KR20170041726A - 공정 오프가스 또는 엔진 배기가스를 정화하기 위한 방법 - Google Patents
공정 오프가스 또는 엔진 배기가스를 정화하기 위한 방법 Download PDFInfo
- Publication number
- KR20170041726A KR20170041726A KR1020177003389A KR20177003389A KR20170041726A KR 20170041726 A KR20170041726 A KR 20170041726A KR 1020177003389 A KR1020177003389 A KR 1020177003389A KR 20177003389 A KR20177003389 A KR 20177003389A KR 20170041726 A KR20170041726 A KR 20170041726A
- Authority
- KR
- South Korea
- Prior art keywords
- filter
- exhaust gas
- gas
- particulate filter
- particulate
- Prior art date
Links
- 238000000034 method Methods 0.000 title claims abstract description 29
- 238000004140 cleaning Methods 0.000 title 1
- 239000004071 soot Substances 0.000 claims abstract description 17
- 229910052751 metal Inorganic materials 0.000 claims abstract description 14
- 239000002184 metal Substances 0.000 claims abstract description 14
- 239000002956 ash Substances 0.000 claims abstract description 9
- 150000002736 metal compounds Chemical class 0.000 claims abstract description 7
- 239000007789 gas Substances 0.000 claims description 55
- 239000003054 catalyst Substances 0.000 claims description 19
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 claims description 18
- 239000013618 particulate matter Substances 0.000 claims description 18
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 17
- XHCLAFWTIXFWPH-UHFFFAOYSA-N [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] XHCLAFWTIXFWPH-UHFFFAOYSA-N 0.000 claims description 17
- 229910001935 vanadium oxide Inorganic materials 0.000 claims description 13
- 230000003647 oxidation Effects 0.000 claims description 12
- 238000007254 oxidation reaction Methods 0.000 claims description 12
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 10
- QGLKJKCYBOYXKC-UHFFFAOYSA-N nonaoxidotritungsten Chemical compound O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 QGLKJKCYBOYXKC-UHFFFAOYSA-N 0.000 claims description 8
- 229910001930 tungsten oxide Inorganic materials 0.000 claims description 7
- 239000003638 chemical reducing agent Substances 0.000 claims description 6
- 229910001385 heavy metal Inorganic materials 0.000 claims description 6
- 229930195733 hydrocarbon Natural products 0.000 claims description 6
- 150000002430 hydrocarbons Chemical class 0.000 claims description 6
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims description 6
- 238000007664 blowing Methods 0.000 claims description 5
- 238000002347 injection Methods 0.000 claims description 5
- 239000007924 injection Substances 0.000 claims description 5
- 229910052763 palladium Inorganic materials 0.000 claims description 5
- XTQHKBHJIVJGKJ-UHFFFAOYSA-N sulfur monoxide Chemical class S=O XTQHKBHJIVJGKJ-UHFFFAOYSA-N 0.000 claims description 5
- 238000010531 catalytic reduction reaction Methods 0.000 claims description 4
- 238000005201 scrubbing Methods 0.000 claims description 4
- 229910052815 sulfur oxide Inorganic materials 0.000 claims description 4
- 238000011144 upstream manufacturing Methods 0.000 claims description 4
- 239000012670 alkaline solution Substances 0.000 claims description 3
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 3
- 229910052721 tungsten Inorganic materials 0.000 claims description 3
- 239000010937 tungsten Substances 0.000 claims description 3
- 229910052720 vanadium Inorganic materials 0.000 claims description 3
- 229910000505 Al2TiO5 Inorganic materials 0.000 claims description 2
- 229910052878 cordierite Inorganic materials 0.000 claims description 2
- JSKIRARMQDRGJZ-UHFFFAOYSA-N dimagnesium dioxido-bis[(1-oxido-3-oxo-2,4,6,8,9-pentaoxa-1,3-disila-5,7-dialuminabicyclo[3.3.1]nonan-7-yl)oxy]silane Chemical compound [Mg++].[Mg++].[O-][Si]([O-])(O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2)O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2 JSKIRARMQDRGJZ-UHFFFAOYSA-N 0.000 claims description 2
- KZHJGOXRZJKJNY-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Si]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O KZHJGOXRZJKJNY-UHFFFAOYSA-N 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- 229910052863 mullite Inorganic materials 0.000 claims description 2
- AABBHSMFGKYLKE-SNAWJCMRSA-N propan-2-yl (e)-but-2-enoate Chemical compound C\C=C\C(=O)OC(C)C AABBHSMFGKYLKE-SNAWJCMRSA-N 0.000 claims description 2
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 claims description 2
- 229910010271 silicon carbide Inorganic materials 0.000 claims description 2
- 239000004408 titanium dioxide Substances 0.000 claims description 2
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 2
- 239000011236 particulate material Substances 0.000 description 6
- 239000012855 volatile organic compound Substances 0.000 description 6
- 239000003921 oil Substances 0.000 description 5
- 238000010926 purge Methods 0.000 description 5
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 description 4
- 238000001914 filtration Methods 0.000 description 4
- 229910017840 NH 3 Inorganic materials 0.000 description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 3
- 229910005965 SO 2 Inorganic materials 0.000 description 3
- 238000002485 combustion reaction Methods 0.000 description 3
- 239000000295 fuel oil Substances 0.000 description 3
- 238000000746 purification Methods 0.000 description 3
- 238000006722 reduction reaction Methods 0.000 description 3
- 239000010936 titanium Substances 0.000 description 3
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- -1 NO x Substances 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- 229910002091 carbon monoxide Inorganic materials 0.000 description 2
- 239000004568 cement Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000003344 environmental pollutant Substances 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 229910010272 inorganic material Inorganic materials 0.000 description 2
- 239000011147 inorganic material Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 231100000719 pollutant Toxicity 0.000 description 2
- 230000000717 retained effect Effects 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 150000003464 sulfur compounds Chemical class 0.000 description 2
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N Furan Chemical compound C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 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 description 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 229910021541 Vanadium(III) oxide Inorganic materials 0.000 description 1
- 229910021542 Vanadium(IV) oxide Inorganic materials 0.000 description 1
- QUEDYRXQWSDKKG-UHFFFAOYSA-M [O-2].[O-2].[V+5].[OH-] Chemical compound [O-2].[O-2].[V+5].[OH-] QUEDYRXQWSDKKG-UHFFFAOYSA-M 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- OVHDZBAFUMEXCX-UHFFFAOYSA-N benzyl 4-methylbenzenesulfonate Chemical compound C1=CC(C)=CC=C1S(=O)(=O)OCC1=CC=CC=C1 OVHDZBAFUMEXCX-UHFFFAOYSA-N 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- TXKMVPPZCYKFAC-UHFFFAOYSA-N disulfur monoxide Inorganic materials O=S=S TXKMVPPZCYKFAC-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 239000003595 mist Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 125000005575 polycyclic aromatic hydrocarbon group Chemical group 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000013535 sea water Substances 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-L sulfite Chemical class [O-]S([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-L 0.000 description 1
- 229910001934 tungsten pentoxide Inorganic materials 0.000 description 1
- ZNOKGRXACCSDPY-UHFFFAOYSA-N tungsten(VI) oxide Inorganic materials O=[W](=O)=O ZNOKGRXACCSDPY-UHFFFAOYSA-N 0.000 description 1
- GRUMUEUJTSXQOI-UHFFFAOYSA-N vanadium dioxide Chemical compound O=[V]=O GRUMUEUJTSXQOI-UHFFFAOYSA-N 0.000 description 1
- IBYSTTGVDIFUAY-UHFFFAOYSA-N vanadium monoxide Chemical compound [V]=O IBYSTTGVDIFUAY-UHFFFAOYSA-N 0.000 description 1
- 238000009423 ventilation Methods 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
- B01D53/92—Chemical or biological purification of waste gases of engine exhaust gases
- B01D53/94—Chemical or biological purification of waste gases of engine exhaust gases by catalytic processes
- B01D53/9459—Removing one or more of nitrogen oxides, carbon monoxide, or hydrocarbons by multiple successive catalytic functions; systems with more than one different function, e.g. zone coated catalysts
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- B01D46/0061—
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D46/00—Filters or filtering processes specially modified for separating dispersed particles from gases or vapours
- B01D46/66—Regeneration of the filtering material or filter elements inside the filter
- B01D46/70—Regeneration of the filtering material or filter elements inside the filter by acting counter-currently on the filtering surface, e.g. by flushing on the non-cake side of the filter
- B01D46/71—Regeneration of the filtering material or filter elements inside the filter by acting counter-currently on the filtering surface, e.g. by flushing on the non-cake side of the filter with pressurised gas, e.g. pulsed air
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- B01D46/00—Filters or filtering processes specially modified for separating dispersed particles from gases or vapours
- B01D46/66—Regeneration of the filtering material or filter elements inside the filter
- B01D46/80—Chemical processes for the removal of the retained particles, e.g. by burning
- B01D46/82—Chemical processes for the removal of the retained particles, e.g. by burning with catalysts
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- 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
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- B01D53/34—Chemical or biological purification of waste gases
- B01D53/92—Chemical or biological purification of waste gases of engine exhaust gases
- B01D53/94—Chemical or biological purification of waste gases of engine exhaust gases by catalytic processes
- B01D53/9404—Removing only nitrogen compounds
- B01D53/9409—Nitrogen oxides
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
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- B01D53/34—Chemical or biological purification of waste gases
- B01D53/92—Chemical or biological purification of waste gases of engine exhaust gases
- B01D53/94—Chemical or biological purification of waste gases of engine exhaust gases by catalytic processes
- B01D53/9404—Removing only nitrogen compounds
- B01D53/9409—Nitrogen oxides
- B01D53/9413—Processes characterised by a specific catalyst
- B01D53/9418—Processes characterised by a specific catalyst for removing nitrogen oxides by selective catalytic reduction [SCR] using a reducing agent in a lean exhaust gas
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01D53/34—Chemical or biological purification of waste gases
- B01D53/92—Chemical or biological purification of waste gases of engine exhaust gases
- B01D53/94—Chemical or biological purification of waste gases of engine exhaust gases by catalytic processes
- B01D53/944—Simultaneously removing carbon monoxide, hydrocarbons or carbon making use of oxidation catalysts
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01D53/94—Chemical or biological purification of waste gases of engine exhaust gases by catalytic processes
- B01D53/9459—Removing one or more of nitrogen oxides, carbon monoxide, or hydrocarbons by multiple successive catalytic functions; systems with more than one different function, e.g. zone coated catalysts
- B01D53/9477—Removing one or more of nitrogen oxides, carbon monoxide, or hydrocarbons by multiple successive catalytic functions; systems with more than one different function, e.g. zone coated catalysts with catalysts positioned on separate bricks, e.g. exhaust systems
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
- B01J21/063—Titanium; Oxides or hydroxides thereof
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- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/20—Vanadium, niobium or tantalum
- B01J23/22—Vanadium
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- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/24—Chromium, molybdenum or tungsten
- B01J23/30—Tungsten
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
- B01J23/44—Palladium
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/56—Platinum group metals
- B01J23/64—Platinum group metals with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
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- B01J23/6527—Tungsten
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- B01J35/19—
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- B01J35/56—
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
- F01N—GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR MACHINES OR ENGINES IN GENERAL; GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR INTERNAL COMBUSTION ENGINES
- F01N13/00—Exhaust or silencing apparatus characterised by constructional features ; Exhaust or silencing apparatus, or parts thereof, having pertinent characteristics not provided for in, or of interest apart from, groups F01N1/00 - F01N5/00, F01N9/00, F01N11/00
- F01N13/009—Exhaust or silencing apparatus characterised by constructional features ; Exhaust or silencing apparatus, or parts thereof, having pertinent characteristics not provided for in, or of interest apart from, groups F01N1/00 - F01N5/00, F01N9/00, F01N11/00 having two or more separate purifying devices arranged in series
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
- F01N—GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR MACHINES OR ENGINES IN GENERAL; GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR INTERNAL COMBUSTION ENGINES
- F01N13/00—Exhaust or silencing apparatus characterised by constructional features ; Exhaust or silencing apparatus, or parts thereof, having pertinent characteristics not provided for in, or of interest apart from, groups F01N1/00 - F01N5/00, F01N9/00, F01N11/00
- F01N13/009—Exhaust or silencing apparatus characterised by constructional features ; Exhaust or silencing apparatus, or parts thereof, having pertinent characteristics not provided for in, or of interest apart from, groups F01N1/00 - F01N5/00, F01N9/00, F01N11/00 having two or more separate purifying devices arranged in series
- F01N13/0093—Exhaust or silencing apparatus characterised by constructional features ; Exhaust or silencing apparatus, or parts thereof, having pertinent characteristics not provided for in, or of interest apart from, groups F01N1/00 - F01N5/00, F01N9/00, F01N11/00 having two or more separate purifying devices arranged in series the purifying devices are of the same type
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
- F01N—GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR MACHINES OR ENGINES IN GENERAL; GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR INTERNAL COMBUSTION ENGINES
- F01N13/00—Exhaust or silencing apparatus characterised by constructional features ; Exhaust or silencing apparatus, or parts thereof, having pertinent characteristics not provided for in, or of interest apart from, groups F01N1/00 - F01N5/00, F01N9/00, F01N11/00
- F01N13/011—Exhaust or silencing apparatus characterised by constructional features ; Exhaust or silencing apparatus, or parts thereof, having pertinent characteristics not provided for in, or of interest apart from, groups F01N1/00 - F01N5/00, F01N9/00, F01N11/00 having two or more purifying devices arranged in parallel
- F01N13/017—Exhaust or silencing apparatus characterised by constructional features ; Exhaust or silencing apparatus, or parts thereof, having pertinent characteristics not provided for in, or of interest apart from, groups F01N1/00 - F01N5/00, F01N9/00, F01N11/00 having two or more purifying devices arranged in parallel the purifying devices are arranged in a single housing
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
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Abstract
공정 오프가스 또는 엔진 배기가스에 존재하는 NOx 및 SOx의 제거와 함께 그을음, 재 및 금속 또는 금속 화합물을 제거하는 방법.
Description
본 발명은 공정 오프가스 또는 엔진 배기가스에 존재하는 재, 그을음, 중금속, 금속 및 금속 화합물 형태의 미립자 물질과 질소 산화물(NOx)을 제거하는 방법에 관한 것이다. 특히 본 발명은 시멘트 또는 유리 제조로부터의 공정 오프가스와 중유로 작동되는 엔진의 배기가스로부터 이들 성분을 제거하는데 유용하다.
이들 입자-함유 가스들은 아주 흔히 복수의 오염원, 예를 들어 NOx, 휘발성 유기 화합물(VOC), SO2, CO, Hg, NH3, 다방향족 탄화수소(PAH's), 디옥산 및 푸란을 함유하는데, 이것들은 농도에 있어서 지역적 규제에 따라 감소되어야 한다.
그을음 및 재는 전형적으로 배기 또는 환기 시스템에 배열된 하나 이상의 필터를 통해서 가스가 통과함으로써 포집되고 제거된다. 스트림 상에서 특정 시간 후 그을음과 재의 포집된 양은 필터 전체에서 증가하는 압력 강하를 야기하며, 필터는 그을음을 연소시키고 압축 공기로 또는 수동 공정에 의해 재 및 다른 무기 미립자 물질을 불어날림으로써 재생되어야 할 필요가 있다.
공지된 미립자 필터 시스템은 비교적 낮은 함량의 황 화합물과 미립자 물질을 가진 오프가스 및 배기가스를 위해 개발되어 있다. 이들 시스템은, 예를 들어 중유, 소위 말하는 벙커유가 연료인 선박용 엔진과, 예를 들어 시멘트 및 유리 제조로부터의 높은 함량의 미립자 물질을 가진 공정 오프가스에는 이용될 수 없다.
벙커유는 매우 무거운 탄화수소들과 다방향족 화합물들을 함유한다. 이 오일은 화합물들로 심하게 오염되어 있는데 이것은 연소되지 않고 배기가스에 재로서 남는다. 벙커유에 함유된 추가의 오염물질은 수용성 금속염들 나트륨(Na), 칼륨(K), 칼슘(Ca), 철(Fe), 금속 황산염(MeSO4) 등뿐만 아니라 지용성 금속들 바나듐(V), 납(Pb), 니켈(Ni) 등을 포함한다.
NOx, VOC, PAH's, 디옥산 및 푸란 같은 가스상 오염물질의 경감은 촉매와의 접촉에 의해서 효과적으로 수행될 수 있다. 특히, 산화바나듐계 촉매는 고정식 및 자동차 용도에서 NH3로 NOx의 선택적 환원에 의한 NOx 감소를 위해 통상 사용되는 촉매이다.
본 발명의 일반적인 목적은 오프가스 또는 배기가스로부터 NOx 및 VOC의 제거와 함께 재와 그을음의 형태인 미립자 물질의 경감을 위한 방법을 제공하는 것이며, 상기 방법은, 이 방법에 이용된 미립자 필터가 재생되어야 할 필요가 있을 때조차도 효과적인 정화 및 연속 작동을 보장한다.
상기 논의된 대로, 공정 오프가스 및 엔진 배기가스에서 미립자 물질은 무기 재를 더 함유하며, 이것은 연소될 수 없어서 경시적으로 필터에 축적되며 압력 강하를 강화시킨다. 결과적으로, 무기 재와 잔류량의 그을음은 필터를 통한 배기가스의 흐름 방향을 주기적으로 역전시키거나 공기의 충격적 분사에 의해 재와 그을음을 불어날림으로써 제거되어야 한다.
본 발명의 본질적인 특징은 NOx의 선택적 촉매 환원(SCR)에서 활성이며 동시에 그을음 연소 및 VOC 산화를 가속하는 촉매로 필터를 촉매화함에 의한 미립자 필터의 수동적 그을음 재생을 동반한 가스상 불순물들의 연속 제거이며, 이로써 미립자 필터 전체에서 압력 강하를 낮게 유지하고 필터의 출구에 공기를 펄스 분사하여 미립자 물질을 주기적으로 그리고 효과적으로 불어날림으로써 여과 과정이 개선된다.
요약하면, 본 발명은 공정 오프가스 또는 엔진 배기가스에 존재하는 탄화수소 및 질소 산화물과 함께 그을음, 재, 금속 및 금속 화합물의 형태인 미립자 물질의 제거를 위한 방법을 제공하며, 이 방법은
질소성 환원제를 함유하거나 오프가스 또는 배기가스에 질소성 환원제를 첨가한 공정 오프가스 또는 엔진 배기가스를 제공하는 단계;
225℃ 내지 550℃의 가스 온도에서 적어도 하나의 미립자 필터를 각각 포함하는 적어도 하나의 필터 유닛을 통해서 오프가스 또는 배기가스를 통과시키고 미립자 물질을 포집하는 단계;
미립자 필터에 배열된 조합된 SCR과 산화 촉매와의 접촉시 질소성 환원제로의 선택적 촉매 환원(SCR) 및 산화에 의해 적어도 하나의 미립자 필터 상에 포집된 그을음의 양을 감소시키고 오프가스 또는 배기가스에서 질소 산화물 및 탄화수소의 양을 감소시키는 단계;
적어도 하나의 필터 유닛을 오프가스 또는 배기가스의 흐름으로부터 주기적으로 단절시키는 단계;
배기가스의 앞선 흐름에 역으로 출구에 공기를 펄스 분사해서 적어도 하나의 미립자 필터의 출구에 공압 펄스를 적용하고 적어도 하나의 미립자 필터로부터 포집된 미립자 물질을 중금속과 함께 불어날리는 단계;
적어도 하나의 미립자 필터의 입구에 흡인을 적용하는 단계, 및
적어도 하나의 미립자 필터로부터 불어날려진 미립자 물질과 중금속을, 선택적으로 외부 보조 필터 유닛을 통해서, 용기로 이송하는 단계
를 포함하고, 여기서 조합된 SCR과 산화 촉매는 이산화티타늄, 바나듐 및 텅스텐의 산화물로 구성된다.
바람직한 실시형태들을 이하에 개시한다. 이들 실시형태는 각각 단독으로 또는 조합으로 이용될 수 있다.
본 발명에서 사용하기 위한 미립자 필터는 바람직하게 탄화규소, 코디어라이트, 뮬라이트, 알루미늄 티타네이트 또는 소결 금속으로 제조된다.
전형적으로, 본 발명에서 사용하기 위한 필터는 최고의 정화 효율을 보장하는 벽유동형 필터로서 성형되지만, 다른 필터 종류도 이용될 수 있다.
촉매는 필터 벽 위에 및/또는 내부에 코팅된다.
촉매 활성 물질은 바나듐 산화물, 텅스텐 산화물 및 티타니아로 구성되는 촉매 조성물이며, 이것은 이후 "V/W/Ti 촉매"라고 칭해진다.
용어 "어떤 바나듐 산화물" 또는 "바나듐 산화물"은 산화바나듐(II)(일산화바나듐), VO; 또는 산화바나듐(III)(바나듐세스퀴옥시드 또는 삼산화바나듐), V2O3; 또는 산화바나듐(IV)(이산화바나듐), VO2; 또는 산화바나듐(V)(오산화바나듐), V2O5을 말한다.
바람직하게, 본 발명에서 사용하기 위한 바나듐 산화물은 산화바나듐(V)(오산화바나듐), V2O5을 포함하거나 그것으로 구성된다.
텅스텐은 몇 개의 산화 상태를 가지며, 따라서 다음의 산화물들이 있다:
산화텅스텐(III)
산화텅스텐(IV)
산화텅스텐(VI)
오산화텅스텐.
본 발명에서 사용하기 위한 바람직한 텅스텐 산화물은 산화텅스텐(VI) WO3를 포함하거나 그것으로 구성된다.
용어 "티타니아"는 이산화티타늄(TiO2)을 말한다.
이 촉매는 탄화수소(VOC)의 제거와 NH3와의 SCR 반응에 의한 NOx의 제거에서 모두 활성이다.
추가의 실시형태에서, V/W/Ti SCR 촉매는 벽유동 필터의 가스 입구측 상에, 그리고 벽 내부에 코팅되고, 바나듐 산화물과 금속 및/또는 산화물 형태의 팔라듐과 티타니아로 구성되거나 또는 바나듐 산화물, 텅스텐 산화물 및 금속 및/또는 산화물 형태의 팔라듐과 티타니아로 구성되는 추가의 촉매 조성물은 벽유동 필터의 가스 출구측에 코팅된다.
필터의 출구측에 V/W/Ti/Pd 또는 V/Ti/Pd 촉매를 제공하는 것의 이점은 필터로부터 암모니아 및 일산화탄소의 낮은 슬립이다.
상기 언급된 대로, 본 발명의 더 이상의 본질적인 특징은 중유의 연소 동안 형성된 포착된 미립자 물질의 제거이다. 미립자 필터는 배기가스 흐름으로부터 필터를 차단함으로써 주기적으로 정화되어야 한다.
바람직하게, 오프가스 또는 배기가스는 1개보다 많은 필터 유닛을 통해서 통과된다. 다음에, 모든 필터 유닛은 이후 더 상세히 설명되는 본 발명에 따른 방법에 의한 순환 정화 루프에서 정화될 수 있다. 적어도 하나의 필터 유닛은 여과 방식을 유지하기 때문에 엔진은 연속 작동 상태를 유지할 수 있다.
미립자 필터의 정화 동안 10 내지 600 msec, 바람직하게 300 msec의 분사 펄스 지속기간으로 배기가스의 앞선 흐름에 역으로 공기가 분사된다.
정화 사이클에서 미립자 필터 또는 필터 유닛의 구역(전체 여과 표면의 5-50%)은 출구에서 폐쇄되고, 예를 들어 폐쇄 밸브 상에 또는 근처에 장착된 밸브 또는 노즐에 의해 출구에 공기가 분사된다. 이렇게 미립자 필터에 포착된 재, 미연소 그을음 및 중금속, 금속, 금속 화합물을 포함하는 미립자 물질을 불어날리는 것은 출구가 개방되는 방식과 비교하여 미립자 필터에 분사되는 공기 펄스의 부피가 더 적기 때문에 더욱더 효과적이다. 후자의 경우, 공기 펄스는 미립자 필터/들을 감싸고 있는 전체 필터 유닛에 전체적으로 전파되고, 따라서 정화 효과를 제한한다.
또는 달리, 각 미립자 필터의 출구는 더욱 강력한 공기 분사 펄스를 사용하여 정화 사이클 동안 개방될 수 있다. 이 실시형태의 이점은 단순성과 더욱 컴팩트한 필터 배열이다.
정화되어야 하는 미립자 필터에 공압 분사 펄스 동안, 높은 농도의 미립자 물질을 가진 정화할 공기 스트림이 미립자 필터의 입구측으로부터 빠져나가고, 이 공기 스트림은 적절한 흡인 시스템에 의해서 포집된다. 다음에, 불어날려진 미립자 물질을 함유하는 공기 스트림은, 선택적으로 미립자 필터의 입구나 입구 근처에 설치된 천공 격자판을 구비한, 흡인 파이프를 통해서 미립자 필터의 입구로부터 멀리 이송된다. 흡인 파이프는 흡인원, 예를 들어 흡인 펌프에 연결되고, 이것은 공기 펄스가 미립자 필터의 출구에 분사되는 동안이나 그 이후에 활성화된다.
미립자 물질은, 선택적으로 상기 설명된 바와 같은 그을음 연소 촉매로 촉매화된, 외부 보조 저온 필터 또는 보조 고온 필터 또는 둘 다를 통해서 흡인 파이프에 흡인될 수 있다. 이로써 주 미립자 필터로부터 제거된 정화하는 공기 스트림에 함유된 미립자 물질은 보조 필터/들에서 스트림으로부터 분리되고, 이후 장차의 폐기를 위해 저장 용기에 배출된다.
또는 달리, 흡인원은 소형 보조 필터가 구비된 외부 흡인 펌프에 의해 이루어질 수 있다. 이 보조 필터는 흡인 가스 유동 라인에서 공기 스트림에 보유된 입자를 수집한다.
또는 달리, 흡인 스트림은 또한 미립자 필터/들을 가로지른 압력 강하를 이용하여 생성될 수 있다. 이 실시형태에서, 흡인 파이프는 필터 유닛/들 또는 미립자 필터/들의 배기가스 입구측을 필터 유닛/들 또는 미립자 필터/들로부터의 배기가스 출구측과 연결하고, 미립자 필터/들로부터 불어날려진 미립자 물질은 흡인 파이프에 설치된 보조 필터를 통해서 흡인된다. 정화 사이클이 중단된 때, 포집된 미립자 물질은 보조 필터로부터 제거될 수 있다.
흡인 파이프에 적용되는 압력은 흡인 파이프에서 미립자 물질의 효율적인 수송을 보장할 만큼 충분히 낮아야 한다.
바람직하게, 흡인 파이프에서 압력은 미립자 필터 내부의 압력보다 30-300 mbar 아래의 범위이다.
본 발명의 추가의 실시형태에서, 펄스 분사를 위한 공기는 4 내지 10 bar abs, 바람직하게는 6.5 bar abs의 압력에서 압축 공기를 가진 축압기 탱크로부터 인출된다.
또 다른 실시형태에서, 유닛/들은 엔진 터보차저 상류의 압력 용기에 배열된다. 다음에, 배기가스는 0 내지 3 bar abs의 압력에서 필터 유닛/들을 통해서 통과될 수 있다.
이 실시형태에서, 그을음 연소 온도는 추가의 배기가스 가열 없이 더욱 최적 수준인 약 400℃에서 유지될 수 있다. 추가의 이점으로서, 미립자 필터(들) 전체에서 압력 강하가 배기가스의 압력 및 온도가 증가할 때 감소된다. 이것은 유익하게 효과적인 여과에 필요한 감소된 미립자 필터 부피를 가져오고, 예를 들어 배기가스 처리를 위한 제한된 공간을 가진 선박 상의 레트로피트 설치를 용이하게 한다.
상기 개시된 본 발명의 더 이상의 특징은 공정 오프가스에서 형성되는 황 산화물 및 엔진에서 중유가 연소할 때 형성되는 황 산화물을 제거할 수 있는 가능성이다. 필터에서 상류 SCR 및 산화 촉매는 황 화합물에 대해 내성이고, 제한된 SO2 내지 SO3 산화 가능성을 가지며, 따라서 SO2 및 SO3 제거를 위한 SOx 스크러버의 사용을 용이하게 한다.
따라서, 추가의 실시형태에서, 본 방법은 수성 알칼리성 용액 또는 해수 중의 알칼리성 용액을 포함하는 스크러빙 액체를 가진 적어도 하나의 필터 유닛의 하류에서 개방된 또는 폐쇄된 루프에서 가스를 스크러빙함으로써 가스에 함유된 황 산화물의 양을 감소시키는 추가의 단계를 포함한다. 알칼리성 스크러빙 액체에서 황 산화물은 무해한 알칼리성 금속 황산염 또는 아황산염으로 전환된다. 황 산화물은 이로써 어떠한 황산 미스트도 없이 오프가스로부터 거의 완전히 제거되고, 투명한 낮은 탁도의 소비된 용액은 추후의 폐기를 위해 보관된다.
Claims (11)
- 공정 오프가스 또는 엔진 배기가스에 존재하는 탄화수소 및 질소 산화물과 함께 그을음, 재, 금속 및 금속 화합물의 형태인 미립자 물질을 제거하는 방법으로서,
질소성 환원제를 함유하거나 오프가스 또는 배기가스에 질소성 환원제를 첨가한 공정 오프가스 또는 엔진 배기가스를 제공하는 단계;
225℃ 내지 550℃의 가스 온도에서 적어도 하나의 미립자 필터를 각각 포함하는 적어도 하나의 필터 유닛을 통해서 오프가스 또는 배기가스를 통과시키고 미립자 물질을 포집하는 단계;
미립자 필터에 배열된 적어도 제1의 조합된 SCR과 산화 촉매와의 접촉시 질소성 환원제로의 선택적 촉매 환원(SCR) 및 산화에 의해 적어도 하나의 미립자 필터 상에 포집된 그을음의 양을 감소시키고 오프가스 또는 배기가스에서 질소 산화물 및 탄화수소의 양을 감소시키는 단계;
적어도 하나의 필터 유닛을 오프가스 또는 배기가스의 흐름으로부터 주기적으로 단절시키는 단계;
배기가스의 앞선 흐름에 역으로 출구에 공기를 펄스 분사해서 적어도 하나의 미립자 필터의 출구에 공압 펄스를 적용하고 적어도 하나의 미립자 필터로부터 포집된 미립자 물질을 중금속 및 금속 화합물과 함께 불어날리는 단계;
적어도 하나의 미립자 필터의 입구에 흡인을 적용하는 단계, 및
적어도 하나의 미립자 필터로부터 불어날려진 미립자 물질과 중금속 및 금속 화합물을, 선택적으로 외부 보조 필터 유닛을 통해서, 용기로 이송하는 단계
를 포함하고, 여기서 적어도 제1의 조합된 SCR과 산화 촉매는 이산화티타늄, 바나듐 및 텅스텐의 산화물로 구성되는, 방법. - 제 1 항에 있어서, 적어도 하나의 미립자 필터는 벽유동 필터의 형태인 것을 특징으로 하는 방법.
- 제 2 항에 있어서, 적어도 제1의 조합된 SCR과 산화 촉매는 벽유동 필터의 가스 입구측의 벽 상에 또는 내부에 코팅되는 것을 특징으로 하는 방법.
- 제 1 항 내지 제 3 항 중 어느 한 항에 있어서, 바나듐 산화물과 금속 및/또는 산화물 형태의 팔라듐과 티타니아로 구성되거나 또는 바나듐 산화물, 텅스텐 산화물 및 금속 및/또는 산화물 형태의 팔라듐과 티타니아로 구성된 제2 산화 촉매가 적어도 하나의 미립자 필터의 가스 출구측에 코팅되는 것을 특징으로 하는 방법.
- 제 1 항 내지 제 4 항 중 어느 한 항에 있어서, 적어도 하나의 미립자 필터의 본체는 탄화규소, 코디어라이트, 뮬라이트, 알루미늄 티타네이트 또는 소결 금속으로 제조되는 것을 특징으로 하는 방법.
- 제 1 항 내지 제 5 항 중 어느 한 항에 있어서, 공기는 10 내지 600 msec, 바람직하게는 300 msec의 분사 펄스 지속기간으로 펄스 분사되는 것을 특징으로 하는 방법.
- 제 1 항 또는 제 6 항에 있어서, 펄스 분사를 위한 공기는 4 내지 10 bar abs, 바람직하게는 6.5 bar abs의 압력에서 압축 공기를 가진 축압기 탱크로부터 인출되는 것을 특징으로 하는 방법.
- 제 1 항 내지 제 7 항 중 어느 한 항에 있어서, 적어도 하나의 필터 유닛은 엔진 터보차저 상류의 압력 용기에 배열되는 것을 특징으로 하는 방법.
- 제 8 항에 있어서, 배기가스는 0 내지 3 bar abs의 압력에서 적어도 하나의 필터 유닛을 통해서 통과되는 것을 특징으로 하는 방법.
- 제 1 항 내지 제 9 항 중 어느 한 항에 있어서, 적어도 하나의 필터 유닛의 하류에서 오프가스 또는 배기가스 중의 질소 산화물의 추가적인 선택적 촉매 환원의 추가 단계를 포함하는 것을 특징으로 하는 방법.
- 제 1 항 내지 제 10 항 중 어느 한 항에 있어서, 적어도 하나의 필터 유닛의 하류에서, 개방되거나 폐쇄된 루프에서 알칼리성 용액 또는 물로 가스를 스크러빙함으로써 배기가스에 함유된 황 산화물의 양을 감소시키는 추가 단계를 포함하는 것을 특징으로 하는 방법.
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CN106574536A (zh) | 2017-04-19 |
US20170216771A1 (en) | 2017-08-03 |
JP2017528637A (ja) | 2017-09-28 |
KR102266312B1 (ko) | 2021-06-18 |
JP6571761B2 (ja) | 2019-09-04 |
WO2016029926A1 (en) | 2016-03-03 |
EP3194737B1 (en) | 2020-06-17 |
ES2818083T3 (es) | 2021-04-09 |
CA2955211A1 (en) | 2016-03-03 |
KR20170043514A (ko) | 2017-04-21 |
EP3194736A1 (en) | 2017-07-26 |
CA2954013A1 (en) | 2016-03-03 |
CA2955211C (en) | 2020-06-02 |
US20170211441A1 (en) | 2017-07-27 |
CN106605045A (zh) | 2017-04-26 |
US10286360B2 (en) | 2019-05-14 |
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