JP7420087B2 - 排ガス浄化システム - Google Patents
排ガス浄化システム Download PDFInfo
- Publication number
- JP7420087B2 JP7420087B2 JP2021006625A JP2021006625A JP7420087B2 JP 7420087 B2 JP7420087 B2 JP 7420087B2 JP 2021006625 A JP2021006625 A JP 2021006625A JP 2021006625 A JP2021006625 A JP 2021006625A JP 7420087 B2 JP7420087 B2 JP 7420087B2
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- JP
- Japan
- Prior art keywords
- exhaust gas
- gas purification
- purification device
- atmosphere
- spinel
- 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 126
- 239000002245 particle Substances 0.000 claims description 54
- 229910020068 MgAl Inorganic materials 0.000 claims description 52
- 239000003054 catalyst Substances 0.000 claims description 39
- 238000002485 combustion reaction Methods 0.000 claims description 29
- 239000007800 oxidant agent Substances 0.000 claims description 16
- 239000003638 chemical reducing agent Substances 0.000 claims description 14
- 238000004438 BET method Methods 0.000 claims description 9
- 239000007789 gas Substances 0.000 description 185
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 85
- 230000000052 comparative effect Effects 0.000 description 38
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 33
- 229910002091 carbon monoxide Inorganic materials 0.000 description 33
- 229930195733 hydrocarbon Natural products 0.000 description 32
- 150000002430 hydrocarbons Chemical class 0.000 description 32
- 239000010948 rhodium Substances 0.000 description 30
- 229910052782 aluminium Inorganic materials 0.000 description 29
- 229910052742 iron Inorganic materials 0.000 description 27
- 238000000034 method Methods 0.000 description 17
- 238000012360 testing method Methods 0.000 description 12
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 10
- 239000001301 oxygen Substances 0.000 description 10
- 229910052760 oxygen Inorganic materials 0.000 description 10
- 229910052596 spinel Inorganic materials 0.000 description 10
- 239000011029 spinel Substances 0.000 description 10
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 9
- 238000006722 reduction reaction Methods 0.000 description 9
- 238000002441 X-ray diffraction Methods 0.000 description 8
- 230000010757 Reduction Activity Effects 0.000 description 7
- 239000000446 fuel Substances 0.000 description 7
- 238000004458 analytical method Methods 0.000 description 6
- 238000011156 evaluation Methods 0.000 description 6
- 239000000843 powder Substances 0.000 description 6
- XNDZQQSKSQTQQD-UHFFFAOYSA-N 3-methylcyclohex-2-en-1-ol Chemical compound CC1=CC(O)CCC1 XNDZQQSKSQTQQD-UHFFFAOYSA-N 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 5
- QZRHHEURPZONJU-UHFFFAOYSA-N iron(2+) dinitrate nonahydrate Chemical compound O.O.O.O.O.O.O.O.O.[Fe+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O QZRHHEURPZONJU-UHFFFAOYSA-N 0.000 description 5
- 229910052703 rhodium Inorganic materials 0.000 description 5
- 238000010586 diagram Methods 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 125000004430 oxygen atom Chemical group O* 0.000 description 4
- 239000002002 slurry Substances 0.000 description 4
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 description 3
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 230000003993 interaction Effects 0.000 description 3
- 239000011777 magnesium Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 3
- VXNYVYJABGOSBX-UHFFFAOYSA-N rhodium(3+);trinitrate Chemical compound [Rh+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VXNYVYJABGOSBX-UHFFFAOYSA-N 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- MFUVDXOKPBAHMC-UHFFFAOYSA-N magnesium;dinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MFUVDXOKPBAHMC-UHFFFAOYSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 239000002105 nanoparticle Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 2
- 238000002336 sorption--desorption measurement Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 238000012916 structural analysis Methods 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910000608 Fe(NO3)3.9H2O Inorganic materials 0.000 description 1
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 1
- ZSBXGIUJOOQZMP-JLNYLFASSA-N Matrine Chemical compound C1CC[C@H]2CN3C(=O)CCC[C@@H]3[C@@H]3[C@H]2N1CCC3 ZSBXGIUJOOQZMP-JLNYLFASSA-N 0.000 description 1
- 241000705939 Shortia uniflora Species 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 150000004703 alkoxides Chemical class 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- WPQBNJRIWONKBL-UHFFFAOYSA-N cerium(3+);oxygen(2-);zirconium(4+) Chemical compound [O-2].[Zr+4].[Ce+3] WPQBNJRIWONKBL-UHFFFAOYSA-N 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 239000002274 desiccant Substances 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 239000002923 metal particle Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 238000011144 upstream manufacturing Methods 0.000 description 1
- 238000009489 vacuum treatment Methods 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
- B01D53/94—Chemical or biological purification of waste gases of engine exhaust gases by catalytic processes
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- 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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- F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
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- F01N2510/00—Surface coverings
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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)
- Biomedical Technology (AREA)
- Environmental & Geological Engineering (AREA)
- Analytical Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Mechanical Engineering (AREA)
- General Engineering & Computer Science (AREA)
- Toxicology (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Catalysts (AREA)
- Exhaust Gas Treatment By Means Of Catalyst (AREA)
- Exhaust Gas After Treatment (AREA)
- Combined Controls Of Internal Combustion Engines (AREA)
Description
《態様1》
内燃機関から排出される排ガスを浄化する、排ガス浄化システムであって、
前記排ガスを浄化する、第1の排ガス浄化装置、及び
前記第1の排ガス浄化装置によって浄化された前記排ガスを更に浄化する、第2の排ガス浄化装置を有しており、
前記排ガスは、ストイキ雰囲気よりも還元剤が過剰な雰囲気、及び前記ストイキ雰囲気よりも酸化剤が過剰な雰囲気が交互に切り替わる排ガスであり、
前記第1の排ガス浄化装置は、三元触媒を有しており、かつ
前記第2の排ガス浄化装置は、Rhが担持されているスピネル型のMgAlxFe2.00-xO4.00担体粒子を含有している、排ガス浄化触媒を有しており、ここで、0.00<x≦1.50である、
排ガス浄化システム。
《態様2》
0.50≦x≦1.50である、態様1に記載の排ガス浄化システム。
《態様3》
前記排ガス浄化触媒における前記Rhの担持量が、前記排ガス浄化触媒の質量全体に対して0.1質量%~1.0質量%である、態様1又は2に記載の排ガス浄化システム。
《態様4》
前記スピネル型のMgAlxFe2.00-xO4.00担体粒子の格子定数aが、8.10Å~8.35Åである、態様1~3のいずれか一つに記載の排ガス浄化システム。
《態様5》
前記スピネル型のMgAlxFe2.00-xO4.00担体粒子の結晶子径が、4nm~43nmである、態様1~4のいずれか一つに記載の排ガス浄化システム。
《態様6》
前記スピネル型のMgAlxFe2.00-xO4.00担体粒子のBET法による比表面積が、11m2/g~150m2/gである、態様1~5のいずれか一つに記載の排ガス浄化システム。
《態様7》
態様1~6のいずれか一つに記載の排ガス浄化システムを搭載している、車両。
本開示の排ガス浄化システムは、内燃機関から排出される排ガスを浄化する、排ガス浄化システムであって、排ガスを浄化する、第1の排ガス浄化装置、及び第1の排ガス浄化装置によって浄化された排ガスを更に浄化する、第2の排ガス浄化装置を有しており、排ガスは、ストイキ雰囲気よりも還元剤が過剰な雰囲気、及びストイキ雰囲気よりも酸化剤が過剰な雰囲気が交互に切り替わる排ガスであり、第1の排ガス浄化装置は、三元触媒を有しており、かつ第2の排ガス浄化装置は、Rhが担持されているスピネル型のMgAlxFe2.00-xO4.00担体粒子を含有している、排ガス浄化触媒を有しており、ここで、0.00<x≦1.50である。
第1の排ガス浄化装置は、内燃機関から出る、ストイキ雰囲気を中心に還元剤過剰な雰囲気及び酸化剤過剰な雰囲気が交互に切り替わる排ガスを浄化する装置である。第1の排ガス浄化装置は、三元触媒を有している。
第1の排ガス浄化装置が有している三元触媒は、内燃機関から出る排ガス中のHC及びCOの酸化反応、並びにNOxの還元反応を触媒することができ、排ガス中のこれらの成分を同時に除去することができる触媒であれば、特に限定されない。このような三元触媒としては、アルミナ、セリア、及びジルコニアの組み合わせを含む金属酸化物担体粒子に、Rh、Pt、及びPd等の貴金属粒子が担持されている触媒を挙げることができる。また、三元触媒は、セリアのような酸素吸蔵機能を有する金属酸化物粒子を含有していることができる。
第2の排ガス浄化装置は、第1の排ガス浄化装置によって浄化された排ガスを更に浄化する装置である。第2の排ガス浄化装置は、Rhが担持されているスピネル型のMgAlxFe2.00-xO4.00担体粒子を含有している、排ガス浄化触媒を有しており、ここで、0.00<x≦1.50である。
第2の排ガス浄化装置が有している排ガス浄化触媒は、Rhが担持されているスピネル型のMgAlxFe2.00-xO4.00担体粒子を含有している。ここで、0.00<x≦1.50である。
Rhが担持されているスピネル型のMgAlxFe2.00-xO4.00担体粒子は、スピネル型のMgAlxFe2.00-xO4.00担体粒子にRhを担持させることにより製造することができる。
本開示の車両は、本開示の排ガス浄化システムを搭載している。
〈実施例1:Rh担持MgAl0.50Fe1.50O4.00〉
12.82g(0.05mol)の硝酸マグネシウム六水和物(Mg(NO3)2・6H2O)、9.38g(0.025mol)の硝酸アルミニウム9水和物(Al(NO3)3・9H2O)、及び30.30g(0.075mol)の硝酸鉄9水和物(Fe(NO3)3・9H2O)を、蒸留水100mLに溶解させ、次いでクエン酸28.82g(0.15mol)を溶解させた。この溶液を85℃で4時間加熱撹拌し、得られたスラリーを120℃で8時間乾燥させて、ペーストを得た。得られたペーストを300℃で2時間仮焼後、750℃で5時間焼成して粉末を得た。
硝酸アルミニウム9水和物の量を18.76g(0.05mol)とし、かつ硝酸鉄9水和物の量を20.20g(0.05mol)としたことを除いて実施例1と同様にして、実施例2の試料を得た。
硝酸アルミニウム9水和物の量を28.13g(0.075mol)とし、かつ硝酸鉄9水和物の量を10.10g(0.025mol)としたことを除いて実施例1と同様にして、実施例3の試料を得た。
硝酸アルミニウム9水和物を用いず、かつ硝酸鉄9水和物の量を40.40g(0.10mol)としたことを除いて実施例1と同様にして、比較例1の試料を得た。
硝酸鉄9水和物を用いず、かつ硝酸アルミニウム9水和物の量を37.51g(0.10mol)としたことを除いて実施例1と同様にして、比較例2の試料を得た。
酸化セリウム-ジルコニウム複合酸化物(Ce/Zr=3/7、SBET=70m2/g)にロジウムを0.5質量%担持したものを比較例3の試料とした。
実施例1~3、並びに比較例1及び2の試料について、X線回折試験による構造解析及びBET法による比表面積の測定を行った。
X線回折試験による構造解析は、リガク製RINT2000を用い、X線源をCuKα(λ=1.5418nm)、走査範囲を10~90deg、ステップ幅を0.02deg、管電圧を50kV、及び管電流を300mAとして行った。また、回折ピーク位置は、JCPDSデータファイルの既知のデータと比較した。
X線回折試験の結果を、図3に示す。
実施例1~3、並びに比較例1及び2の試料について、走査型電子顕微鏡(SEM)による観察を行った。
観察には、JEOL製のJEM-1000(加速電圧:200kV)を用いた。また、各試料をエタノールに分散させ、銅グリッドに滴下後、乾燥させたものを観察した。
比較例1、実施例1~3、及び比較例2の試料のSEM画像を、図6A~Eにそれぞれこの順に示す。
実施例1~3及び比較例1~3の試料について、NOx還元活性を評価した。
NOx還元活性は、流通型反応器に各例の試料(4g)を配置し、FT-IR分析計(ベスト測器製のSESAM-HL)で各ガスの転化挙動を分析して評価した。具体的には、450℃で5分間、還元前処理を行った後に、以下の表2に示すNO雰囲気ガス及びCO/HC雰囲気ガス(窒素ガスバランス)をそれぞれ交互に20L/minで60秒間導入するサイクルを5回繰り返して行い、NO雰囲気ガス導入中のNOx還元量の、2~5サイクルでの平均値を比較した。評価は450℃又は300℃の温度で行った。評価温度を変える際は、同流量で1%H2/N2を流通させた。
図7にNOx還元活性の評価結果を示す。
実施例1~3及び比較例1~3の試料について、H2-TPR試験を行った。
測定には日本ベル製のBelcat Aを用いた。各例の試料粉末約50mgを精秤してサンプル管に導入した。次いで、サンプル管内にO2が20体積%かつ残部がHeの雰囲気を30mL/minの流量で流通させつつ600℃まで昇温後、10分間温度を保持し、その後、同雰囲気下で約-80℃まで冷却した。-80℃において雰囲気をArガスで置換した後、サンプル管内にH2が5体積%かつ残部がArの雰囲気を30mL/minの流量で流通させつつ、10℃/minで試料を加熱しながら、600℃まで昇温させ、H2消費量を分析した。分析は熱伝導検出器(TCD)で行った。TCD前段に乾燥材を配置して、生成する水をトラップした。CuO粉末を用いて同様の分析を行い、各試料のH2消費量を定量した。
図8及び9にH2-TPR試験結果を示す。
20 第2の排ガス浄化装置
21 スピネル型のMgAlxFe2.00-xO4.00担体粒子
22 Bサイト
24 酸素原子
24’ 酸素空孔
25 Rh
30a 第1の流路
30b 第2の流路
100 排ガス浄化システム
200 内燃機関
Claims (6)
- 内燃機関から排出される排ガスを浄化する、排ガス浄化システムであって、
前記排ガスを浄化する、第1の排ガス浄化装置、及び
前記第1の排ガス浄化装置によって浄化された前記排ガスを更に浄化する、第2の排ガス浄化装置を有しており、
前記排ガスは、ストイキ雰囲気よりも還元剤が過剰な雰囲気、及び前記ストイキ雰囲気よりも酸化剤が過剰な雰囲気が交互に切り替わる排ガスであり、
前記第1の排ガス浄化装置は、三元触媒を有しており、かつ
前記第2の排ガス浄化装置は、Rhが担持されているスピネル型のMgAlxFe2.00-xO4.00担体粒子を含有している、排ガス浄化触媒を有しており、ここで、0.50≦x≦1.50である、
排ガス浄化システム。 - 前記排ガス浄化触媒における前記Rhの担持量が、前記排ガス浄化触媒の質量全体に対して0.1質量%~1.0質量%である、請求項1に記載の排ガス浄化システム。
- 前記スピネル型のMgAlxFe2.00-xO4.00担体粒子の格子定数aが、8.10Å~8.35Åである、請求項1又は2に記載の排ガス浄化システム。
- 前記スピネル型のMgAlxFe2.00-xO4.00担体粒子の結晶子径が、4nm~43nmである、請求項1~3のいずれか一項に記載の排ガス浄化システム。
- 前記スピネル型のMgAlxFe2.00-xO4.00担体粒子のBET法による比表面積が、11m2/g~150m2/gである、請求項1~4のいずれか一項に記載の排ガス浄化システム。
- 請求項1~5のいずれか一項に記載の排ガス浄化システムを搭載している、車両。
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