KR940019353A - 가스 혼합물의 반응물을 변환시키는 촉매변환기 - Google Patents

가스 혼합물의 반응물을 변환시키는 촉매변환기 Download PDF

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KR940019353A
KR940019353A KR1019940002781A KR19940002781A KR940019353A KR 940019353 A KR940019353 A KR 940019353A KR 1019940002781 A KR1019940002781 A KR 1019940002781A KR 19940002781 A KR19940002781 A KR 19940002781A KR 940019353 A KR940019353 A KR 940019353A
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catalytic
catalytic converter
gas mixture
flow direction
reaction
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로타르 발링
클라우스 휘텐호퍼
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디터 크리스트, 게르하르트 퀼
지멘스 악티엔게젤샤프트
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Publication of KR940019353A publication Critical patent/KR940019353A/ko

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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
    • F01N3/00—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust
    • F01N3/08—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous
    • F01N3/10—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous by thermal or catalytic conversion of noxious components of exhaust
    • F01N3/18—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous by thermal or catalytic conversion of noxious components of exhaust characterised by methods of operation; Control
    • F01N3/20—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous by thermal or catalytic conversion of noxious components of exhaust characterised by methods of operation; Control specially adapted for catalytic conversion ; Methods of operation or control of catalytic converters
    • F01N3/2066—Selective catalytic reduction [SCR]
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
    • B01D53/86—Catalytic processes
    • B01D53/8621—Removing nitrogen compounds
    • B01D53/8625—Nitrogen oxides
    • B01D53/8628—Processes characterised by a specific catalyst
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
    • B01D53/86—Catalytic processes
    • B01D53/8621—Removing nitrogen compounds
    • B01D53/8625—Nitrogen oxides
    • B01D53/8631—Processes characterised by a specific device
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
    • B01D53/86—Catalytic processes
    • B01D53/864—Removing carbon monoxide or hydrocarbons
    • 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
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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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
    • B01D53/9459—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
    • 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
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • 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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    • 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
    • B01J23/16—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
    • B01J23/28—Molybdenum
    • 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
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • 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
    • 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
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/19—Catalysts containing parts with different compositions
    • 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
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
    • B01J35/56—Foraminous structures having flow-through passages or channels, e.g. grids or three-dimensional monoliths
    • 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
    • F01N13/0097—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 arranged in a single housing
    • 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
    • F01N3/00—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust
    • F01N3/08—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous
    • F01N3/10—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous by thermal or catalytic conversion of noxious components of exhaust
    • F01N3/18—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous by thermal or catalytic conversion of noxious components of exhaust characterised by methods of operation; Control
    • F01N3/20—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous by thermal or catalytic conversion of noxious components of exhaust characterised by methods of operation; Control specially adapted for catalytic conversion ; Methods of operation or control of catalytic converters
    • F01N3/206—Adding periodically or continuously substances to exhaust gases for promoting purification, e.g. catalytic material in liquid form, NOx reducing agents
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
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    • F01N3/00—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust
    • F01N3/08—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous
    • F01N3/10—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous by thermal or catalytic conversion of noxious components of exhaust
    • F01N3/24—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous by thermal or catalytic conversion of noxious components of exhaust characterised by constructional aspects of converting apparatus
    • F01N3/28—Construction of catalytic reactors
    • F01N3/2803—Construction of catalytic reactors characterised by structure, by material or by manufacturing of catalyst support
    • F01N3/2825—Ceramics
    • F01N3/2828—Ceramic multi-channel monoliths, e.g. honeycombs
    • 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
    • F01N3/00—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust
    • F01N3/08—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous
    • F01N3/10—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous by thermal or catalytic conversion of noxious components of exhaust
    • F01N3/24—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous by thermal or catalytic conversion of noxious components of exhaust characterised by constructional aspects of converting apparatus
    • F01N3/28—Construction of catalytic reactors
    • F01N3/2882—Catalytic reactors combined or associated with other devices, e.g. exhaust silencers or other exhaust purification devices
    • F01N3/2889—Catalytic reactors combined or associated with other devices, e.g. exhaust silencers or other exhaust purification devices with heat exchangers in a single housing
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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
    • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/32—Details relating to packing elements in the form of grids or built-up elements for forming a unit of module inside the apparatus for mass or heat transfer
    • B01J2219/322—Basic shape of the elements
    • B01J2219/32296—Honeycombs
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • F01N2610/00—Adding substances to exhaust gases
    • F01N2610/02—Adding substances to exhaust gases the substance being ammonia or urea
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Abstract

가스혼합물의 반응물을 촉매변환시킬 경우, 계획된 촉매 반응과 함께 대개 바라지 않던 촉매부반응도 나타난다.
바라지 않던 부반응의 동시적으로 양호한 억제시에 가스혼합물의 적어도 2개의 반응물을 충분히 양호하게 촉매변환하기 위해 본 발명에 따라 반응물의 반응을 촉진시키는 촉매변환기가 고려되고, 이 경우 촉매활성제의 화학적 조성이 가스혼합물의 흐름방향으로 변한다.
그 때문에, 바라지 않던 부반응이, 예를들어 DeNOx-촉매변환기의 이용시 SO2/SO3-변환 또는 산화촉매변환기에서 산화질소의 발생이 화학적 화합물의 적당한 선택으로 광범위하게 억제될 수 있다.

Description

가스 혼합물의 반응물을 변환시키는 촉매변환기
본 내용은 요부공개 건이므로 전문내용을 수록하지 않았음
제 1 도는 연소 장치의 연소가스의 산화질소를 감소시키는 촉매변환기의 도면
제 2 도는 탄화수소와 일산화탄소의 산화를 위한 촉매변환기의 도면
제 3 도는 열교환을 위한 수단으로 연소가스의 산화 질소를 감소시키는 촉매 변환기의 도면

Claims (10)

  1. 혼합물의 흐름방향(23,36)으로 원하지 않던 부반응을 억제하기 위해 가변적 화학화합물을 가지는 촉매 활성제(18a 내지 18e, 33a 내지 33d, 42a 내지 42e)와 촉매변환기 캐리어를 포함하며 가스혼합물(23,36)의 적어도 2개의 반응물 사이의 적어도 하나의 반응을 가속시키기 위한 촉매변환기(2,24,38).
  2. 제 1 항에 있어서, 육안으로 볼 수 있을 만한 형성이 가스혼합물의 흐름방향으로 가변되는 것을 특징으로 하는 촉매변환기.
  3. 제 1 항 또는 2항에 있어서, 가스혼합물(23,26)의 흐름 방향으로 촉매변환기(2,24)의 이용된 촉매활성체(18a 내지 18e, 33a 내지 33d)의 촉매활성이 반응물의 발열반응의 결과로 야기된 온도상승의 경우에 감소되고 반응물의 흡열반응의 결과로 야기된 온도강하의 경우에 증가하는 것을 특징으로 하는 촉매변환기.
  4. 제 3 항에 있어서, 촉매활성이 단계적으로 감소 내지 증가하는 것을 특징으로 하는 촉매변환기.
  5. 제1 내지 4항 중 어느 한 항에 있어서, 본질적으로 산화티타늄(TiO2), 오산화바나딘(V2O5) 및/또는 첨가제 삼산화텅스텐(WO3)과 삼산화몰리브덴(M0O3)중 하나 또는 다수를 가진 VxMoyO32-Z(단 X+Y≤12; X,Y≥1; Z≤1)가 촉매활성체(18a 내지 18e)에 포함되어 있고 이에서 가스혼합물(23,36)의 흐름방향으로 오산화바나딘 및/또는 VxMoyO32-Z의 함량이 NH3- 함량의 감소에 상응하여 감소되는 것을 특징으로 하는 촉매변환기.
  6. 제1 내지 5항 중 어느 한 항에 있어서, 본질적으로 이산화티타늄(TiO2), 오산화바나딘(V2O5) 및/또는 첨가제 삼산화텅스텐(WO3)과 삼산화몰리브덴(M0O3)중 하나 또는 다수를 가진 VxMoyO32-Z(단 X+Y≤12; X,Y≥1; Z≤1)가 촉매활성체(18a 내지 18e)에 포함되어 있고, 이에서 오산화바나딘 및/또는 VxMoyO32-Z의 농도가 가스혼합물(23,36)의 흐름방향에서 발열반응의 경우 감소하고 흡열반응의 경우 증가하는 것을 특징으로 하는 촉매변환기.
  7. 제 6 항에 있어서, 오산화바나딘 및/또는 VxMoyO32-Z의 농도가 반응조건의 온도 상승 또는 감소에 따라 최대 10중량 퍼센트로부터 감소하거나 최대 10중량 퍼센트로 증가하는 것을 특징으로 하는 촉매변환기.
  8. 제1 내지 4항 중 어느 한 항에 있어서, 촉매활성체(33a 내지 33d)로서 백금(Pt) 및/또는 산화 제 2 동(CuO) 및/또는 산화 제 2 철(FeO)이 이용되고, 이에서 촉매활성제의 농도가 가스혼합물(36)의 흐름방향으로 반응조건의 온도상승 또는 감소에 따라 감소 내지 증가되게 조절되어 있는 것을 특징으로 하는 촉매변환기.
  9. 제 8 항에 있어서, 촉매활성체의 농도는 최대 10중량 퍼센트로부터 시작하여 감소 내지 최대 10중량 퍼센트로 증가하는 것을 특징으로 하는 촉매변환기.
  10. 제1,2 또는 4항 중 어느 한 항에 있어서, 본질적으로 산화티타늄(TiO2), 오산화바나딘(V2O5) 및/또는 첨가제 삼산화텅스텐(WO3)과 삼산화몰리브덴(M0O3)중 하나 또는 다수를 가진 VxMoyO32-Z(단 X+Y≤12; X,Y≥1; Z≤1)가 촉매활성체(18a 내지 18e)에 포함되어 있고, 이 촉매변환기 안에서의 DeNOx 반응처럼, 발열반응의 경우 가스혼합물의 흐름도를 따라 온도강하 수단이 이용되고, 이에서 오산화바나딘 및/또는 VxMoyO32-Z의 함량이 가스혼합물의 흐름방향에서 온도 강하로 인한 활성감소를 보상하기 위해 증가하는 것을 특징으로 하는 촉매변환기.
    ※ 참고사항 : 최초출원 내용에 의하여 공개하는 것임.
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