JP2022525282A - 三元触媒分解における劣化に対して安定なランタン系ペロブスカイト型触媒組成物 - Google Patents
三元触媒分解における劣化に対して安定なランタン系ペロブスカイト型触媒組成物 Download PDFInfo
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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
- B01D53/92—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
- B01D53/9445—Simultaneously removing carbon monoxide, hydrocarbons or nitrogen oxides making use of three-way catalysts [TWC] or four-way-catalysts [FWC]
- B01D53/945—Simultaneously removing carbon monoxide, hydrocarbons or nitrogen oxides making use of three-way catalysts [TWC] or four-way-catalysts [FWC] characterised by a specific catalyst
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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
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Abstract
Description
式(I):LazB1-qB’qO3±δ
本発明の触媒組成物は、ペロブスカイト型化合物を含有する。いくつかの実施形態において、ペロブスカイト型化合物は式(I):LazB1-qB’qO3±δを有する。
式中、B又はB’は、Fe、Mn、Co、Ni、Cu、Ti、又はZrであり、好ましくは、B又はB’は、Fe又はMnである。いくつかの実施形態において、B又はB’はFeである。別の実施形態では、B又はB’はMnである。
qは、0~0.5、好ましくは、0~0.2の範囲であり、より好ましくは0である。
zは、約0.6~約1.1、好ましくは、約0.7~約1.0、より好ましくは、約0.7~約0.9の範囲である。
δは、約0~約0.6、好ましくは、約0~約0.5、より好ましくは、約0.15~約0.3の範囲である。
%純度=Iペロブスカイト相/(Iペロブスカイト相+I混入物相)を意味し、
式中、I=XRDによって同定される結晶性相の強度である。
いくつかの実施形態において、ペロブスカイト型化合物は、式(II):[BOx]y:[LazBO3±δ]1-yの化合物であり、の
式中、Bは、Fe、Mn、Co、又はNiであり、好ましくは、BはFe又はMnである。いくつかの実施形態において、BはFeである。他の実施形態では、BはMnである。
xは、約1~約2.5である。
yは、約1~約30wt%である。
zは、約0.7~約1.1である。
δは、約0~約0.6の範囲、好ましくは、約0~約0.5、より好ましくは、約0.1~約0.3である。
いくつかの実施形態において、BはMnである。更なる実施形態では、LazMnO3±δは、結晶性ペロブスカイト相である。また、独立した代替的又は追加的な実施形態において、(BがMnである実施形態において)引用した組成物又はMnOx又はLazMnO3±δそれ自体に関して、必要に応じて、
(a)xは、約1~約1.1、約1.1~約1.2、約1.2~約1.3、約1.3~約1.4、約1.4~約1.5、約1.5~約1.6、約1.6~約1.7、約1.7~約1.8、約1.8~約1.9、約1.9~約2.0、約2.0~約2.1、約2.1~約2.2、約2.2~約2.3、約2.3~約2.4、約2.4~約2.5の範囲の値、又はこれらの範囲の2つ以上を含む範囲によって定義される値、例えば、約1.6~約2.5であり得る。誤解を避けるために、ここで「MnOx」という表記は、O:Mnの原子数比がxであるマンガンの任意の2元酸化物を指す。例えば、表記にはMn3O4(x=1.33)、Mn5O8(x=1.6)などが含まれる。このように、値xによって、本明細書の他の箇所に記載されるように、マンガンの酸化物又はそれらの混合物の個々の式のいずれかの組成が定義される。特定の独立した実施形態では、MnOxは、主にMn3O4(x=1.33)、Mn5O8(x=1.6)、又はこれらの組合せであり、
(b)yは、前述の項の範囲よりも大きい又は小さい値であってもよい。特定の実施形態において、yは、約0~約1wt%の範囲の値(すなわち、LazMnO3それ自体のみとみなされる)、1~約2wt%、約2~約3wt%、約3~約4wt%、約4~約5wt%、約5~約6wt%、約6~約7wt%、約7~約8wt%、約8~約9wt%、約9~約10wt%、約10~約11wt%、約11~約12wt%、約12~約13wt%、約13~約14wt%、約14~約15wt%、約15~約16wt%、約16~約17wt%、約17~約18wt%、約18~約19wt%、約19~約20wt%、約20~約21wt%、約21~約22wt%、約22~約23wt%、約23~約24wt%、約24~約25wt%、約25~約26wt%、約26~約27wt%、約27~約28wt%、約28~約29wt%、約29~約30wt%の範囲の値であり得、又は、yは、これらの範囲のいずれか2つ以上で定義することができ、例えば、約2~約5wt%であり得、
(c)zは、約0.7~約0.75、約0.75~約0.8、約0.8~約0.85、約0.85~約0.9、約0.9~約0.95、約0.95~約0.98、約0.98~約0.99、約0.99~約1、約1~約1.05、約1.05~約1.1の範囲の値であり得、又は、zは、これらの範囲の任意の2つ以上で定義することができ、例えば、約0.75~約1.1、又は約0.8~約1、又は約0.8~約0.99、又は約0.8~約0.95であり得る。
本発明の触媒組成物は、1つ以上の非レドックス活性酸化物などの非レドックス活性成分を含有する。好適な非レドックス活性酸化物としては、例えば、アルミナ、ZrO2、ドープされたZrO2、例えばNb、Nd、Y、又はLaでドープされたZrO2、又はそれらの組合せが挙げられる。好適な種類のアルミナとしては、例えば、γ-、δ-、θ-、及びα-アルミナが挙げられる。
本開示の別の態様は、ペロブスカイト型化合物と非レドックス活性成分とを含む、三元触媒組成物に関する。いくつかの態様において、三元触媒は白金族金属を全く含まない。いくつかの態様において、三元触媒は、白金族金属を実質的に含まない。いくつかの態様において、三元触媒は、白金族金属を本質的に含まない。
本発明の触媒物品は、本明細書に記載の触媒組成物と基材とを含んでもよい。いくつかの態様において、触媒物品は、最大約2g/in3、例えば、約0.5g/in3~約2g/in3、約0.5g/in3~約1.5g/in3、又は約1g/in3の担持量でペロブスカイト型化合物を含む。いくつかの態様において、触媒物品は、最大約3g/in3、例えば、約0.5g/in3~約3g/in3、約1g/in3~約3g/in3、約1.5g/in3~約2.5g/in3、約1g/in3~約2g/in3、約2g/in3、又は約1g/in3の担持量で非レドックス活性成分を含む。
驚くべきことに、ペロブスカイト型化合物と非レドックス活性成分とを混合することにより、高温劣化条件を含む劣化条件にさらされた後であっても活性である三元触媒組成物が得られることを見出した。この高温安定性は、従来のペロブスカイト型三元触媒組成物が劣化後に失活することが認められているため、有益である。
用語「ウォッシュコート」は、当該技術分野において公知であり、通常、触媒の製造中の基材に適用される接着性コーティングを指す。
全ての試薬材料は市販されており、特に記載のない限り、既知の供給元から入手した。
FSPペロブスカイト材料は、典型的には、液体供給火炎熱分解によって合成する。前駆体を、特定の温度で好適な溶媒に溶解させる。次いで、溶液を酸素流と共に火炎に供給する。粒子を、エアフィルタバッグを備えたバッグハウスにステンレス鋼のダクトを通して搬送し、フィルタバッグを逆パルス洗浄して回収する。
ランタン(III)2-エチルヘキサノエート溶液(27.78g、0.02mole)及び鉄(III)アセチルアセトネート(8.84g、0.025mole)を150mLのキシレンに溶解させた。次いで、溶液(200mL、0.33mol/L)を、酸素流(分散、シース流量20L/分)と共に、10mL/minの速度でCH4/O2(1.5/3.2 L/min、混合)の火炎に供給した。粒子を、エアフィルタバッグ(Whatman GF/D濾紙)を備えたバッグハウスにステンレス鋼のダクトを通して搬送し、フィルタバッグを逆パルス洗浄して回収した。得られた比較触媒1は、XRDから明らかなように、12nmの平均結晶子サイズを有する純相であった。比較触媒1は、球状の粒子形態を有し、80m2g-1の比表面積、及びLa/Fe=1.1の表面組成を有した(XPS)。
触媒2は、比較触媒1の粉末をγアルミナ(Al2O3)と2:1の重量比で物理的に混合することによって調製した。
触媒3は、比較触媒1の粉末を単斜晶ジルコニア(ZrO2)と2:1の重量比で物理的に混合することによって調製した。
比較触媒1、触媒2、及び触媒3を、500℃~600℃の温度の標準的な摂動ガソリン条件下で試験した。次いで、触媒を、水蒸気の存在下、及びリッチ/リーン条件下、700℃以上の温度を伴い、20時間劣化させた。具体的な条件を以下に示す:
・試験条件:摂動ガス混合物(WHSV=750Lg-1h-1)、λ±0.05:0.73~2.2%CO+666ppmC3H6+333ppmC3H8+2200ppmNO+0.23~0.69%H2+*O2+14%CO2+4%H2O(N2を加えて100%)、3s/摂動、
・劣化条件:摂動ガス混合物、λ=0.93~1.06:0.5%CO+1000ppmC3H8+1000ppmNO+0.27~1.07%O2+10%H2O(N2を加えて100%)、5min/摂動。
KOH(85%、8.41g、0.127mol)を水(200mL)に溶解させ、マグネチックスターラーバーを用いて400rpmで溶液を撹拌し、60℃に加熱した。硝酸ランタン六水和物(7.58g、0.0175mol)及び硝酸マンガン(50wt/w%溶液、8.95g、0.025mol)を水に溶解させ、溶液の全容積を100mLにした。塩溶液を10mL/minで塩基に添加した。添加の終了後、沈殿物を60℃で30分間撹拌して熟成した。濾過して材料を回収し、洗浄して吸着したイオンを除去し、105℃で乾燥させた。試料を700℃で2時間、空気中で焼成して、ペロブスカイト相を形成させた。ペロブスカイトの結晶子のサイズは12.5nmであり、90.9%がペロブスカイト相であった。
混合物(MnOx:La0.9MnO3-ドープされたZrO2)を、MnOx:La0.9MnO3とドープされたZrO2[ドーパント:10.1wt%Nb2O5(5A)、13.05%Y2O3(5B)、又は14.7%Nd2O3(5C)]を別個に水に分散させ、続いて6~7μmのd90に湿式粉砕して調製した。次いで、MnOx:La0.9MnO3とドープされたZrO2のスラリーを2:1の比で3~4時間混合して、乾燥させ、粉砕して粉末にして、700℃で焼成した。
図1及び2に示されるように、比較触媒4は、ドープされたZrO2が存在する場合(10.1%Nb2O5;触媒5A)、劣化させた後、TEM画像から、一次粒子のサイズが安定化されることが示される。比較触媒4では、MnOx:La0.9MnO3の粒子のサイズは、新鮮な時の初期の20~80nmから劣化後に200~1000nmに増加する。ドープされたZrO2が存在する場合(例えば、触媒5A)、MnOx:La0.9MnO3の一次粒子は200~500nmとより小さいままである。
比較触媒4、及び触媒5Aを、500℃の標準的な摂動ガソリン条件下で試験した。次いで、水蒸気の存在下、及びリッチ/リーン条件下、950℃以上の温度を伴い、16時間触媒を劣化させた。具体的な条件を以下に示す:
試験条件:摂動ガス混合物(WHSV=750Lg-1h-1)、λ±0.05:0.73~2.2%CO+666ppmC3H6+333ppmC3H8+2200ppmNO+0.23~0.69%H2+*O2+14%CO2+4%H2O(N2を加えて100%)、3s/摂動、
劣化条件:摂動ガス混合物、λ=0.93~1.06:0.5%CO+1000ppmC3H8+1000ppmNO+0.27~1.07%O2+10%H2O(N2を加えて100%)、5min/摂動。
Claims (23)
- 式(I):LazB1-qB’qO3±δ又は式(II):[BOx]y:[LazBO3±δ]1-yのペロブスカイト型化合物と非レドックス活性成分とを含む三元触媒組成物であって、式中、
B又はB’が、Fe、Mn、Co、Ni、Cu、Ti、又はZrであり、
qが、約0~約0.5の範囲であり、
δが、約0~約0.6の範囲であり、
xが、約1~約2.5であり、
yが、約1~約30wt%であり、
zが、約0.6~約1.1である、三元触媒組成物。 - 前記ペロブスカイト型化合物が式(I):LazBO3±δの化合物である、請求項1に記載の三元触媒組成物。
- BがFeである、請求項2に記載の三元触媒組成物。
- BがMnである、請求項2に記載の三元触媒組成物。
- 前記ペロブスカイト型化合物が、式(II):[BOx]y:[LazBO3±δ]1-yの化合物である、請求項1に記載の三元触媒組成物。
- BがMnである、請求項5に記載の三元触媒組成物。
- 前記非レドックス活性成分が酸化物を含む、請求項1~6のいずれか一項に記載の三元触媒組成物。
- 前記非レドックス活性成分がアルミナを含む、請求項1~7のいずれか一項に記載の三元触媒組成物。
- 前記非レドックス活性成分がZrO2を含む、請求項1~8のいずれか一項に記載の三元触媒組成物。
- 前記ZrO2がドープされている、請求項9に記載の三元触媒組成物。
- 前記触媒が白金族金属を実質的に含まない、請求項1~10のいずれか一項に記載の三元触媒組成物。
- 前記触媒が白金族金属を含まない、請求項1~11のいずれか一項に記載の三元触媒組成物。
- 前記ペロブスカイト型化合物が前記触媒組成物の約5wt%~約75wt%の量で存在する、請求項1~12のいずれか一項に記載の三元触媒組成物。
- 前記非レドックス活性成分が前記触媒組成物の約25wt%~約95wt%の量で存在する、請求項1~13のいずれか一項に記載の三元触媒組成物。
- 前記ペロブスカイト型化合物と前記非レドックス活性成分とが約0.5:1~約3:1の重量比で存在する、請求項1~14のいずれか一項に記載の三元触媒組成物。
- 前記ペロブスカイト型化合物が火炎噴霧熱分解によって調製された、請求項1~15のいずれか一項に記載の三元触媒組成物。
- 前記ペロブスカイト型化合物が少なくとも40m2/gの高表面積を有する、請求項1~16のいずれか一項に記載の三元触媒組成物。
- 排気ガスを処理するための触媒物品であって、
a.基材と、
b.請求項1~17のいずれか一項に記載の三元触媒組成物とを含む、触媒物品。 - 内燃機関からの排気ガスを処理する方法であって、前記排気ガスを、基材と請求項1~17のいずれか一項に記載の三元触媒組成物とを含む触媒物品に接触させることを含む、方法。
- 前記三元触媒組成物が、
(1)新鮮な時の500~600℃でのNO変換率、及び
(2)水蒸気の存在下で、少なくとも700℃の温度で20時間、前記触媒を劣化させた後の劣化後の500~600℃でのNO変換率をもたらし、
前記新鮮な時のNO変換率と前記劣化後のNO変換率との間の差が20%未満の低下である、請求項19に記載の方法。 - 前記新鮮な時のNO変換率と前記劣化後のNO変換率との差が15%未満の低下である、請求項21に記載の方法。
- 前記三元触媒組成物が、
(1)新鮮な時の500℃でのHC又はCO変換率、及び
(2)水蒸気の存在下で、少なくとも700℃の温度で20時間、前記触媒を劣化させた後の劣化後の500℃でのHC又はCO変換率をもたらし、
前記新鮮な時のHC又はCO変換率と前記劣化後のHC又はCO変換率との間の差が50%未満の低下である、請求項19に記載の方法。 - 前記新鮮な時のHC又はCO変換率と前記劣化後のHC又はCO変換率との差が40%未満の低下である、請求項22に記載の方法。
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