JP6896624B2 - Al2O3−CeO2/ZrO2の被覆複合物及びそれらの製造方法 - Google Patents
Al2O3−CeO2/ZrO2の被覆複合物及びそれらの製造方法 Download PDFInfo
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- JP6896624B2 JP6896624B2 JP2017522898A JP2017522898A JP6896624B2 JP 6896624 B2 JP6896624 B2 JP 6896624B2 JP 2017522898 A JP2017522898 A JP 2017522898A JP 2017522898 A JP2017522898 A JP 2017522898A JP 6896624 B2 JP6896624 B2 JP 6896624B2
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- 239000002131 composite material Substances 0.000 title claims description 46
- 238000000034 method Methods 0.000 title claims description 30
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 title claims description 28
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 title claims description 22
- 239000011162 core material Substances 0.000 claims description 159
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- 238000000576 coating method Methods 0.000 claims description 48
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- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 31
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- 238000005470 impregnation Methods 0.000 claims description 24
- 239000000463 material Substances 0.000 claims description 24
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- KRKNYBCHXYNGOX-UHFFFAOYSA-K Citrate Chemical compound [O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O KRKNYBCHXYNGOX-UHFFFAOYSA-K 0.000 claims description 6
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- POILWHVDKZOXJZ-ARJAWSKDSA-M (z)-4-oxopent-2-en-2-olate Chemical compound C\C([O-])=C\C(C)=O POILWHVDKZOXJZ-ARJAWSKDSA-M 0.000 claims description 2
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- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical compound [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 description 9
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- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 8
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 8
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- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 7
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 description 7
- 238000001914 filtration Methods 0.000 description 7
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- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 6
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- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 4
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- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 229910002706 AlOOH Inorganic materials 0.000 description 2
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- 238000002474 experimental method Methods 0.000 description 2
- 150000004820 halides Chemical class 0.000 description 2
- 150000004679 hydroxides Chemical class 0.000 description 2
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
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- 150000002823 nitrates Chemical class 0.000 description 2
- 238000010606 normalization Methods 0.000 description 2
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- 239000002002 slurry Substances 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- 229910000314 transition metal oxide Inorganic materials 0.000 description 2
- BWLBGMIXKSTLSX-UHFFFAOYSA-N 2-hydroxyisobutyric acid Chemical compound CC(C)(O)C(O)=O BWLBGMIXKSTLSX-UHFFFAOYSA-N 0.000 description 1
- 229910052779 Neodymium Inorganic materials 0.000 description 1
- 125000000218 acetic acid group Chemical group C(C)(=O)* 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- FRHBOQMZUOWXQL-UHFFFAOYSA-L ammonium ferric citrate Chemical compound [NH4+].[Fe+3].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O FRHBOQMZUOWXQL-UHFFFAOYSA-L 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
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- 229910003455 mixed metal oxide Inorganic materials 0.000 description 1
- -1 rhodium aluminate Chemical class 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
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Description
Iγ−Al2O3/ICZ
一方、正規化された比は、
(Iγ−Al2O3/ICZ)・(100wt%/(wt%Al2O3))
となる。
i) Al/Ce/Zrコアであって、(020)反射で計測される4nmと40nmの間の結晶サイズを有するベーマイト結晶構造のアルミナ前駆体によって特徴付けられ、両方ともに均一な混合物を形成する2つの相、即ち、La安定化Al2O3相及びCe/Zr/RE2O3混合酸化物相で構成される、Al/Ce/Zrコアを調製するステップと、
ii) か焼Al/Ce/Zrコアを形成するためにAl/Ce/Zrコアをか焼するステップであって、か焼コアは、0.2ml/gを上回る細孔容積、及び50Åと200Åの間に細孔サイズ分布の極大を有する、Al/Ce/Zrコアをか焼するステップと、
iii) か焼Al/Ce/Zrコアに金属酸化物前駆体を含浸させるステップであって、金属酸化物がコアの周りに被覆を形成し、金属酸化物が被覆Al/Ce/Zr複合物の1重量%から50重量%の間を形成して被覆がコアに付けられるように、含浸させるステップと、
iv) 含浸させたコアをか焼して被覆Al/Ce/Zr複合物を形成するステップと、
を含む方法が提供される。
特許文献2(引用により本明細書に組み入れられる)により、Al/Ce/Zrコアは、固溶体の形態で、酸化アルミニウム及びセリウム/ジルコニウム混合酸化物を含むことができ、ここでAl2O3及びCe/Zr混合酸化物は均一な混合物を形成する。Al/Ce/Zrコアは、Al2O3として計算して、20重量%から80重量%の間のアルミニウム、好ましくは40重量%と70重量%の間のアルミニウム、ZrO2として計算して、5重量%から80重量%の間のジルコニウム、CeO2として計算して、5重量%から80重量%の間のセリウム、及び0%から12%の間の希土類金属を含むことができる。
か焼Al/Ce/Zrコアの細孔容積は、好ましくは0.2ml/gと1.0ml/gの間、より好ましくは0.3ml/gと0.7ml/gの間、最も好ましくは0.4ml/gから0.6ml/gの間である。
適切なか焼Al/Ce/Zrコア材料の多孔性は、細孔サイズ分布が50Åと200Åの間、より好ましくは70Åと150Åの間、最も好ましくは80Åから130Åの間のメソ細孔範囲内に顕著な極大を示すことで特徴付けられる。
図2の例で示されるように、か焼Al/Ce/Zrコア材料の細孔容積はアルミナ含量の増加とともに増加する。しかし、細孔半径分布曲線の極大の位置は、アルミナ含量にあまり敏感ではなく、20%と80%の間のアルミナ含量を有するAl/Ce/Zrコア材料に対して、80Åと130Åの間にある顕著な極大を示す。
金属酸化物前駆体は、アルカリ土類元素、遷移金属又は好ましくは希土類金属の酸化物の前駆体を含む。
か焼Al/Ce/Zrコアに金属酸化物前駆体を含浸させるために種々のタイプの含浸技術を使用することができる。これらは、例えば、初期湿潤含浸、平衡析出ろ過、又は湿潤含浸を含む。
La浸出抑制に関して用いられる試験は以下に含まれる。
金属酸化物表面層のない本発明のコア材料、及び金属酸化物又は混合金属酸化物表面層で被覆された本発明のコア材料のLa浸出試験を、pH=3のHNO3水溶液中で粉末を処理することによって行った。この混合物を室温で1時間撹拌し、次いで遠心分離し、ろ過した。ろ過溶液を、誘導結合プラズマ発光分光法(ICP−OES:inductively coupled plasma optical emission spectroscopy)によって分析し、試料から浸出するランタン%(La浸出%)を決定した。
種々のAl/Ce/Zrコア材料の調製を従来技術に従って行い、以下に詳しく説明する。
Al/Ce/Zr複合コア材料の調製を、特許文献1に従って行った。
このAl/Ce/Zrコア材料を、特許文献2の実施例4に従って調製した。
種々のアルミナ含量を有するAl/Ce/Zr複合コアC材料の調製を、特許文献1に記載の方法に従って行った。
このAl/Ce/Zrコア材料は、特許文献3の実施例1の同じステップに従って調製した。
Ce(NO3)3の水溶液を、Al/Ce/ZrコアA材料に連続的に混合しながら、初期湿潤点に達するまで、即ち、Al/Ce/Zrコア材料の細孔容積が溶液で完全に満たされるまで、加えた。
Al/Ce/ZrコアA材料を、1重量%のCeO2の濃度の、必要量のCe酢酸塩水溶液の中に再懸濁させた。得られた懸濁液に撹拌しながらアンモニア溶液を加えてpHを9.0にした。次に、混合物を撹拌しながら50℃で3時間加熱した。その後、試料をろ過し、120℃で一晩乾燥させ、550℃で3時間か焼した。最終的な材料のICP分析は、Al/Ce/Zrコア材料の上への17重量%のCeO2の組み込みを示した。
クエン酸アンモニウム2塩基性塩を脱イオン水に溶解させ、アンモニア溶液を加えてpHを10に調節した。このクエン酸塩溶液に、Ceクエン酸塩錯体を調製するために、1:1のクエン酸塩:CeO2のモル比を用いてCe酢酸塩溶液を滴加した。錯体を室温で2時間熟成させた。次に、この溶液にAl/Ce/ZrコアA材料を加え、得られた懸濁液を一定撹拌しながら室温で24時間熟成させた。その後、懸濁液をロータリ・エバポレータ内で温度及び真空を適用して乾燥させ、乾燥粉末を最終的に550℃で3時間か焼した。
初めに、エチレンジアミン四酢酸(EDTA:ethylenediaminetetraacetic acid)を脱イオン水に、アンモニア溶液でpHを10に調節したのちに溶解させた。このEDTA溶液に、Ce−EDTA錯体を調製するために、1:1のEDTA:CeO2のモル比を用いてCe酢酸塩溶液を滴加した。錯体を室温で2時間熟成させた。
最終的に50重量%のCeO2を組み込むために、6.4重量%のCeO2濃度を有するCe酢酸塩水溶液の必要量の中にAl/Ce/ZrコアA材料を再懸濁させた。この懸濁液をロータリ・エバポレータ内で温度及び真空を適用して乾燥させ、乾燥粉末を最終的に550℃で3時間か焼した。最終的な材料のICP分析は、Al/Ce/Zrコア材料への46重量%の実際のCeO2の組み込みを確かめた。
Al/Ce/Zrコア材料に総量で10重量%のZrO2を組み込むために、1重量%のZrO2濃度を有するZr酢酸塩水溶液の必要量の中にAl/Ce/ZrコアA材料を再懸濁させた。この結果として得られた懸濁液に撹拌しながらアンモニア溶液を加えてpH9.0にした。次に、混合物を撹拌しながら50℃で3時間加熱した。その後、試料をろ過し、120℃で一晩乾燥させ、550℃で3時間か焼した。最終的な材料のICP分析は、Al/Ce/Zrコア材料への9重量%のZrO2の組み込みを示した。
Al/Ce/Zrコア材料に総量で40重量%の混合酸化物を組み込むために、総濃度で1重量%のMxOy(MxOy=CeO2+ZrO2+Nd2O3)を有する、Ce酢酸塩、Zr酢酸塩及びNd酢酸塩を含んだ水溶液の必要量の中に、Al/Ce/ZrコアA材料を再懸濁させた。この結果として得られた懸濁液に撹拌しながらアンモニア溶液を加えてpH9.0にした。次に、混合物を撹拌しながら50℃で3時間加熱した。その後、試料をろ過し、120℃で一晩乾燥させ、550℃で3時間か焼した。最終的な材料のICP分析は、Al/Ce/Zrコア材料への39重量%の混合酸化物の組み込みを示した。
20gのAl/Ce/ZrコアB材料を、(NH4)2Ce(NO3)6の水溶液を加えることにより2ステップで含浸させる。各含浸ステップに対して、およそ10重量%のCeO2を各含浸ステップにおいて組み込むために、総体積16.6mlの水中の6.9gの(NH4)2Ce(NO3)6塩で構成される溶液を用いた。含浸ステップと含浸ステップの間で、粉末を120℃で2時間乾燥させた。第2の含浸の後、試料を120℃で16時間乾燥させ、550℃で3時間か焼した。
特許文献3に従って調製した20gのAl/Ce/ZrコアD材料を、(NH4)2Ce(NO3)6の水溶液を加えることにより2ステップで含浸させる。各含浸ステップに対して、およそ10重量%のCeO2を各含浸ステップにおいて組み込むために、総体積16.6mlの水中の6.9gの(NH4)2Ce(NO3)6塩で構成される溶液を用いた。含浸ステップと含浸ステップの間で、粉末を120℃で2時間乾燥させた。第2の含浸の後、試料を120℃で16時間乾燥させ、550℃で3時間か焼した。
Claims (14)
- か焼Al/Ce/Zrコアを含む被覆Al/Ce/Zr複合物であって、前記コアは2つの相、即ち、La安定化Al2O3相及びCe/Zr/RE2O3混合酸化物相で構成され、両相は均一な混合物を形成し、前記か焼Al/Ce/Zrコアは、0.2ml/gを上回る細孔容積(DIN66133による)、及び50Åと200Åの間に極大を有する細孔サイズ分布(DIN66133による)を有することによって特徴付けられ、前記コアは金属酸化物被覆を含み、前記金属酸化物被覆は、前記被覆Al/Ce/Zr複合物の少なくとも1重量%から50重量%を形成し、前記被覆複合物中の前記Al/Ce/Zrコアは、2θ≒67°におけるガンマ・アルミナの特性反射ピーク強度と、2θ≒29°におけるCe/Zr固溶体の特性反射ピーク強度との間の、Al2O3重量%で正規化された、1に等しいか又は1より大きい強度比によって特徴付けられ、前記金属酸化物被覆は、CeO 2 、ZrO 2 、セリア/ジルコニアの混合酸化物、及びセリアとは異なる1つ又はそれ以上の希土類金属酸化物から成る群から選択される1つ又はそれ以上の部材を含む、被覆複合物。
- 前記金属酸化物被覆はCeO2を含み、好ましくはCeO2から成る、請求項1に記載の被覆複合物。
- 前記か焼Al/Ce/Zrコアの前記細孔容積は、0.2ml/gから1.0ml/gの間、好ましくは0.4ml/gから0.6ml/gの間である、請求項1又は2に記載の被覆複合物。
- 前記か焼Al/Ce/Zrコアの前記細孔サイズ分布は、70Åから150Åの間の極大、好ましくは80Åから130Åの間の極大を有する、請求項1〜3のいずれか1項に記載の被覆複合物。
- 前記金属酸化物被覆は、前記被覆Al/Ce/Zr複合物の4重量%から27重量%の間を形成する、請求項1〜4のいずれか1項に記載の被覆複合物。
- 被覆Al/Ce/Zr複合物を製造する方法であって、
i) Al/Ce/Zrコア材料であって、前記コアは、(020)反射において計測される4nmと40nmの間の結晶サイズを有するベーマイト結晶構造のアルミナ前駆体によって特徴付けられ、前記コアは2相、即ち、両相ともに均一な混合物を形成するLa安定化Al2O3相及びCe/Zr/RE2O3混合酸化物相から成る、Al/Ce/Zrコア材料を調製するステップと、
ii) か焼Al/Ce/Zrコアを形成するために前記Al/Ce/Zrコアを焼するステップであって、前記か焼Al/Ce/Zrコアは、0.2ml/gを上回る細孔容積、及び50Åと200Åの間に細孔サイズ分布の極大を有することによってさらに特徴付けられる、か焼するステップと、
iii) 前記か焼Al/Ce/Zrコアを、金属酸化物前駆体で、前記金属酸化物前駆体が、前記コアの上の被覆を形成するように、含浸させるステップであって、前記金属酸化物前駆体が、前記コアに被覆が付けられるように、前記被覆Al/Ce/Zr複合物の1重量%から50重量%の間を形成する、含浸させるステップと、
iv) 前記含浸されたコアを、金属酸化物被覆が前記コアに付けられて前記被覆Al/Ce/Zr複合物を形成するように、か焼するステップであり、前記金属酸化物被覆が、前記被覆Al/Ce/Zr複合物のか焼の後、1重量%から50重量%の間を形成する、か焼するステップであって、前記金属酸化物被覆は、CeO 2 、ZrO 2 、セリア/ジルコニアの混合酸化物、及びセリアとは異なる1つ又はそれ以上の希土類金属酸化物から成る群から選択される1つ又はそれ以上の部材を含む、か焼するステップと、
を含む方法。 - 前記ベーマイトは、6.05Åから6.20Åまで、好ましくは6.11Åの前記(020)反射のD値によってさらに特徴付けられる、請求項6に記載の方法。
- 前記金属酸化物前駆体は、アルカリ土類元素、遷移金属又は希土類金属の酸化物の前駆体を含む、請求項6又は7に記載の方法。
- 前記金属酸化物前駆体は、CeO2、ZrO2、セリア/ジルコニアの混合酸化物、及びセリアとは異なる1つ又はそれ以上の希土類金属酸化物の前駆体から成る群から選択される1つ又はそれ以上の部材を含む、請求項6〜8のいずれか1項に記載の方法。
- 前記金属酸化物前駆体は、CeO2の前駆体から成り、好ましくはCeO2のみの前駆体から成る、請求項6〜9のいずれか1項に記載の方法。
- 前記CeO2前駆体は、Ce硝酸塩、(NH4)2Ce(NO3)6、Ce酢酸塩、Ce炭酸塩、Ce硫酸塩、Ce水酸化物、Ceシュウ酸塩、Ceアセチルアセトネート、Ceクエン酸錯体及びCe−EDTA錯体からなる群から選択される1つまたはそれ以上の部材である、請求項9又は10に記載の方法。
- 前記か焼Al/Ce/Zrコアは、2θ≒67°におけるガンマ・アルミナの特性反射ピーク強度と、2θ≒29°におけるCe/Zr固溶体の特性反射ピーク強度との間の、Al2O3の重量%で正規化された、1に等しいか又は1より大きい強度比で特徴付けられる、請求項6〜11のいずれか1項に記載の方法。
- 前記Al/Ce/Zrコアのか焼は、400℃から900℃、好ましくは500℃から850℃の温度において行われる、請求項6〜12のいずれか1項に記載の方法。
- 含浸後のか焼は、400℃から900℃、好ましくは500℃から700℃の温度において行われる、請求項6〜13のいずれか1項に記載の方法。
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