CN110177611A - Arsenic removal is gone from flue gas - Google Patents
Arsenic removal is gone from flue gas Download PDFInfo
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- CN110177611A CN110177611A CN201780074407.0A CN201780074407A CN110177611A CN 110177611 A CN110177611 A CN 110177611A CN 201780074407 A CN201780074407 A CN 201780074407A CN 110177611 A CN110177611 A CN 110177611A
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- ionic liquid
- ion
- arsenic
- method described
- active carbon
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- 229910052785 arsenic Inorganic materials 0.000 title abstract description 24
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 title abstract description 22
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 title description 2
- 239000003546 flue gas Substances 0.000 title description 2
- 239000002608 ionic liquid Substances 0.000 claims abstract description 36
- 238000000034 method Methods 0.000 claims abstract description 32
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 31
- 239000007789 gas Substances 0.000 claims abstract description 21
- 239000012071 phase Substances 0.000 claims abstract description 11
- -1 carboxylic acid ion anion Chemical class 0.000 claims abstract description 7
- JUJWROOIHBZHMG-UHFFFAOYSA-N pyridine Substances C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims abstract description 6
- 238000005516 engineering process Methods 0.000 claims abstract description 5
- 239000002912 waste gas Substances 0.000 claims abstract description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims abstract description 4
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 claims abstract description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims abstract description 3
- RWRDLPDLKQPQOW-UHFFFAOYSA-N Pyrrolidine Chemical class C1CCNC1 RWRDLPDLKQPQOW-UHFFFAOYSA-N 0.000 claims abstract description 3
- 229940006460 bromide ion Drugs 0.000 claims abstract description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 32
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 10
- 150000001450 anions Chemical class 0.000 claims description 7
- 238000003723 Smelting Methods 0.000 claims description 6
- 239000000377 silicon dioxide Substances 0.000 claims description 5
- 150000001721 carbon Chemical group 0.000 claims description 4
- 150000002430 hydrocarbons Chemical class 0.000 claims description 3
- 239000004215 Carbon black (E152) Substances 0.000 claims description 2
- COHDHYZHOPQOFD-UHFFFAOYSA-N arsenic pentoxide Inorganic materials O=[As](=O)O[As](=O)=O COHDHYZHOPQOFD-UHFFFAOYSA-N 0.000 claims description 2
- 229910052736 halogen Inorganic materials 0.000 claims description 2
- 229930195733 hydrocarbon Natural products 0.000 claims description 2
- 150000005837 radical ions Chemical class 0.000 claims description 2
- 125000001424 substituent group Chemical group 0.000 claims description 2
- RAXXELZNTBOGNW-UHFFFAOYSA-N 1H-imidazole Chemical class C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims 1
- 239000004411 aluminium Substances 0.000 claims 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims 1
- 229910052782 aluminium Inorganic materials 0.000 claims 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims 1
- 229910052760 oxygen Inorganic materials 0.000 claims 1
- 239000001301 oxygen Substances 0.000 claims 1
- 238000001179 sorption measurement Methods 0.000 abstract description 17
- 229910000413 arsenic oxide Inorganic materials 0.000 abstract description 3
- 229960002594 arsenic trioxide Drugs 0.000 abstract description 2
- 230000002708 enhancing effect Effects 0.000 abstract description 2
- 150000002460 imidazoles Chemical class 0.000 abstract description 2
- 238000006467 substitution reaction Methods 0.000 abstract description 2
- KTTMEOWBIWLMSE-UHFFFAOYSA-N diarsenic trioxide Chemical compound O1[As](O2)O[As]3O[As]1O[As]2O3 KTTMEOWBIWLMSE-UHFFFAOYSA-N 0.000 abstract 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 9
- 239000000463 material Substances 0.000 description 9
- 229910052751 metal Inorganic materials 0.000 description 7
- 239000002184 metal Substances 0.000 description 7
- 238000010521 absorption reaction Methods 0.000 description 5
- 239000003463 adsorbent Substances 0.000 description 5
- 229910052753 mercury Inorganic materials 0.000 description 4
- 239000000758 substrate Substances 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 229910000831 Steel Inorganic materials 0.000 description 3
- 229910052793 cadmium Inorganic materials 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 3
- 238000005272 metallurgy Methods 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 229910052711 selenium Inorganic materials 0.000 description 3
- 239000010959 steel Substances 0.000 description 3
- 229910052725 zinc Inorganic materials 0.000 description 3
- 239000011701 zinc Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 229910052787 antimony Inorganic materials 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 239000003245 coal Substances 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 229910052745 lead Inorganic materials 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000011490 mineral wool Substances 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- HCGMDEACZUKNDY-UHFFFAOYSA-N 1-butyl-3-methyl-1,2-dihydroimidazol-1-ium;acetate Chemical compound CC(O)=O.CCCCN1CN(C)C=C1 HCGMDEACZUKNDY-UHFFFAOYSA-N 0.000 description 1
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 235000011941 Tilia x europaea Nutrition 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- IKWTVSLWAPBBKU-UHFFFAOYSA-N a1010_sial Chemical compound O=[As]O[As]=O IKWTVSLWAPBBKU-UHFFFAOYSA-N 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 150000001495 arsenic compounds Chemical class 0.000 description 1
- GOLCXWYRSKYTSP-UHFFFAOYSA-N arsenic trioxide Inorganic materials O1[As]2O[As]1O2 GOLCXWYRSKYTSP-UHFFFAOYSA-N 0.000 description 1
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 231100000584 environmental toxicity Toxicity 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 229940093920 gynecological arsenic compound Drugs 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 230000005802 health problem Effects 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 239000004571 lime Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005259 measurement 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
- 239000012621 metal-organic framework Substances 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 150000002892 organic cations Chemical class 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 230000002688 persistence Effects 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000013049 sediment Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 231100001234 toxic pollutant Toxicity 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
Classifications
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- 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
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28054—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their surface properties or porosity
- B01J20/28057—Surface area, e.g. B.E.T specific surface area
- B01J20/28066—Surface area, e.g. B.E.T specific surface area being more than 1000 m2/g
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- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28054—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their surface properties or porosity
- B01J20/28069—Pore volume, e.g. total pore volume, mesopore volume, micropore volume
- B01J20/28073—Pore volume, e.g. total pore volume, mesopore volume, micropore volume being in the range 0.5-1.0 ml/g
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28054—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their surface properties or porosity
- B01J20/28078—Pore diameter
- B01J20/28083—Pore diameter being in the range 2-50 nm, i.e. mesopores
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/30—Processes for preparing, regenerating, or reactivating
- B01J20/32—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating
- B01J20/3202—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating characterised by the carrier, support or substrate used for impregnation or coating
- B01J20/3204—Inorganic carriers, supports or substrates
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/30—Processes for preparing, regenerating, or reactivating
- B01J20/32—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating
- B01J20/3231—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating characterised by the coating or impregnating layer
- B01J20/3287—Layers in the form of a liquid
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- B01D2252/30—Ionic liquids and zwitter-ions
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- 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
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- B01D2253/102—Carbon
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01D2253/00—Adsorbents used in seperation treatment of gases and vapours
- B01D2253/30—Physical properties of adsorbents
- B01D2253/302—Dimensions
- B01D2253/306—Surface area, e.g. BET-specific surface
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01D2258/0283—Flue gases
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- 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
- B01D53/02—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 by adsorption, e.g. preparative gas chromatography
- B01D53/025—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 by adsorption, e.g. preparative gas chromatography with wetted adsorbents; Chromatography
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- Oil, Petroleum & Natural Gas (AREA)
- Inorganic Chemistry (AREA)
- Biomedical Technology (AREA)
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- Health & Medical Sciences (AREA)
- Nanotechnology (AREA)
- Treating Waste Gases (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
The invention is related to a kind of method for removing the arsenic oxide in technology waste gas, and the method includes making exhaust gas pass through the ionic liquid phase bed of load, it is characterised in that the ionic liquid includes one or more selected from substitution, ammonium, imidazoles, pyrrolidinesAnd pyridine
Description
The present invention relates to a kind of gas cleaning process, the method is especially suitable for removing the trace arsenic oxidation in exhaust gas
The exhaust gas generated in object, especially metallurgy smelting process or coal burning process.
Arsenic is present in many mineral, concentrate and the metal-containing material of recycling.Arsenic and many arsenic compounds are at high temperature
Also relatively volatile.Therefore, most of metallurgical operations, which generate, contains arsenic gas, is especially even more when using fire metallurgy process
So.Example is the burning of coal, or recycles metal such as copper and lead using smelting process.The discharge of smelting furnace and converter can lead to
The health problem of workplace, and/or the content of the toxic pollutant of such as lead and arsenic near smeltery is caused to increase.
It according to known methods, can be by condensation, filtering or activated carbon adsorption come most of arsenic in recovery air-flow.
Condensation and filtering are so that the content of arsenic is reduced to about 0.2-0.8mg/Nm in gas phase3.White lime Ca (OH)2It can infuse
Enter in gas, acts not only as condensing surface, it can also be by forming Ca-As sediment come arsenic-adsorbing.It then usually can be with
Arsenic is further reduced to 0.05mg/Nm3。
However, it is contemplated that the eco-toxicity of the metal and its compound, needs more completely to eliminate arsenic.In addition, typical
Industrial operation is related to continuously discharging bulk gas, to exacerbate environmental problem.
The known method for being further reduced arsenic be pass the gas through it is active-carbon bed.
It has realized that the adsorption effect of arsenic on the activated carbon reduces as the temperature rises.Therefore, air-flow must be cold
But to far below 100 DEG C.Unfortunately, at such a temperature adsorption dynamics adsorption kinetics is fairly slow.It is abundant between active carbon and gas
Time of contact can only be realized by using large volume bed, it is therefore desirable to contain a large amount of active carbon.This causes huge and expensive
Equipment.In addition, active carbon is utilized effectively not yet, because it will not be saturated in arsenic during normal service life.
The purpose of the present invention is to propose to a kind of schemes to solve the above problems, and arsenic is especially accelerated compared with active carbon
Adsorption dynamics adsorption kinetics, while the content of arsenic being made to decrease below 0.01mg/Nm3.The program utilizes the SILP (ionic liquid of load
Phase) bed, the SILP is the porous carrier usually prepared and being mutually immersed in carrier in selected ionic liquid.
It has been described before and mutually captures metal or the method for its oxide using the ionic liquid of load.However, they
Do not optimized for elimination arsenic.
US20140001100 discloses the method using ionic liquid from hydrocarbon fluid capturing element mercury.Suitable ionic liquid
Body includes organic cation, metal cation and anion.Ionic liquid has dual function.Firstly, the metal of ionic liquid
Cationic portion mercury oxide.Then, the mercury of oxidation unstable in its organic environment is effectively trapped in ionic liquid.
US20070123660 similarly relates to the side of the element of capture gaseous form or the mercury and lead of oxidation, zinc and cadmium
Method.It uses the combinations of ligand and ionic liquid.When needing capturing element substance, oxidant is added.
A kind of method for removing the arsenic oxide in technology waste gas is disclosed, the method includes keeping exhaust gas logical
The step of ionic liquid phase bed of overload, it is characterised in that the ionic liquid includes one or more selected from substitution、
Ammonium, imidazoles, pyrrolidinesAnd pyridineCation and it is one or more selected from chloride ion, bromide ion and carboxylate radical from
The anion of son.
Technology waste gas refers to from metallurgical smelting process or from the gas of other burning process.
Preferably, substitutedCation is according to formula [Pm n o p]+, and the ammonium cation replaced is according to formula
[Nm n o p]+, wherein substituent group is that the hydrocarbon chain containing m, n, o and p carbon atom, condition are when anion is halogen respectively
M+n+o+p > 10 when ion, the m+n+o+p < 30 when anion is carboxylic acid ion.
The hydrocarbon chain substituent of cation is preferably unbranched and saturation.Anion is preferably containing 1-8 carbon atom
Unbranched, unsaturated monocarboxylic radical ion.
Most preferred ionic liquid is [P6 6 6 14]Cl.The product is commercially available101。
This method is best suited for removing comprising As2O3And/or As2O5Arsenic oxide.
Preferably, the ionic liquid of load mutually includes the carrier phase selected from aluminium oxide, silica and active carbon.BET is big
In 50m2What the carrier of/g was mutually desirable to.The weight ratio of carrier phase and ionic liquid weight is most suitable between 3: 1 and 50: 1
's.
The advantages of disclosed method and relevant device, is:
The volume of adsorbent bed can be reduced；
Cleaning device itself can be more compact；
The pressure drop on adsorbent bed can be reduced.
Therefore, investment when investment can be lower than using active carbon, and reduce operating cost.
Depending on selected specific ionic liquid, this SILP can be with the element except absorption arsenic removal, these yuan
Element can also exist in gas phase, such as Zn, Hg, Cd, Pb, Sb and Se.For example, being confirmed as three hexyls-myristyl-chlorination[P6 6 6 14] Cl ionic liquid be very suitable to capture As, be also applied for capture Pb, Cu, Cd, Se and Zn.As use acetic acid 1-
Butyl -3- methylimidazole[C4C1im][C1CO2] when, also there is clear evidence to show the absorption of Sb and Se.Use active carbon base
Material tests these ionic liquids.
Supporting substrates should be ionic liquid wetting that is highly porous and should being designed.Typical candidate is two
Silica, aluminium oxide, titanium oxide, zirconium oxide, active carbon, porous polymer, zeolite and metal-organic framework.
When using arsenic-adsorbing as target, hence it is evident that the ionic liquid of preferred soluble a large amount of arsenic.
When the source exhaust gas by arsenic pollution is when metallurgical smelting process, discarded SILP can be recycled directly in the work
In skill.Then need to establish catch mechanism before SILP adsorption step to avoid the accumulation of the metal captured by SILP.Recycling
SILP can even is that valuable reactant.Such as when utilizing activated carbon substrates and the fire metallurgy process for needing reducing agent
Situation is such when processing.Similarly, silica or aluminum oxide base material can be recycled effectively in needing fluxing agent
To be formed in the technique of clinker.
In one embodiment, it was demonstrated that the capacity of SILP increases.
In order to prepare active carbon base SILP, using from ChemvironActive carbon WS 490.By 1 weight
Part ion liquid dissolving is in the methanol of 9 parts by volume.The solution is added in the active carbon of 9 parts by weight and is stood overnight with true
Protect absorption completely.Divide three steps to remove solvent: keeping 1.5h under 45 DEG C and 300mbar, is kept under 65 DEG C and 300mbar
1.5h keeps 1.5h under 65 DEG C and 250mbar.
In this way, using ionic liquid [P6 6 6 14] Cl and [C4C1im][C1CO2] production batch SILP.
BET is measured to characterize the specific surface area of SILP material obtained.According to the analysis, determined using BJH analysis
Kong Rong and aperture.These measurements are carried out using SILP sample of the nitrogen to untreated active carbon (AC) and above-mentioned preparation.This
It is reported in table 1.
Table 1: the BET result of untreated active carbon (AC) and SILP
| Material | Kong Rong (cm3g-1) | Pore area (m2g-1) |
| AC (uncoated) | 0.78 | 1191.8 |
| With 10 weight % [P6 6 6 14] Cl AC | 0.63 | 1021.4 |
| With 10 weight % [C4C1im][C1CO2] AC | 0.68 | 1088.7 |
The aperture of all three materials is also recorded.In all three materials, it is less thanAperture be main.This
It demonstrates after coating active carbon with ionic liquid, the persistence of pore structure.However, coating after these apertures ratio slightly
It reduces.It is therefore assumed that ionic liquid covers the inner hole of active carbon.
As is dissolved according to them2O3Ability select ionic liquid.The list is reported in table 2, and as temperature letter
Several saturation limits.
Table 2: the As in selected ionic liquid2O3Solubility
As can be drawn from Table 1, the coating of selected ionic liquid enables to the As of SILP absorption per ton about 10kg2O3.Assuming that
Activated carbon substrates also contribute adsorption capacity, can estimate that the total capacity of SILP is twice of independent active carbon capacity.It is this
The increase of capacity is first advantage being immersed in active carbon in selected ionic liquid.
In the second embodiment, it is shown that the adsorption dynamics adsorption kinetics of enhancing.
In the first step, two adsorption columns are prepared, one filled with unsoaked active carbon as reference, another filling
Have in [P as described in example 1 above6 6 6 14] active carbon that impregnates in Cl.Each column includes a small amount of mineral wool in bottom, is connect
Be steel mesh and the adsorbent material of 10g.Two layers of additional adsorbent material is added, every layer is all separated with steel mesh.Every layer of mean height
Degree is 1.63cm.Steel mesh and mineral wool are added in top layer, to stablize adsorbent bed.The internal diameter of column is about 4.2cm.
In second step, As will be contained2O3Gas be sent into column in.For this purpose, to from the effluent in the exhaust gas that lead blast furnace generates
It is sampled.After the first dust filter, gas is divided into three parallel air-flows.One air-flow is passed directly into a company
To analyze entrance concentration in string wash-bottle.To the As in wash-bottle2O3It is analyzed, so that determining input concentration.Other two strands
Air-flow passes through corresponding adsorption column.The outlet of each column is connected respectively to independent concatenated wash-bottle.It is dry after every group of series connection
Dry tower and pump, wherein the gas flow rate of per share air-flow is adjusted to 3L/ minutes.Gas temperature into column is about 140 DEG C.Test into
Row 48 hours.
As summarized in table 3, observe when the active carbon impregnated using ionic liquid replaces unsoaked active carbon, it is defeated
The concentration of arsenic out is reduced to 1/3.Since operating condition is identical, and since level is far below saturation effect, therefore, it is considered that from
Sub- liquid provides the adsorption dynamics adsorption kinetics of acceleration.This is the second advantage being immersed in active carbon in selected ionic liquid.
Even if using the substrate in addition to active carbon, such as silica or aluminium oxide, the advantage there is also.Table 3: arsenic absorption and yield
Claims (7)
1. a kind of for removing the As in technology waste gas2O3And/or As2O5Method, the method includes so that exhaust gas is passed through load
Ionic liquid phase bed the step of, it is characterised in that the ionic liquid include it is one or more selected from replaceAmmonium, imidazolesPyrrolidinesAnd pyridineCation and it is one or more selected from chloride ion, bromide ion and carboxylic acid ion yin from
Son.
2. according to the method described in claim 1, wherein described substitutedCation is according to formula [Pm n o p]+, and it is described
Substituted ammonium cation is according to formula [Nm n o p]+, wherein substituent group is the hydrocarbon containing m, n, o and p carbon atom respectively
Chain, condition are m+n+o+p > 10, the m+n+o+p when the anion is carboxylic acid ion when the anion is halogen ion
< 30.
3. method according to claim 1 or 2, it is characterised in that the carboxylic acid ion is containing 1-8 carbon atom
Unbranched, unsaturated monocarboxylic radical ion.
4. method described in any one of -3 according to claim 1, wherein the ionic liquid of the load mutually includes selected from oxygen
Change the carrier phase of aluminium, silica and active carbon.
5. according to the method described in claim 4, wherein the BET of the carrier phase is greater than 50m2/g。
6. method described in any one of -5 according to claim 1, wherein carrier phase and the weight ratio of ionic liquid be 3: 1 to
50∶1。
7. according to the method described in claim 6, wherein the technology waste gas is the exhaust gas from metallurgical smelting process, feature
It is mutually to recycle the ionic liquid of the load in the technique.
Applications Claiming Priority (3)
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| EP16202195.0 | 2016-12-05 | ||
| EP16202195 | 2016-12-05 | ||
| PCT/EP2017/081435 WO2018104257A1 (en) | 2016-12-05 | 2017-12-05 | Removal of arsenic from flue-gas |
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| EP (1) | EP3548163A1 (en) |
| JP (1) | JP2019535511A (en) |
| KR (1) | KR20190087630A (en) |
| CN (1) | CN110177611A (en) |
| AU (1) | AU2017371115A1 (en) |
| CA (1) | CA3043671A1 (en) |
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| WO2021231336A1 (en) * | 2020-05-12 | 2021-11-18 | W.L. Gore & Associates, Inc. | Sorbent polymer composites including phophonium halides, flue gas treatment devices and flue gas treatment methods utilizing the same |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4908191A (en) * | 1987-07-21 | 1990-03-13 | Ethyl Corporation | Removing arsine from gaseous streams |
| CN1356267A (en) * | 1990-10-30 | 2002-07-03 | 法国石油公司 | Process for removing arsenic or arsenic compound from fluid |
| KR20100042110A (en) * | 2008-10-15 | 2010-04-23 | 한국과학기술연구원 | Gas-absorbing ionic liquids containing a phosphorus group |
| CN103958052A (en) * | 2011-08-14 | 2014-07-30 | 布吕歇尔有限公司 | Filter materials for treating and purifying gases |
| US20160271559A1 (en) * | 2015-03-16 | 2016-09-22 | University Of Wyoming | Methods and Compositions for the Removal of Mercury From Gases |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8118916B2 (en) | 2005-10-21 | 2012-02-21 | The University Of Cincinnati | High capacity materials for capture of metal vapors from gas streams |
| GB2484301B8 (en) | 2010-10-05 | 2017-11-22 | The Queen's Univ Of Belfast | Process for removing metals from hydrocarbons |
| WO2014205200A1 (en) * | 2013-06-19 | 2014-12-24 | Calgon Carbon Corporation | Methods for mitigating the leaching of heavy metals from activated carbon |
| FR3009204B1 (en) * | 2013-07-31 | 2015-07-24 | IFP Energies Nouvelles | METHOD FOR CAPTURING HEAVY METAL CONTENT IN WET GAS WITH DILUTION OF WET GAS TO CONTROL RELATIVE GAS MOISTURE |
| CN103877844B (en) * | 2014-03-13 | 2016-01-13 | 华能国际电力股份有限公司 | Demercuration absorption liquid |
-
2017
- 2017-12-05 EA EA201991235A patent/EA201991235A1/en unknown
- 2017-12-05 KR KR1020197019391A patent/KR20190087630A/en not_active Withdrawn
- 2017-12-05 EP EP17808482.8A patent/EP3548163A1/en not_active Withdrawn
- 2017-12-05 WO PCT/EP2017/081435 patent/WO2018104257A1/en not_active Ceased
- 2017-12-05 CN CN201780074407.0A patent/CN110177611A/en active Pending
- 2017-12-05 AU AU2017371115A patent/AU2017371115A1/en not_active Abandoned
- 2017-12-05 CA CA3043671A patent/CA3043671A1/en not_active Abandoned
- 2017-12-05 JP JP2019530096A patent/JP2019535511A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4908191A (en) * | 1987-07-21 | 1990-03-13 | Ethyl Corporation | Removing arsine from gaseous streams |
| CN1356267A (en) * | 1990-10-30 | 2002-07-03 | 法国石油公司 | Process for removing arsenic or arsenic compound from fluid |
| KR20100042110A (en) * | 2008-10-15 | 2010-04-23 | 한국과학기술연구원 | Gas-absorbing ionic liquids containing a phosphorus group |
| CN103958052A (en) * | 2011-08-14 | 2014-07-30 | 布吕歇尔有限公司 | Filter materials for treating and purifying gases |
| US20160271559A1 (en) * | 2015-03-16 | 2016-09-22 | University Of Wyoming | Methods and Compositions for the Removal of Mercury From Gases |
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| EP3548163A1 (en) | 2019-10-09 |
| JP2019535511A (en) | 2019-12-12 |
| KR20190087630A (en) | 2019-07-24 |
| EA201991235A1 (en) | 2020-01-16 |
| WO2018104257A1 (en) | 2018-06-14 |
| CA3043671A1 (en) | 2018-06-14 |
| AU2017371115A1 (en) | 2019-05-30 |
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