JP6453233B2 - 排ガス浄化装置 - Google Patents
排ガス浄化装置 Download PDFInfo
- Publication number
- JP6453233B2 JP6453233B2 JP2015552430A JP2015552430A JP6453233B2 JP 6453233 B2 JP6453233 B2 JP 6453233B2 JP 2015552430 A JP2015552430 A JP 2015552430A JP 2015552430 A JP2015552430 A JP 2015552430A JP 6453233 B2 JP6453233 B2 JP 6453233B2
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- JP
- Japan
- Prior art keywords
- catalyst
- upstream
- exhaust gas
- downstream
- zeolite
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- 238000000746 purification Methods 0.000 title claims description 88
- 239000003054 catalyst Substances 0.000 claims description 365
- 238000011144 upstream manufacturing Methods 0.000 claims description 125
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 96
- 239000010457 zeolite Substances 0.000 claims description 96
- 229910021536 Zeolite Inorganic materials 0.000 claims description 95
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 52
- 239000011148 porous material Substances 0.000 claims description 28
- 229910021529 ammonia Inorganic materials 0.000 claims description 26
- 239000003638 chemical reducing agent Substances 0.000 claims description 18
- 238000002485 combustion reaction Methods 0.000 claims description 15
- 229910000510 noble metal Inorganic materials 0.000 claims description 11
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 131
- 239000007789 gas Substances 0.000 description 94
- 239000010949 copper Substances 0.000 description 30
- 238000005342 ion exchange Methods 0.000 description 27
- WTHDKMILWLGDKL-UHFFFAOYSA-N urea;hydrate Chemical compound O.NC(N)=O WTHDKMILWLGDKL-UHFFFAOYSA-N 0.000 description 20
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 19
- 238000005192 partition Methods 0.000 description 18
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 17
- 239000000243 solution Substances 0.000 description 16
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 15
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 14
- 230000000052 comparative effect Effects 0.000 description 13
- 239000000463 material Substances 0.000 description 13
- 239000013618 particulate matter Substances 0.000 description 12
- 239000002002 slurry Substances 0.000 description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- 230000009257 reactivity Effects 0.000 description 7
- 239000000377 silicon dioxide Substances 0.000 description 7
- 239000000758 substrate Substances 0.000 description 7
- 238000000034 method Methods 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 239000000919 ceramic Substances 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 229910052697 platinum Inorganic materials 0.000 description 4
- 230000001603 reducing effect Effects 0.000 description 4
- 239000007921 spray Substances 0.000 description 4
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 3
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 3
- 239000004202 carbamide Substances 0.000 description 3
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 description 3
- 238000002347 injection Methods 0.000 description 3
- 239000007924 injection Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 229910052698 phosphorus Inorganic materials 0.000 description 3
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 3
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 3
- 229910010271 silicon carbide Inorganic materials 0.000 description 3
- -1 Al and P Chemical class 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- 229910002091 carbon monoxide Inorganic materials 0.000 description 2
- 238000010531 catalytic reduction reaction Methods 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 229910052878 cordierite Inorganic materials 0.000 description 2
- 230000007423 decrease Effects 0.000 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 description 2
- 239000000446 fuel Substances 0.000 description 2
- 239000003779 heat-resistant material Substances 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- 239000010948 rhodium Substances 0.000 description 2
- 238000007789 sealing Methods 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- 229910000505 Al2TiO5 Inorganic materials 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910052581 Si3N4 Inorganic materials 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 238000003915 air pollution Methods 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000011246 composite particle Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 150000002500 ions Chemical group 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- PVFSDGKDKFSOTB-UHFFFAOYSA-K iron(3+);triacetate Chemical compound [Fe+3].CC([O-])=O.CC([O-])=O.CC([O-])=O PVFSDGKDKFSOTB-UHFFFAOYSA-K 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 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 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
Images
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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
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Combustion & Propulsion (AREA)
- Health & Medical Sciences (AREA)
- Mechanical Engineering (AREA)
- General Engineering & Computer Science (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Biomedical Technology (AREA)
- Environmental & Geological Engineering (AREA)
- Analytical Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Toxicology (AREA)
- Crystallography & Structural Chemistry (AREA)
- Exhaust Gas Treatment By Means Of Catalyst (AREA)
- Catalysts (AREA)
- Exhaust Gas After Treatment (AREA)
- Processes For Solid Components From Exhaust (AREA)
Description
なお、本国際出願は2013年12月9日に出願された日本国特許出願第2013−254478号に基づく優先権を主張しており、その出願の全内容は本明細書中に参照として組み入れられている。
ここで開示される排ガス浄化装置100は、上記内燃機関1の排気通路(排気管)3に設けられている。排ガス浄化装置100は、上流側(図1の左側)から下流側(図1の右側)に向かって順に、還元剤溶液供給手段50、上流側フィルタ触媒部10、上流側ハニカム触媒部20、下流側ハニカム触媒部30を備え、上記排出される排ガスに含まれる窒素酸化物(NOx)を浄化する。燃焼室から排気された排ガスは、排気マニホルド5から排気管3を通じて上流側フィルタ触媒部10に導かれ、さらに上流側ハニカム触媒部20および下流側ハニカム触媒部30へと導かれる。
還元剤溶液供給手段50は、フィルタ触媒部10よりも排気管3の上流側に配置されている。還元剤溶液供給手段50は、フィルタ触媒部10の排ガス流通方向における上流からアンモニアを生成するための還元剤溶液(ここでは尿素水)を供給する。この実施形態では、還元剤溶液供給手段50は、噴霧ノズル52とポンプ54とタンク56とを備えている。噴霧ノズル52は、ポンプ54を介してタンク56に接続されている。ポンプ54は、タンク56内の尿素水を噴霧ノズル52へ供給する。噴霧ノズル52へ供給された尿素水は、排気管3内に噴霧され、該排気管3内で上流から流れてくる排ガスとともに下流へと流されるとともに、加水分解してアンモニアを発生させる。このアンモニアが後述するフィルタ10、第1ハニカム触媒20および第2ハニカム触媒30のSCR触媒に吸着し、吸着したアンモニアの還元作用により排ガス中のNOxが浄化される。なお、還元剤溶液供給手段の数は1つに限らず2つ以上であってもよい。例えば、更なる還元剤溶液供給手段をフィルタ触媒部10と上流側ハニカム触媒部20との間に配置してもよい。
上流側フィルタ触媒部10は、還元剤溶液供給手段50よりも排気管3の下流側に配置されている。上流側フィルタ触媒部10は、排ガスに含まれる粒子状物質(PM)を捕集可能な多孔質フィルタであり、PMの通過不能な多数の細孔が設けられている。また、フィルタ触媒部10は、SCR(Selective Catalytic Reduction:選択的接触還元)触媒を担持することで、排ガス中の窒素酸化物(NOx)を浄化するものとして構成されている。
上流側ハニカム触媒部20は、図1に示すように、上流側フィルタ触媒部10よりも排気管3の下流側に配置されている。下流側ハニカム触媒部30は、上流側ハニカム触媒部20よりも排気管3の下流側(ここでは最下流側)に配置されている。上流側ハニカム触媒部20および下流側ハニカム触媒部30は、ストレートフロー構造の基材上に触媒層が形成されることによって構成されている。
(1)上流側フィルタ触媒
シリカ・アルミナ・燐から形成されるSAPO34をイオン交換水に分散させた後、酢酸銅を添加し、80℃で12時間攪拌し、ろ過、洗浄した。その後、200℃で5時間乾燥させ、Cuイオン交換ゼオライト(Cu担持量3質量%)を調製した。このCuイオン交換ゼオライト1000gとシリカゾル500gと純水1000gとを混合した後、ボールミルで1時間攪拌し、Cuイオン交換SAPO34スラリーを得た。得られたCuイオン交換SAPO34スラリーをウォールフロー型のセラミック基材(径160mm×長さ100mm)に塗布し、余分なスラリーを除去した後、100℃で乾燥、500℃で熱処理して上流側フィルタ触媒(上流側フィルタ触媒部10(図1参照))を作製した。得られた触媒のCuイオン交換SAPO34のコート量は、基材1L当たり100gであった。
シリカ・アルミナ・燐から形成されるSAPO34をイオン交換水に分散させた後、酢酸銅を添加し、80℃で12時間攪拌し、ろ過、洗浄した。その後、200℃で5時間乾燥させ、Cuイオン交換ゼオライト(Cu担持量3質量%)を調製した。このCuイオン交換ゼオライト1000gとシリカゾル500gと純水1000gとを混合した後、ボールミルで1時間攪拌し、Cuイオン交換SAPO34スラリーを得た。得られたCuイオン交換SAPO34スラリーをストレートフロー型のセラミック基材(径160mm×長さ100mm)に塗布し、余分なスラリーを除去した後、100℃で乾燥、500℃で熱処理して上流側ハニカム触媒(上流側ハニカム触媒部20(図1参照))を作製した。得られた上流側ハニカム触媒のCuイオン交換SAPO34のコート量は、基材1L当たり160gであった。
シリカ・アルミナ比が25のβ型ゼオライトをイオン交換水に分散させた後、酢酸鉄を添加し、80℃で12時間攪拌し、ろ過、洗浄した。その後、200℃で5時間乾燥させ、Feイオン交換ゼオライト(Fe担持量2質量%)を調製した。このFeイオン交換ゼオライト1000gとシリカゾル500gと純水1000gとを混合した後、ボールミルで1時間攪拌し、Feイオン交換β型ゼオライトスラリーを得た。得られたFeイオン交換β型ゼオライトスラリーをストレートフロー型のセラミック基材(径160mm×長さ100mm)に塗布し、余分なスラリーを除去した後、100℃で乾燥、500℃で熱処理してFeイオン交換β型ゼオライトをコートしたハニカム触媒を得た。
下流側ハニカム触媒に用いるSCR触媒をCuイオン交換β型ゼオライトに変更したこと以外は実施例1と同様にして排ガス浄化装置を作製した。具体的には、シリカ・アルミナ比が25のβ型ゼオライトをイオン交換水に分散させた後、酢酸銅を添加し、80℃で12時間攪拌し、ろ過、洗浄した。その後、200℃で5時間乾燥させ、Cuイオン交換β型ゼオライト(Cu担持量2質量%)を調製した。かかるCuイオン交換β型ゼオライトを用いて、実施例1と同様の手順で下流側ハニカム触媒を作製した。
上流側フィルタ触媒、上流側ハニカム触媒および下流側ハニカム触媒に用いるSCR触媒を何れもCuイオン交換SAPO34(骨格密度15.1T/1000Å3、平均細孔径3.7Å)に変更したこと以外は実施例1と同様にして排ガス浄化装置を作製した。
上流側フィルタ触媒、上流側ハニカム触媒および下流側ハニカム触媒に用いるSCR触媒を何れもシリカ・アルミナ比が25のFeイオン交換β型ゼオライト(骨格密度15.3T/1000Å3、平均細孔径5.9Å)に変更したこと以外は実施例1と同様にして排ガス浄化装置を作製した。
上流側フィルタ触媒、上流側ハニカム触媒および下流側ハニカム触媒に用いるSCR触媒を何れもシリカ・アルミナ比が25のCuイオン交換Y型ゼオライト(骨格密度13.3T/1000Å3、平均細孔径7.4Å)に変更したこと以外は実施例1と同様にして排ガス浄化装置を作製した。
上流側フィルタ触媒、上流側ハニカム触媒および下流側ハニカム触媒に用いるSCR触媒を何れもシリカ・アルミナ比が25のCuイオン交換ZSM5ゼオライト(骨格密度18.4T/1000Å3、平均細孔径4.6Å)に変更したこと以外は実施例1と同様にして排ガス浄化装置を作製した。
Claims (6)
- 内燃機関の排気通路に配置され、該内燃機関から排出される排ガスを浄化する排ガス浄化装置であって、
前記排気通路の上流側に配置された上流触媒部と、
前記上流触媒部よりも前記排気通路の下流側に配置された下流触媒部と、
前記上流触媒部よりも上流からアンモニアを生成するための還元剤溶液を供給する還元剤溶液供給手段と
を備え、
前記上流触媒部および前記下流触媒部は、それぞれアンモニアを吸着して排ガス中のNOxを還元するゼオライトからなるSCR触媒を含んでおり、
前記上流触媒部に含まれるゼオライトからなるSCR触媒は、国際ゼオライト学会の定める構造コードがCHA(チャバサイト)であり、
前記下流触媒部に含まれるゼオライトからなるSCR触媒は、国際ゼオライト学会の定める構造コードがBEA(ベータ)であり、
前記上流触媒部に含まれるゼオライトからなるSCR触媒の骨格密度Aが、前記下流触媒部に含まれるゼオライトからなるSCR触媒の骨格密度Bよりも小さい(A<B)、排ガス浄化装置。 - 前記上流触媒部に含まれるゼオライトからなるSCR触媒の骨格密度Aと、前記下流触媒部に含まれるゼオライトからなるSCR触媒の骨格密度Bとの差が、0.1(T/1000Å3)≦B−Aである、請求項1に記載の排ガス浄化装置。
- 前記上流触媒部に含まれるゼオライトからなるSCR触媒の骨格密度Aと、前記下流触媒部に含まれるゼオライトからなるSCR触媒の骨格密度Bとの双方が、14(T/1000Å3)以上17(T/1000Å3)以下である、請求項1または2に記載の排ガス浄化装置。
- 前記上流触媒部に含まれるゼオライトからなるSCR触媒の平均細孔径と、前記下流触媒部に含まれるゼオライトからなるSCR触媒の平均細孔径との双方が、2Å以上7Å以下である、請求項1〜3の何れか一つに記載の排ガス浄化装置。
- 前記排気通路の上流側に配置されたフィルタ触媒部と、
前記フィルタ触媒部よりも前記排気通路の下流側に配置された複数のハニカム触媒部と
を備えており、
前記フィルタ触媒部として、前記上流触媒部が設けられており、
前記複数のハニカム触媒部のうち前記排気通路の最下流側に配置されたハニカム触媒部として、前記下流触媒部が設けられている、請求項1〜4の何れか一つに記載の排ガス浄化装置。 - 前記最下流側に配置されたハニカム触媒部には、貴金属が担持されている、請求項5に記載の排ガス浄化装置。
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