied mainly is concentrated
In SCR catalyst, carbon base catalyst and metal/metal oxide catalyst.Such as Chinese patent CN102527205A (2012)
A kind of flue gas hydrargyrum-removing method based on low-temperature catalytic oxidation is disclosed, catalyst selects Pt-Mn/TiO2-ZrO2, 100~200
In the range of DEG C demercuration is carried out using the method for catalyst mercury oxidation combination alkali liquor absorption；On the other hand it is the adsorption technology of mercury, it is main
If adsorbing the Hg in flue gas using adsorbent2+And HgP, recycle cleaner that mercury is removed from flue gas, such as China is special
Sharp CN103223290A (2013) discloses flue gas conditioning agent and its purification method of a kind of fume mercury-removing, and modulator selects bromination
Ammonium, implements to activate using flue gas own temperature to flue gas conditioning agent, and oxidation, the absorption of the flue gas conditioning agent of activation to mercury are entered simultaneously
OK, the existing flue gas purifying equipment of reutilization system realizes flue gas demercuration.
However, on conventional SCR catalyst surface, NH3There is competitive Adsorption, NH in activated centre position with Hg3Absorption it is past
Toward being dominant, the absorption to Hg plays inhibitory action, and relies on very big, flue gas to chlorinity in flue gas during these catalyst mercury oxide
Middle without chlorine or during few chlorine, these catalyst mercury oxidation abilities are substantially reduced, and Hg in gas mercury0Compared to Hg2+Also it is more difficult to be converted into
Hgp, these all limit follow-up dust arrester and wet absorption device cooperates with the ability of demercuration.
It is mainly the monotechnicses such as oxidative absorption or absorption in the demercuration technology of business application at present, if be effectively combined
Both technologies, are not only further excavating the cooperation-removal potentiality of mercury, and more effectively control technology cost.
The content of the invention
It is an object of the invention to provide a kind of smoke catalytic absorbing synergic mercury removal device, including the boiler being sequentially connected, take off
Nitre reactor, air preheater, dust arrester, absorption plant and chimney, it is characterised in that also including sorbent injection device,
Demercuration catalyst layer, denitration catalyst oxidant layer, ammonia-spraying grid；The exhaust opening connection of the Benitration reactor import and boiler, air
Preheater flue gas side-entrance is connected with Benitration reactor outlet, and air preheater flue gas side outlet is connected with dust arrester import,
Sorbent injection device is located between air preheater downstream and dust arrester upstream flue；The demercuration catalyst layer, denitration
Catalyst layer is arranged in the Benitration reactor of air preheater upstream with ammonia-spraying grid, and described demercuration catalyst layer is located at de-
Nitre ammonia-spraying grid upstream or/and catalyst for denitrating flue gas layer downstream.
Further, the dust arrester is electrostatic precipitator, sack cleaner or electrostatic fabric filter.
Further, the absorption plant uses wet absorption device or other absorption plants, and its absorbing liquid is using conventional
Alkali lye.
Further, the absorption plant uses packed tower, bubble tower, plate tower or rotating stream tray scrubber.
A kind of smoke catalytic absorbing synergic demercuration method, is entered using demercuration catalyst and in duct sorbent injection adsorbent coordination technique
Row demercuration；
(1) air enters boiler auxiliary combustion through air preheater and flue gas heat exchange, and the flue gas that fuel combustion is produced passes through demercuration
Catalytic oxidation occurs for mercury during catalyst layer in flue gas, Hg0 is changed into oxidation state mercury；
(2) flue gas after mercury catalysis oxidation is discharged by the flue gas side outlet of air preheater, is discharged into dust arrester,
In the upstream of dust arrester, the adsorbent that flue gas sprays with sorbent injection device is well mixed, and is then adsorbed with the absorption of mercury
Agent enters dust arrester with flue gas, and removes adsorbent in dust arrester；
(3) flue gas after handling is discharged into absorption plant, after mercury remaining in flue gas is absorbed in absorption plant, flue gas
Via chimney and discharge.
Further, described demercuration catalyst layer is arranged in ammonia-spraying grid upstream, or is arranged under denitration catalyst oxidant layer
Trip, or ammonia-spraying grid upstream and denitration catalyst oxidant layer downstream are arranged in simultaneously.
Further, demercuration catalyst included in described demercuration catalyst layer, should using Al2O3 or TiO2 as carrier
Demercuration catalyst main active component is Mn or Co oxides or Mn-Co mixed oxides.
Further, the load capacity 1.0wt% that Mn load capacity is 1.0%~10%, Co in described demercuration catalyst
~10wt%, Mn and Co mol ratio are 0.5~2.0.
Further, described demercuration catalyst layer is arranged in flue.
Further, the flue temperature scope where described demercuration catalyst layer is 300~380 DEG C.
Further, described catalytic oxidation is carried out under 5000~15000h-1 air speed；
Further, described adsorbent is activated carbon or the modified activated carbon for carrying Br.
Further, the mass ratio of the emitted dose of described adsorbent and mercury in flue gas is 1000~5000：1.
It is an object of the invention to provide a kind of smoke catalytic absorbing synergic demercuration method and device, this method is urged using demercuration
Agent, promotes Hg to Hg under demercuration catalyst effect2+Conversion, while in duct sorbent injection adsorbent, system is improved to greatest extent
System demercuration rate.The demercuration catalyst reaction temperature window of the present invention is wider, also has preferable demercuration ability under the conditions of low chlorine,
And NOx and SO in flue gas2Existence condition under also have good mercury oxidation ability.
The smoke catalytic absorbing synergic demercuration method that the present invention is provided maximizes collaboration demercuration, and utilizes ready-made
Pollutant removing equipment, thus it is simple with technique, and easy to operate, demercuration efficiency is high, low cost and other advantages.The present invention can be used for
Outside boiler smoke demercuration, the flue gas demercuration of the industries such as metal smelt, cement, chemical industry, petroleum refining can be also used for.
Brief description of the drawings
Accompanying drawing 1 is a kind of smoke catalytic absorbing synergic demercuration method schematic diagram of the present invention；
Accompanying drawing 2 is smoke catalytic absorbing synergic demercuration method signal under a kind of demercuration catalyst layer arrangement of the invention
Figure；
Accompanying drawing 3 is smoke catalytic absorbing synergic demercuration method signal under another demercuration catalyst arrangement of the invention
Figure.
Drawing reference numeral explanation：
1-boiler, 2-Benitration reactor, 3-air preheater, 4-sorbent injection device, 5-dust arrester, 6-
Absorption plant, 7-chimney, 8-demercuration catalyst layer, 9-denitration catalyst oxidant layer, 10-denitration ammonia-spraying grid.
Embodiment
The embodiment of the present invention is described in detail below in conjunction with accompanying drawing.The embodiment is used to illustrate the present invention
And it is not limited to the scope of the present invention.
The smoke catalytic absorbing synergic demercuration method of the present invention is implemented by following technology：
Demercuration catalyst layer 8 be arranged in the upstream of denitration ammonia-spraying grid 10 or (and) catalyst for denitrating flue gas layer 9 downstream, effectively
Avoid NH3To Hg competitive Adsorption, mercury catalysis potentiality are played to greatest extent, while ensureing catalyst optimum temperature window again.
A kind of smoke catalytic absorbing synergic mercury removal device as shown in Figure 1, it is pre- by boiler 1, Benitration reactor 2, air
Hot device 3, sorbent injection 4, dust arrester 5, absorption plant 6, chimney 7, demercuration catalyst layer 8, denitration catalyst oxidant layer 9, denitration
The grade of ammonia-spraying grid 10 is constituted.The import of Benitration reactor 2 is connected with the exhaust opening of boiler 1, and the flue gas side-entrance of air preheater 3 is with taking off
The outlet of nitre reactor 2 connection, the flue gas side outlet of air preheater 3 is connected with the import of dust arrester 5, the position of sorbent injection 4 position
Between the downstream of air preheater 3 and the upstream flue of dust arrester 5, dust arrester 5, absorption plant 6 and chimney 7 are successively by flue
Connection.
Demercuration catalyst layer 8 is arranged on the upstream flue of ammonia-spraying grid 10 or the downstream of denitration catalyst oxidant layer 9, and positioned at temperature window
In the range of 200~400 DEG C of mouth.Described demercuration catalyst is using leaching method method, precipitation sedimentation, hydro-thermal method or sol-gel process
Prepare.Described demercuration catalyst is with Al2O3Or TiO2For carrier, main active component is one kind or Mn- of Mn or Co oxides
Co mixed oxides.Mn load capacity is 1.0wt%~10wt%, Co load capacity 1.0wt% in described demercuration catalyst
~10wt%, Mn and Co mol ratio are 0.5~2.0.Demercuration catalyst is arranged on temperature window in 300~380 DEG C of models
Flue；The catalytic oxidation occurred in demercuration catalyst is in 5000~15000h-1Air speed under carry out；
Dust arrester 5 uses electrostatic precipitator, sack cleaner, one kind of electrostatic fabric filter,
Absorption plant 6 is wet absorption device or other absorbers, and its absorbing liquid is using conventional alkali lye, and absorption plant 6 can be with
It is packed tower, bubble tower, plate tower or rotating stream tray scrubber etc., the present invention relates to a kind of smoke catalytic absorbing synergic demercuration method, uses
Demercuration catalyst and in duct sorbent injection adsorbent coordination technique carry out demercuration；
(1) by the mercury in flue gas during demercuration catalyst layer 8 catalytic oxidation occurs for flue gas, makes Hg0Change into oxidation
State mercury；
(2) flue gas after mercury catalysis oxidation is discharged by the flue gas side outlet of air preheater 3, is discharged into dust arrester
5, in the upstream of dust arrester 5, the adsorbent that flue gas sprays with sorbent injection device 4 is well mixed, so that mercury in flue gas
Fully mixed with being injected into the adsorbent of flue gas, react absorption, the mercury being adsorbed by adsorbent is in dust arrester 5 with particulate matter one
And remove, mercury not to be adsorbed is further absorbed in absorption plant 6, so that the mercury in efficient removal flue gas.Adsorbent is
The mass ratio of activated carbon or the modified activated carbon for carrying Br, sorbent injection amount and mercury in flue gas is 1000~5000：1.
(3) flue gas after handling is discharged into absorption plant 6, after mercury remaining in flue gas is absorbed in absorption plant 6, cigarette
Gas is via chimney 7 and discharges.
As illustrated in the accompanying drawings from 1 to 3, the present invention implements cigarette on the basis of the flue gas purification systems such as dust arrester 5, absorption plant 6
Qi exhaustion mercury, the effect of dust arrester 5 is by the absorbent powder trapping of Adsorption of Mercury；The effect of absorption plant 6 is absorbed in flue gas
Remaining solvable Hg2+。
Base case
Pending flue gas SO2Concentration 800ppm, NO concentration 300ppm, Hg0The μ g/m of concentration 25~303, HC1 concentration 30ppm,
340 DEG C of reaction temperature, is not provided with demercuration catalyst, does not spray adsorbent.Under this base condition, flue gas passes through denitration reaction
System demercuration efficiency after device, dust arrester, absorption plant is no more than 45%.
Embodiment 1MnOx/Al2O3It is catalyzed demercuration
As shown in Figure 2, it is combined in the upstream flue filling infusion process of ammonia-spraying grid 10 with sol-gel process obtained
MnOx/Al2O3Demercuration catalyst, wherein MnOx load capacity are 10wt%, demercuration catalyst reaction velocity 15000h-1, HC1 concentration
20ppm, 300 DEG C of reaction temperature, remaining condition is identical with base case, and as a result system demercuration rate reaches 90%；Secondly such as accompanying drawing 3
It is shown, MnOx/Al2O3Demercuration catalyst is loaded into the downstream of denitration catalyst oxidant layer 9, and wherein MnOx load capacity is 1wt%, demercuration
Catalyst reaction air speed 5000h-1, HC1 concentration 20ppm, 380 DEG C of reaction temperature, remaining condition is same as Example 1, is as a result
System demercuration rate reaches 85%.
Embodiment 2CoOx/TiO2It is catalyzed demercuration
As shown in Figure 2, CoOx/TiO made from the upstream flue filling infusion process of ammonia-spraying grid 102Demercuration catalyst, its
Middle CoOx load capacity is 5wt%, reaction velocity 10000h-1, HC1 concentration 20ppm, 320 DEG C of reaction temperature, remaining condition and benchmark
Situation is identical, and as a result system demercuration rate reaches 87%.
Embodiment 3MnOx/Al2O3Catalytic adsorption cooperates with demercuration
As shown in Figure 2, the upstream flue filling infusion process of ammonia-spraying grid 10 is combined obtained with sol-gel process
MnOx/Al2O3Demercuration catalyst, wherein MnOx load capacity are 5wt%, reaction velocity 10000h-1, HC1 concentration 20ppm, reaction
320 DEG C of temperature, adsorbent is respectively adopted activated carbon and carries Br modified activated carbons, and property charcoal emitted dose is with activated carbon：Total mercury in flue gas
Weight compares 5000:1 determines, modified activated carbon emitted dose is with modified activated carbon：Total mercury weight compares 1000 in flue gas:1 determines,
Remaining condition is identical with base case.As a result system demercuration rate respectively reaches 91.5%, 92%.
Embodiment 4Mn-Co-Ox/Al2O3Catalytic adsorption cooperates with demercuration
As shown in Figure 2, the upstream flue filling infusion process of ammonia-spraying grid 10 is combined obtained Mn- with sol-gel process
Co-Ox/Al2O3Demercuration catalyst, wherein Mn-Co-Ox load capacity are respectively 0.5 for 5wt%, Mn and Co mol ratio:1、2:1,
Reaction velocity 10000h-1, HC1 concentration 20ppm, 320 DEG C of reaction temperature, adsorbent is using load Br modified activated carbons, modified active
Charcoal emitted dose is with modified activated carbon：Total mercury weight compares 1000 in flue gas:1 determines, remaining condition is identical with base case.As a result
System demercuration rate respectively reaches 93%, 94%.
The smoke catalytic absorbing synergic demercuration method that the present invention is provided maximizes collaboration demercuration, and utilizes ready-made
Pollutant removing equipment, thus it is simple with technique, and easy to operate, demercuration efficiency is high, low cost and other advantages.The present invention can be used for
Outside boiler smoke demercuration, the flue gas demercuration of the industries such as metal smelt, cement, chemical industry, petroleum refining can be also used for.
Claims (13)
1. a kind of smoke catalytic absorbing synergic mercury removal device, including the boiler (1) being sequentially connected, Benitration reactor (2), air is pre-
Hot device (3), dust arrester (5), absorption plant (6) and chimney (7), it is characterised in that also including sorbent injection device (4),
Demercuration catalyst layer (8), denitration catalyst oxidant layer (9), ammonia-spraying grid (10)；Benitration reactor (2) import and boiler (1)
Exhaust opening is connected, and air preheater (3) flue gas side-entrance is connected with Benitration reactor (2) outlet, air preheater (3) fume side
Outlet is connected with dust arrester (5) import, and sorbent injection device (4) is located at air preheater (3) downstream and dust arrester (5)
Between the flue of upstream；The demercuration catalyst layer (8), denitration catalyst oxidant layer (9) are arranged on air preheat with ammonia-spraying grid (10)
In the Benitration reactor (2) of device (3) upstream, described demercuration catalyst layer (8) be located at denitration ammonia-spraying grid (10) upstream or/and
Catalyst for denitrating flue gas layer (9) downstream.
2. smoke catalytic absorbing synergic mercury removal device according to claim 1, it is characterised in that the dust arrester (5)
For electrostatic precipitator, sack cleaner or electrostatic fabric filter.
3. smoke catalytic absorbing synergic mercury removal device according to claim 1, it is characterised in that the absorption plant (6)
Using wet absorption device or other absorption plants, its absorbing liquid is using conventional alkali lye.
4. smoke catalytic absorbing synergic mercury removal device according to claim 1, it is characterised in that the absorption plant (6)
Using packed tower, bubble tower, plate tower or rotating stream tray scrubber.
5. a kind of smoke catalytic absorbing synergic demercuration method, it is characterised in that use demercuration catalyst and in duct sorbent injection adsorbent
Coordination technique carries out demercuration；
(1) air is combustion-supporting into boiler (1) through air preheater (3) and flue gas heat exchange, and the flue gas that fuel combustion is produced passes through de-
Catalytic oxidation occurs for mercury during mercury catalyst layer (8) in flue gas, makes Hg0Change into oxidation state mercury；
(2) flue gas after mercury catalysis oxidation is discharged by the flue gas side outlet of air preheater (3), is discharged into dust arrester
(5), in the upstream of dust arrester (5), the adsorbent that flue gas sprays with sorbent injection device (4) is well mixed, then absorption
The adsorbent for having mercury enters dust arrester (5) with flue gas, and removes adsorbent in dust arrester (5)；
(3) flue gas after handling is discharged into absorption plant (6), after mercury remaining in flue gas is absorbed in absorption plant (6), cigarette
Gas is via chimney (7) and discharges.
6. smoke catalytic absorbing synergic demercuration method according to claim 5, it is characterised in that described demercuration catalyst
Layer (8) is arranged in ammonia-spraying grid (10) upstream, or is arranged in denitration catalyst oxidant layer (2) downstream, or is arranged in ammonia-spraying grid simultaneously
(10) upstream and denitration catalyst oxidant layer (2) downstream.
7. the smoke catalytic absorbing synergic demercuration method according to claim 5 or 6, it is characterised in that described demercuration is urged
Included demercuration catalyst is with Al in agent layer (8)2O3Or TiO2For carrier, the demercuration catalyst main active component is Mn
Or Co oxides or Mn-Co mixed oxides.
8. the method for the smoke catalytic absorbing synergic demercuration stated according to claim 7, it is characterised in that described demercuration catalyst
The load capacity 1.0wt% that middle Mn load capacity is 1.0%~10%, Co~10wt%, Mn and Co mol ratio is 0.5~2.0.
9. the method for the smoke catalytic absorbing synergic demercuration according to claim 7 or 8, it is characterised in that described demercuration
Catalyst layer (8) is arranged in flue.
10. the method for smoke catalytic absorbing synergic demercuration according to claim 12, it is characterised in that described demercuration is urged
Flue temperature scope where agent layer (8) is 300~380 DEG C.
11. the method for the smoke catalytic absorbing synergic demercuration according to claim 7,8 or 9, it is characterised in that described urges
Oxidation is in 5000~15000h-1Air speed under carry out.
12. the method for smoke catalytic absorbing synergic demercuration according to claim 5, it is characterised in that described adsorbent
For activated carbon or load Br modified activated carbon.
13. smoke catalytic absorbing synergic demercuration method according to claim 5, it is characterised in that described adsorbent
The mass ratio of emitted dose and mercury in flue gas is 1000~5000：1.
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