CN109908721A - A method for removing heavy metal arsenic in low temperature flue gas by sodium salt method - Google Patents
A method for removing heavy metal arsenic in low temperature flue gas by sodium salt method Download PDFInfo
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- CN109908721A CN109908721A CN201910269810.XA CN201910269810A CN109908721A CN 109908721 A CN109908721 A CN 109908721A CN 201910269810 A CN201910269810 A CN 201910269810A CN 109908721 A CN109908721 A CN 109908721A
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- flue gas
- arsenic
- sodium
- sodium bicarbonate
- heavy metal
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- 239000003546 flue gas Substances 0.000 title claims abstract description 126
- 229910052785 arsenic Inorganic materials 0.000 title claims abstract description 112
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 title claims abstract description 111
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 title claims abstract description 106
- 238000000034 method Methods 0.000 title claims abstract description 64
- 229910001385 heavy metal Inorganic materials 0.000 title claims abstract description 33
- 159000000000 sodium salts Chemical class 0.000 title claims abstract description 23
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims abstract description 116
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims abstract description 58
- 235000017557 sodium bicarbonate Nutrition 0.000 claims abstract description 57
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 54
- 230000003647 oxidation Effects 0.000 claims abstract description 49
- 238000001179 sorption measurement Methods 0.000 claims abstract description 47
- 239000007921 spray Substances 0.000 claims abstract description 42
- 238000010521 absorption reaction Methods 0.000 claims abstract description 20
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims abstract description 14
- 239000000126 substance Substances 0.000 claims abstract description 11
- 150000001495 arsenic compounds Chemical class 0.000 claims abstract description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910000029 sodium carbonate Inorganic materials 0.000 claims abstract description 7
- 239000007788 liquid Substances 0.000 claims description 28
- 239000000843 powder Substances 0.000 claims description 26
- 239000003795 chemical substances by application Substances 0.000 claims description 23
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 17
- 239000011734 sodium Substances 0.000 claims description 17
- 229910052708 sodium Inorganic materials 0.000 claims description 17
- 238000000197 pyrolysis Methods 0.000 claims description 5
- 239000002250 absorbent Substances 0.000 claims description 4
- 230000002745 absorbent Effects 0.000 claims description 4
- GOLCXWYRSKYTSP-UHFFFAOYSA-N Arsenious Acid Chemical compound O1[As]2O[As]1O2 GOLCXWYRSKYTSP-UHFFFAOYSA-N 0.000 claims description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 claims description 3
- 239000001257 hydrogen Substances 0.000 claims description 3
- 229910052739 hydrogen Inorganic materials 0.000 claims description 3
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims description 3
- 239000000463 material Substances 0.000 claims description 2
- 239000000779 smoke Substances 0.000 claims description 2
- 235000017550 sodium carbonate Nutrition 0.000 claims description 2
- CSMWJXBSXGUPGY-UHFFFAOYSA-L sodium dithionate Chemical compound [Na+].[Na+].[O-]S(=O)(=O)S([O-])(=O)=O CSMWJXBSXGUPGY-UHFFFAOYSA-L 0.000 claims description 2
- 229940075931 sodium dithionate Drugs 0.000 claims description 2
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 claims description 2
- 235000019345 sodium thiosulphate Nutrition 0.000 claims description 2
- 239000011800 void material Substances 0.000 claims description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims 1
- WBZKQQHYRPRKNJ-UHFFFAOYSA-N disulfurous acid Chemical compound OS(=O)S(O)(=O)=O WBZKQQHYRPRKNJ-UHFFFAOYSA-N 0.000 claims 1
- 238000003379 elimination reaction Methods 0.000 claims 1
- 239000001301 oxygen Substances 0.000 claims 1
- 229910052760 oxygen Inorganic materials 0.000 claims 1
- 239000002245 particle Substances 0.000 claims 1
- 235000015424 sodium Nutrition 0.000 claims 1
- 230000001590 oxidative effect Effects 0.000 abstract description 8
- 239000007800 oxidant agent Substances 0.000 abstract description 5
- 238000005979 thermal decomposition reaction Methods 0.000 abstract description 5
- 230000000694 effects Effects 0.000 abstract description 4
- 238000006243 chemical reaction Methods 0.000 abstract description 3
- 238000000746 purification Methods 0.000 abstract description 3
- 230000007797 corrosion Effects 0.000 abstract description 2
- 238000005260 corrosion Methods 0.000 abstract description 2
- 239000011259 mixed solution Substances 0.000 abstract description 2
- 229940093920 gynecological arsenic compound Drugs 0.000 abstract 2
- 238000003795 desorption Methods 0.000 abstract 1
- 239000011148 porous material Substances 0.000 abstract 1
- 239000003245 coal Substances 0.000 description 18
- 239000007789 gas Substances 0.000 description 14
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 9
- RAHZWNYVWXNFOC-UHFFFAOYSA-N sulfur dioxide Inorganic materials O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 9
- 238000001514 detection method Methods 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 6
- 238000007689 inspection Methods 0.000 description 6
- 239000003463 adsorbent Substances 0.000 description 4
- 235000019504 cigarettes Nutrition 0.000 description 4
- 238000004140 cleaning Methods 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 239000011575 calcium Substances 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 239000000428 dust Substances 0.000 description 3
- 239000003344 environmental pollutant Substances 0.000 description 3
- 239000003517 fume Substances 0.000 description 3
- 231100000719 pollutant Toxicity 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 238000012216 screening Methods 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 2
- 229920000049 Carbon (fiber) Polymers 0.000 description 2
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 239000004917 carbon fiber Substances 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- DVUATXGAAOINPS-UHFFFAOYSA-N dimethoxyarsinic acid Chemical compound CO[As](O)(=O)OC DVUATXGAAOINPS-UHFFFAOYSA-N 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- FRLCRPUWDUKNGO-UHFFFAOYSA-N methoxyarsonic acid Chemical compound CO[As](O)(O)=O FRLCRPUWDUKNGO-UHFFFAOYSA-N 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 229910017251 AsO4 Inorganic materials 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- WJEIYVAPNMUNIU-UHFFFAOYSA-N [Na].OC(O)=O Chemical compound [Na].OC(O)=O WJEIYVAPNMUNIU-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- -1 acticarbon Substances 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 239000010882 bottom ash Substances 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000006477 desulfuration reaction Methods 0.000 description 1
- 230000003009 desulfurizing effect Effects 0.000 description 1
- VDQVEACBQKUUSU-UHFFFAOYSA-M disodium;sulfanide Chemical compound [Na+].[Na+].[SH-] VDQVEACBQKUUSU-UHFFFAOYSA-M 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 239000010881 fly ash Substances 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000002920 hazardous waste Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 239000013618 particulate matter Substances 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- HRZFUMHJMZEROT-UHFFFAOYSA-L sodium disulfite Chemical compound [Na+].[Na+].[O-]S(=O)S([O-])(=O)=O HRZFUMHJMZEROT-UHFFFAOYSA-L 0.000 description 1
- 235000010262 sodium metabisulphite Nutrition 0.000 description 1
- 229910052979 sodium sulfide Inorganic materials 0.000 description 1
- 239000002910 solid waste Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 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
- 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
- B01D53/48—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
- B01D53/504—Sulfur oxides by treating the gases with a solution or a suspension of an alkali or earth-alkali or ammonium compound 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
- B01D53/46—Removing components of defined structure
- B01D53/48—Sulfur compounds
- B01D53/50—Sulfur oxides
- B01D53/508—Sulfur oxides by treating the gases with solids
-
- 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
- B01D53/81—Solid phase processes
- B01D53/82—Solid phase processes with stationary reactants
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/30—Sulfur compounds
- B01D2257/302—Sulfur oxides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/40—Nitrogen compounds
- B01D2257/404—Nitrogen oxides other than dinitrogen oxide
-
- 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
-
- 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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- Environmental & Geological Engineering (AREA)
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- Oil, Petroleum & Natural Gas (AREA)
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Abstract
本发明提供了一种钠盐法脱除低温烟气中重金属砷的方法，采取以具有强氧化作用和强吸附作用的碳酸氢钠为烟气净化吸附氧化剂床层，利用碳酸氢钠热分解产生的高比表面积碳酸钠的孔隙吸附烟气中的颗粒态砷Asp，利用碳酸氢钠与烟气中SO2反应产生的大量活性氧化物质对烟气中的三价砷化合物进行氧化，使之转化为水溶性更好的五价砷化合物，经氧化吸收后的烟气进入喷淋塔，以热解吸附氧化后的碳酸氢钠和新鲜碳酸氢钠混合溶液喷淋液，进一步脱除烟气中各种形态的砷，从而实现了对烟气中砷的净化。本发明提供的低温烟气重金属砷的钠盐脱除方法，工艺简单，投资少，运营成本较低，对烟气净化设备无腐蚀。The invention provides a method for removing heavy metal arsenic in low-temperature flue gas by a sodium salt method. The sodium bicarbonate with strong oxidizing effect and strong adsorption effect is used as the bed layer of flue gas purifying and adsorbing oxidant, and the thermal decomposition of sodium bicarbonate is used to generate The pores of sodium carbonate with high specific surface area adsorb particulate arsenic As p in the flue gas, and use a large number of active oxidizing substances produced by the reaction of sodium bicarbonate and SO 2 in the flue gas to oxidize the trivalent arsenic compounds in the flue gas, making it It is converted into pentavalent arsenic compounds with better water solubility. The flue gas after oxidation and absorption enters the spray tower, and the mixed solution of sodium bicarbonate after oxidation and fresh sodium bicarbonate is sprayed by thermal desorption to further remove the flue gas. various forms of arsenic in the flue gas, thus realizing the purification of arsenic in the flue gas. The method for removing sodium salt of heavy metal arsenic from low-temperature flue gas provided by the invention has the advantages of simple process, low investment, low operating cost and no corrosion to flue gas purification equipment.
Description
Technical field
The invention belongs to environment-friendly engineering technical field, it is related to removing the technical method of harmful substances from flue gases, specifically
Ground is said, is to be related to a kind of method that sodium salt method removes heavy metal arsenic in low-temperature flue gas.
Background technique
With the development of economy, the demand of industrial production, people's lives to electric power is constantly promoted.Although China is energetically
Energy-saving power generation is advocated, tap a new source of energy equal measures, but energy resource structure of the China based on coal will not change in a short time.
Coal is the most abundant fossil fuel of China's reserves.However a large amount of SO can be generated after coal burningx、NOxAnd heavy metal,
Biggish middle harm includes arsenic, mercury, lead etc., causes high risks to the ecosystem and the mankind.Currently, arsenic content in China's coal
Average value is 4.7g/t, slightly below world's mean value, but China's coal huge number, and each coal contains arsenic between 0~476g/t, difference
Greatly.By higher with arsenic content in the coal of the provinces such as Sichuan, Chongqing, Guizhou, Yunnan.It is 5g/t calculating with arsenic content, China is annual
There are about 195.0t or so to atmosphere discharge arsenic amount for fire coal.In the air of the big cities such as China Fushun, Shenyang, Lanzhou, Chengdu at present
There are different degrees of arsenic pollutions.Arsenic pollution caused by fire coal is the problem and challenge of mankind's facing, more becomes and restricts me
One key factor of state's economy and society sustainable development.
In order to reduce the pollution of heavy metal arsenic in atmosphere, it is necessary to handle flue gas.The object of different shape arsenide
Physicochemical property and toxicity have very big difference, and heavy metal in flue gas arsenic is mainly trivalent arsenic (As3+), pentavalent arsenic (As5+), also
It include the organoarsenium compounds such as trace monomethyl arsenic acid (MMA), dimethyl arsenate (DMA).The compound of arsenic is volatile, simultaneously
Easily condensation is gasified in the high-temp combustion process China arsenic almost all of coal and is discharged, and gaseous state arsenic is cold in 300 DEG C or so beginnings
It is solidifying, and be easily enriched on fine particle, therefore traditional flue gas dearsenification thinking mainly to the condensation in flue gas and is enriched in
To arsenic and its compound collaboration removal on particulate matter, but the gaseous state arsenic for not being fully condensed absorption can enter atmosphere with flue gas emission
In environment.
The processing method of traditional heavy metal arsenic can substantially be divided into dearsenification before burning, be taken off in burning after dearsenification and burning
Arsenic.Dearsenification major technique is coal washing before burning, and can achieve 70% or more, but coal washing skill to the separating by extraction of inorganic forms in coal
The arsenic cost that art is used to remove in coal is excessively high, takes up a large area, technology is also not mature enough, and the relation between supply and demand of coal also affects
Coal enters to wash rate, so that such technology is subject to certain restrictions in actual use and popularization.
Dearsenification is mainly using in-furnace calcium spraying technology as representative in burning, with As in coal-burning boiler exiting flue gas2O3Based on, CaO is easy
With As2O3Reaction generates Ca3(AsO4)2On fly ash, in general, arsenic content is higher in coal, and arsenic removal efficiency is higher for absorption,
Generally 3.05~37.35%, but the conversion ratio reacted is limited, and the arsenic adsorbed in bottom ash is fewer, and the efficiency of dearsenification also compares
It is low.
Dearsenification is the main means for controlling arsenic pollution after burning, improves the direct side that efficiency of dust collection is flue gas dearsenification after burning
Method, but operating cost is improved, technical aspect is also incomplete；Sodium sulfide method can also reach the dearsenification efficiency on 90%, but
With the disadvantages of more demanding to dust content, acid solution easily generates corrosion to equipment, absorption process is mainly inhaled using injection
Attached dose of method is adsorbed the arsenic in flue gas to reach dearsenification purpose.Common adsorbent mainly has: flying dust, calcium base, silicon
Aluminium base adsorbent, acticarbon, carbon fiber adsorption agent etc..But the active carbon of heavy metal in flue gas arsenic, carbon fiber are adsorbed
Adsorbent etc. belongs to hazardous waste, and subsequent processing steps are still cumbersome.
In conclusion with the development of the social economy, country and the people to environmental improvement, more stringent requirements are proposed, it is existing
The technology of removing heavy metal in flue gas arsenic has been difficult to meet the requirement of environmental improvement, is badly in need of developing dearsenification skill in more effective flue gas
Art.The present invention uses main active component for sodium bicarbonate, has preferable to arsenic removal efficiency in flue gas, active higher, former
The advantages that material is easy to get, is a kind of potential method to dearsenification in flue gas.
Summary of the invention
The technical problem to be solved by the present invention is to overcome heavy metal in flue gas arsenic adsorption and oxidation agent under existing cryogenic conditions living
Property deficiency problem, find a kind of good adsorption and oxidation agent of adsorption activity under cryogenic, can efficiently promote in coal-fired flue-gas
Trivalent arsenic (As3+) it is transformed into water pentavalent arsenic (As5+), to solve arsenic (predominantly As in flue gas2O3) be difficult to be caught by traditional technology
Collect problem, provides a kind of method that sodium salt method removes heavy metal arsenic in low-temperature flue gas, this method based on the adsorption and oxidation agent found
Simply, small investment, operation cost is lower, corrosion-free to flue gas purifying equipment.
The technical thought that the present invention solves its technical problem is, under cryogenic (90~150 DEG C) using sodium bicarbonate
Decompose the particulate form arsenic (As in the high-specific surface area hole absorption flue gas generatedp), while existing in flue gas using sodium bicarbonate
SO2In the case of a large amount of active materials for generating by trivalent arsenic (As3+) it is oxidized to water-soluble preferably pentavalent arsenic (As5+), then pass through
Wet sprinkling removes the arsenic of various forms in flue gas.
The method of heavy metal arsenic in sodium salt method removing low-temperature flue gas provided by the invention, mainly comprises the following steps that:
(1) heavy metal arsenic, SO will be contained2The flue gas for being 90 DEG C~150 DEG C with NO temperature, which is passed through with sodium bicarbonate powder, is
The bed of adsorption and oxidation agent carries out pyrolysis adsorption oxidation reaction with the sodium bicarbonate as adsorption and oxidation agent, and sodium bicarbonate is warm
Solution is the sodium carbonate in high-specific surface area gap, and sodium carbonate adsorbs the particulate form arsenic As in flue gas by its voidp, oxidation is instead
Trivalent arsenic compound is transformed into pentavalent arsenic compound by the active oxidation substance that should be generated；
(2) be sent into spray column from the lower part of spray column through step (1) treated flue gas, under the spray of top by carbonic acid
The absorption spray liquid that sodium bicarbonate powder behind hydrogen sodium powder end and pyrolysis adsorption and oxidation adds water to prepare, which comes into full contact with, remove instead
It answers, removes the pentavalent arsenic As in flue gas5+The particulate form arsenic As not being removed with step (1)pAnd a small amount of unoxidized trivalent arsenide
Object is closed, is removed into the arsenic in solution eventually by the mode of condensing crystallizing；
(3) smoke exhaust system of the arsenic content lower than national emission standard after step (2) processing.
In above-mentioned technical proposal of the invention, SO in flue gas2Mass ratio with NO is preferably in the range of 1:1~10.
In above-mentioned technical proposal of the invention, in step (1) dosage of sodium bicarbonate can according to flue gas air speed 20000~
30000h-1It is determined.
In above-mentioned technical proposal of the invention, sodium bicarbonate powder partial size priority acccess control is in 10-150 μ m.
In above-mentioned technical proposal of the invention, SO in sodium bicarbonate and flue gas2The active oxidation substance generated is reacted,
Active principle includes at least one of sodium dithionate, sodium pyrosulfite, sodium thiosulfate, sodium bicarbonate and sodium carbonate.
In above-mentioned technical proposal of the invention, the volume ratio priority acccess control of spray liquid and flue gas is in 3~5:1 range.
In above-mentioned technical proposal of the invention, model of the mass concentration priority acccess control of the spray liquid 1%~10%
It encloses.
Sodium bicarbonate and fresh bicarbonate after being pyrolyzed adsorption and oxidation in above-mentioned technical proposal of the invention, in spray liquid
The quality of sodium is than priority acccess control in the range of 1:1~3.
In above-mentioned technical proposal of the invention, total arsenic preferably in through step (1) step (2) treated flue gas
When removal efficiency is lower than 60%, fresh sodium bicarbonate absorbent is replaced.
In above-mentioned technical proposal of the invention, preferably when spray liquid pH value is less than 8, sodium bicarbonate powder need to be added
It is recycled to adjust pH to 8-10.
In above-mentioned technical proposal of the invention, the flue gas includes boiler fired coal flue gas, also includes that other industry generates
The exhaust gas containing arsenic.
In above-mentioned technical proposal of the invention, it is the bed for absorbing oxidant with sodium bicarbonate powder, can be one layer,
It is also possible to multilayer.The bed of absorbent can be set in the adsorption oxidation reaction device specially designed, also can be set in cigarette
In road.
The method of heavy metal arsenic in sodium salt method provided by the invention removing low-temperature flue gas, wherein sodium salt absorbent and spray liquid
Dosage, according to flue gas pollutant changes of contents (objectively flue gas pollutant with raw materials and fuel change and operating condition change and change)
And the requirement that on-line checking pollutant emission is up to standard, can real-time perfoming adjust so that discharge flue gas reach emission request.
Trace heavy metal arsenic in flue gas is removed using method of the invention, if continuous processing is taken to be taken off
It removes, the equipment in technique for being laid with sodium bicarbonate powder bed will at least be set side by side two, the carbonic acid in an equipment
When replacing fresh sodium bicarbonate powder after hydrogen sodium adsorption and oxidation reduced performance, need other to be equipped with sodium bicarbonate powder bed
Equipment start operation, guarantee removing is carried out continuously to arsenic in flue gas.
The present invention has found a kind of adsorption and oxidation agent-sodium bicarbonate that the activity of adsorption and oxidation under cryogenic is good, takes
Using the sodium bicarbonate with strong oxidation and strong suction-operated as gas cleaning adsorption and oxidation agent bed, sodium bicarbonate heat is utilized
Decompose the particulate form arsenic As in the hole absorption flue gas of the high-specific surface area carbonic acid sodium generatedp, using in sodium bicarbonate and flue gas
SO2The trivalent arsenic compound reacted in a large amount of activating oxide confrontation flue gases generated is aoxidized, and is allowed to be converted into water solubility
Better pentavalent arsenic compound, solves in flue gas that trivalent arsenic compound is difficult to trap problem by traditional technology, to remove flue gas
Middle heavy metal arsenic is laid a good foundation, and the flue gas after oxidative absorption enters spray column, the sodium bicarbonate after being pyrolyzed adsorption and oxidation
The arsenic that various forms in flue gas are further removed under the good alkalinity removing environment built with fresh sodium bicarbonate mixed solution, from
And realize the purification to arsenic in flue gas.The sodium salt removal methods of low-temperature flue gas heavy metal arsenic provided by the invention, simple process,
Small investment, operation cost is lower, corrosion-free to flue gas purifying equipment.
The method of heavy metal arsenic in sodium salt method removing low-temperature flue gas provided by the invention, in removing flue gas during arsenic
The sulfur dioxide and nitrogen oxides of flue gas is utilized, while arsenic is removed, the sulfur dioxide in flue gas is also enable to take off
It removes, the NO in flue gas is made first to be converted to NO through dry oxidation2, then NO is eventually converted into after spraying3 -(nitrate ion), for into
Nitrogen oxides in one-step removal flue gas provides advantage.Process i.e. of the invention can not only remove in flue gas
Arsenic, also for removing flue gas in sulfur dioxide and nitrogen oxides create condition.
It is not high to compensate for the universal desulfuration efficiency of conventional dry to method of the invention compared with existing conventional dry technique
Weakness, desulfurizing byproduct bring secondary pollution, the higher problem of running cost；Compared with existing Wet technique, the wet process of sodium salt method
Spray system is the system of a high dissolution, and the alkaline section that operation pH value is 8-10 just meets needed for heavy metal removing
Alkaline section；Liquid air volume ratio is not more than 3, greatly reduces power consumption.It is molten using oxidation sodium bicarbonate and sodium bicarbonate mixing
Liquid is as spray liquid, since the dissolubility of sodium salt is good, risk is blocked caused by no fouling, and insensitive, raising is fluctuated to flue gas
The adaptability of device overcomes secondary sewage that conventional wet denounced and the problem of secondary solid waste pollutes.
Specific embodiment
Below by taking the specific implementation of process of the invention in Luzhou, Sichuan factory as an example, to further illustrate this hair
It is bright, but it should be strongly noted that therefore protection scope of the present invention cannot be limited among the embodiment confining spectrum.
Embodiment 1
The flue gas of Luzhou, Sichuan factory 130t/h coal-fired steam boiler discharge, tunnel gas amount are 158627m3/ h, cigarette
Total arsenic content is 23.22 μ g/Nm in gas3, SO in flue gas2And NO2Volume ratio be 1.Factory's flue gas is originally after deduster dedusting
Spray column is entered by chimney air flue and carries out subsequent processing.Gas cleaning in the present embodiment, using sodium bicarbonate as adsorption and oxidation
Agent, dosage are 20000h according to flue gas air speed-1It is determined, aoxidizes space by ADSORPTION IN A FIXED BED of existing flue stack.
Specific removing operation is as follows:
(1) preparation of sodium base oxidant and spray-absorption liquid: commercially available sodium bicarbonate is ground, screening is processed as partial size and is about
75 μm of powder, using sodium bicarbonate powder as adsorption and oxidation agent；It is pressed with aoxidizing sodium bicarbonate with sodium bicarbonate powder is not aoxidized
Mass ratio is 1:1 mixing, and water is added to be configured to the spray-absorption liquid that mass concentration is 5%；
(2) ADSORPTION IN A FIXED BED aoxidizes: the resulting sodium base adsorption and oxidation agent powder of step (1) is placed in consolidating in flue
In fixed bed, fixed bed is set as one layer, and the arsenical fume that 108 DEG C of temperature is by being loaded with the fixed bed of sodium base adsorption and oxidation agent
When, the hole that thermal decomposition generates high-specific surface area occurs for sodium base adsorption and oxidation agent, adsorbs the particulate form arsenic (As in flue gasp)；And it produces
Raw a large amount of active oxidation substance, by trivalent arsenic (As in flue gas3+) it is oxidized to pentavalent arsenic (As5+), flue gas inspection after adsorption and oxidation
Sample detection arsenic content is 18.64 μ g/Nm3；
(3) spray column spray removing: introducing spray column for the flue gas in step (2) after ADSORPTION IN A FIXED BED oxidation processes,
The spray-absorption liquid for the mass concentration 5% that step (1) is prepared sprays process liquid air volume ratio by circulating pump circulated sprinkling
For 1:1.5, the entire system running pH that sprays is 8.9, and flue gas inspection sample detection arsenic content is 3.35 μ g/ after spray removing
Nm3, the removal efficiency of arsenic is 86%；
(4) for flue gas after step (3) processing, arsenic content is lower than 5 μ g/Nm of national emission standard3Tail gas discharge system.
The present embodiment is in SO2The sodium bicarbonate with strong oxidation is placed in chimney air flue under existence condition
In fixed bed reactors, with the oxide of high activity substance of generation, by the trivalent arsenic (As in flue gas3+) it is oxidized to pentavalent arsenic (As5 +), and hole is generated by the thermal decomposition of sodium bicarbonate, adsorb the particulate form arsenic (As in flue gasp).Again by molten with sodium bicarbonate
Liquid is that spray-absorption liquid traps the heavy metal arsenic in flue gas, makes the arsenic content in flue gas no more than 5 μ of national emission standard
g/Nm3。
Embodiment 2
The flue gas of Luzhou, Sichuan factory 130t/h coal-fired steam boiler discharge, tunnel gas amount are 138137m3/ h, cigarette
Arsenic content is 21.44 μ g/Nm in gas3, SO in flue gas2And NO2Volume ratio be 2.0.Factory's flue gas is originally after deduster dedusting
Spray column is entered by chimney air flue and carries out subsequent processing.Gas cleaning in the present embodiment, using sodium bicarbonate as adsorption and oxidation
Agent, dosage are 20000h according to flue gas air speed-1It is determined, aoxidizes space by ADSORPTION IN A FIXED BED of existing flue stack.
Specific removing operation is as follows:
(1) preparation of sodium base oxidant and spray-absorption liquid: commercially available sodium bicarbonate is ground, screening is processed as partial size and is about
50 μm of powder, using sodium bicarbonate powder as adsorption and oxidation agent；It is pressed with aoxidizing sodium bicarbonate with sodium bicarbonate powder is not aoxidized
Mass ratio is 1:1 mixing, and water is added to be configured to the spray-absorption liquid that mass concentration is 10%；
(2) ADSORPTION IN A FIXED BED aoxidizes: the resulting sodium base adsorption and oxidation agent powder of step (1) is placed in consolidating in flue
In fixed bed, fixed bed is set as one layer, and the arsenical fume that 126 DEG C of temperature is by being loaded with the fixed bed of sodium base adsorption and oxidation agent
When, the hole that thermal decomposition generates high-specific surface area occurs for sodium base adsorption and oxidation agent, adsorbs the particulate form arsenic (As in flue gasp)；And it produces
Raw a large amount of active oxidation substance, by trivalent arsenic (As in flue gas3+) it is oxidized to pentavalent arsenic (As5+), flue gas inspection after adsorption and oxidation
Sample detection arsenic content is 19.31 μ g/Nm3；
(3) spray column spray removing: introducing spray column for the flue gas in step (2) after ADSORPTION IN A FIXED BED oxidation processes,
The spray-absorption liquid for the mass concentration 10% that step (1) is prepared sprays process liquid air volume ratio by circulating pump circulated sprinkling
For 1:3, the entire system running pH that sprays is 9, and flue gas inspection sample detection arsenic content is 4.47 μ g/Nm after spray removing3, arsenic
Removal rate be 79%；
(4) for flue gas after step (3) processing, arsenic content is lower than 5 μ g/Nm of national emission standard3Tail gas discharge system.
Embodiment 3
The flue gas of Luzhou, Sichuan factory 130t/h coal-fired steam boiler discharge, tunnel gas amount are 158453m3/ h, cigarette
Arsenic content is 20.08 μ g/Nm in gas3, SO in flue gas2And NO2Volume ratio be 2.Factory's flue gas originally after deduster dedusting by
Chimney air flue enters spray column and carries out subsequent processing.Gas cleaning in the present embodiment, using sodium bicarbonate as adsorption and oxidation agent,
Its dosage is 30000h according to flue gas air speed-1It is determined, aoxidizes space by ADSORPTION IN A FIXED BED of existing flue stack.Specifically
Removing operation is as follows:
(1) preparation of sodium base oxidant and spray-absorption liquid: commercially available sodium bicarbonate is ground, screening is processed as partial size and is about
100 μm of powder, using sodium bicarbonate powder as adsorption and oxidation agent；It is pressed with aoxidizing sodium bicarbonate with sodium bicarbonate powder is not aoxidized
Quality: 1:3 mixing adds water to be configured to the spray-absorption liquid that mass concentration is 10%；
(2) ADSORPTION IN A FIXED BED aoxidizes: the resulting sodium base adsorbent oxidation powder of step (1) is placed in consolidating in flue
In fixed bed, fixed bed is set as one layer, and the arsenical fume that 100 DEG C of temperature is by being loaded with the fixed bed of sodium base adsorption and oxidation agent
When, the hole that thermal decomposition generates high-specific surface area occurs for sodium base adsorption and oxidation agent, adsorbs the particulate form arsenic (As in flue gasp)；And it produces
Raw a large amount of active oxidation substance, by trivalent arsenic (As in flue gas3+) it is oxidized to pentavalent arsenic (As5+), flue gas inspection after adsorption and oxidation
Sample detection arsenic content is 16.44 μ g/Nm3；
(3) spray column spray removing: introducing spray column for the flue gas in step (2) after ADSORPTION IN A FIXED BED oxidation processes,
The spray-absorption liquid for the mass concentration 10% that step (1) is prepared sprays process liquid air volume ratio by circulating pump circulated sprinkling
For 1:2, the entire system running pH that sprays is 8.5, and flue gas inspection sample detection arsenic content is 3.88 μ g/Nm after spray removing3,
The removal rate of arsenic is 81%；
(4) for flue gas after step (3) processing, arsenic content is lower than 5 μ g/Nm of national emission standard3Tail gas discharge system.
Claims (10)
1. a kind of method of heavy metal arsenic in sodium salt method removing low-temperature flue gas, which comprises the following steps:
(1) heavy metal arsenic, SO will be contained2It is absorption oxygen that the flue gas for being 90 DEG C~150 DEG C with NO temperature, which is passed through with sodium bicarbonate powder,
The bed of agent carries out pyrolysis adsorption oxidation reaction with the sodium bicarbonate as adsorption and oxidation agent, and sodium bicarbonate is pyrolyzed as height
The sodium carbonate in specific surface area gap, sodium carbonate adsorb the particulate form arsenic As in flue gas by its voidp, oxidation reaction generation
Active oxidation substance by trivalent arsenic compound (predominantly As2O3) it is transformed into pentavalent arsenic compound；
(2) be sent into spray column from the lower part of spray column through step (1) treated flue gas, under the spray of top by sodium bicarbonate
The absorption spray liquid that sodium bicarbonate powder after powder and pyrolysis adsorption and oxidation adds water to prepare comes into full contact with carry out elimination reaction, takes off
Except the pentavalent arsenic compound and the particulate form arsenic As that is not removed of step (1) in flue gaspAnd a small amount of unoxidized trivalent arsenic chemical combination
Object, the arsenic in solution are removed eventually by the mode of condensing crystallizing；
(3) smoke exhaust system of the arsenic content lower than national emission standard after step (2) processing.
2. the method for heavy metal arsenic in sodium salt method removing low-temperature flue gas according to claim 1, which is characterized in that in flue gas
SO2Volume ratio with NO is 1:1~10.
3. the method for heavy metal arsenic in sodium salt method removing low-temperature flue gas according to claim 1, which is characterized in that step
(1) dosage of sodium bicarbonate is according to 20000~30000h of flue gas air speed in-1It is determined.
4. the method for heavy metal arsenic in sodium salt method removing low-temperature flue gas according to claim 1, which is characterized in that bicarbonate
Sodium powder material particle size range is at 25-100 μm.
5. the method for heavy metal arsenic in sodium salt method removing low-temperature flue gas according to claim 1, which is characterized in that carbonic acid
SO in hydrogen sodium and flue gas2The active oxidation substance generated is reacted, active principle includes at least sodium dithionate, pyrosulfurous acid
One of sodium, sodium thiosulfate, sodium bicarbonate and sodium carbonate.
6. the method for heavy metal arsenic, feature exist in sodium salt method removing low-temperature flue gas according to one of claims 1 to 5
In the volume ratio of spray liquid and flue gas is 3~5:1.
7. the method for heavy metal arsenic in sodium salt method removing low-temperature flue gas according to claim 6, which is characterized in that the spray
The mass concentration for drenching liquid is 1%~10%.
8. the method for heavy metal arsenic in sodium salt method removing low-temperature flue gas according to claim 7, which is characterized in that spray liquid
The mass ratio of sodium bicarbonate and sodium bicarbonate after middle pyrolysis adsorption and oxidation is 1:1~3.
9. the method for heavy metal arsenic, feature exist in sodium salt method removing low-temperature flue gas according to one of claims 1 to 5
In replacing fresh sodium bicarbonate when the removal efficiency through arsenic total in step (1) step (2) treated flue gas is lower than 60%
Absorbent.
10. the method for heavy metal arsenic, feature exist in sodium salt method removing low-temperature flue gas according to one of claims 1 to 5
In, when spray liquid pH value is less than 8, need to be added sodium bicarbonate powder adjust pH to 8-10 it is recycled.
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| CN201811568577.7A CN109569224A (en) | 2018-12-21 | 2018-12-21 | A kind of process removing heavy metal in flue gas lead |
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| CN201811568577.7A Pending CN109569224A (en) | 2018-12-21 | 2018-12-21 | A kind of process removing heavy metal in flue gas lead |
| CN201910269652.8A Pending CN109908719A (en) | 2018-12-21 | 2019-04-04 | A kind of technological method of removing heavy metal lead in flue gas |
| CN201910269826.0A Pending CN109908722A (en) | 2018-12-21 | 2019-04-04 | Method for removing metalloid selenium from low temperature flue gas by sodium salt method |
| CN201910269783.6A Pending CN109908720A (en) | 2018-12-21 | 2019-04-04 | A method for removing heavy metal mercury in low-temperature flue gas by sodium salt method |
| CN201910269810.XA Pending CN109908721A (en) | 2018-12-21 | 2019-04-04 | A method for removing heavy metal arsenic in low temperature flue gas by sodium salt method |
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| CN201910269826.0A Pending CN109908722A (en) | 2018-12-21 | 2019-04-04 | Method for removing metalloid selenium from low temperature flue gas by sodium salt method |
| CN201910269783.6A Pending CN109908720A (en) | 2018-12-21 | 2019-04-04 | A method for removing heavy metal mercury in low-temperature flue gas by sodium salt method |
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| CN109908720A (en) | 2019-06-21 |
| CN109569224A (en) | 2019-04-05 |
| CN109908719A (en) | 2019-06-21 |
| CN109908722A (en) | 2019-06-21 |
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Application publication date: 20190621 |
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