JP2009515693A - 還元剤の存在下に異方性金属ナノ粒子をベースとする触媒の製造方法 - Google Patents
還元剤の存在下に異方性金属ナノ粒子をベースとする触媒の製造方法 Download PDFInfo
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- JP2009515693A JP2009515693A JP2008540649A JP2008540649A JP2009515693A JP 2009515693 A JP2009515693 A JP 2009515693A JP 2008540649 A JP2008540649 A JP 2008540649A JP 2008540649 A JP2008540649 A JP 2008540649A JP 2009515693 A JP2009515693 A JP 2009515693A
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- ABKQFSYGIHQQLS-UHFFFAOYSA-J sodium tetrachloropalladate Chemical compound [Na+].[Na+].Cl[Pd+2](Cl)(Cl)Cl ABKQFSYGIHQQLS-UHFFFAOYSA-J 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 235000011150 stannous chloride Nutrition 0.000 description 1
- 238000007619 statistical method Methods 0.000 description 1
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- KGYLMXMMQNTWEM-UHFFFAOYSA-J tetrachloropalladium Chemical compound Cl[Pd](Cl)(Cl)Cl KGYLMXMMQNTWEM-UHFFFAOYSA-J 0.000 description 1
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- AXZWODMDQAVCJE-UHFFFAOYSA-L tin(II) chloride (anhydrous) Chemical compound [Cl-].[Cl-].[Sn+2] AXZWODMDQAVCJE-UHFFFAOYSA-L 0.000 description 1
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- 238000004627 transmission electron microscopy Methods 0.000 description 1
- ZMBHCYHQLYEYDV-UHFFFAOYSA-N trioctylphosphine oxide Chemical compound CCCCCCCCP(=O)(CCCCCCCC)CCCCCCCC ZMBHCYHQLYEYDV-UHFFFAOYSA-N 0.000 description 1
- 238000001947 vapour-phase growth Methods 0.000 description 1
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Abstract
【解決手段】元素周期律表の8、9,10族から選ばれた少なくとも一つの金属の源(ソース)に接触する、二つの異なった還元剤を用いる工程を含む、異方性(anisotropic)金属ナノ粒子の製法であり、該製法は少なくとも以下から構成される。a)以下の工程の一つ。a1)元素周期律表の8族、9属、10族から選ばれた少なくとも一つの金属の源を含む水溶液で担体を含浸し、ついで該担体を還元剤R1と接触させる。またはa2)元素周期律表の8族、9属、10族から選ばれた少なくとも一つの金属の源を含む水溶液を還元剤R1と接触させる。b)工程a)で得られた溶液または担体をR1と異なる還元剤R2と接触させる異方性金属ナノ粒子を生成する工程。c)工程a)が工程a2)である場合は、場合によっては担体上に異方性金属ナノ粒子を担持する。
【選択図】 なし
Description
Y.Sun,Y Xia(Advanced Materials,2002、14、833-837) Chaudret et al(C R Chimie,6,2003,1019-1034) Gomez et al(Chem Comm,2001、1474) B Veisz and Z Kirali(Langmuir 2003、19、4817-) Filamkembo et al(J Phys Chem B,2003,107,7492) Busbee et al(Advanced Materials,2003、15、414-)
a2)元素周期律表の8族、9属、10族から選ばれた少なくとも一つの金属の源を含む水溶液を還元剤R1と接触させる。
c)工程a)が工程a2)である場合は、場合によっては担体上に異方性金属ナノ粒子を担持する。
生成するナノ粒子の金属は元素周期律表の8、9、10族に属する金属から選ばれる。好ましくは生成するナノ粒子の金属はニッケル、コバルト、鉄、ルテニウム、白金、パラジウム、インジウム、さらに好ましくはコバルト、ニッケル、白金またはパラジウムである。本来還元に対して良い性能を有している金、銀、銅と比べ、上に述べた金属は驚くことに本発明の製造方法に使用できることを見出した。
二つの異なる還元剤R1とR2
本発明の方法のさらなる分野において、R1とは異なる第二の還元剤R2が加えられる。用語「異なる還元剤」は異なる還元力を有する還元剤を意味する。
・有機還元剤としてはカルボン酸、アルコール、ポリオール、アルデヒド、ケトンおよびそれらのイオン。
・還元剤R1は、水素、ヒドラジン、ヒドロキシルアミン、水素化物とボロンハイドライドから構成されるグループから選択され、および/または
・還元剤R2は、カルボン酸、アルコール、ポリオール、アルデヒド、ケトンおよびそれらのイオンから構成されるグループから選択される。
少なくとも一つの安定化剤の添加(任意)
好ましくは少なくとも一つの安定化剤が還元剤の一つと接触する少なくとも一つの溶液に添加される。
・zとdは0から2の範囲
・Rは1から25、好ましくは8から18を含む炭化水素鎖である。
・カルボニル基を有するどの有機化合物でもよい。例えばクエン酸、酢酸またはアセチルアセトン基、ポリビニルピロリドンのようなポリマーまたは脂肪酸またはオレイン酸のようなカルボン酸である。
・チオフェノール、ジホスフィンまたはアルコール基を有するどの有機化合物でもよい。同様に
・上にリストアップした官能基のいくつかと関連したどの他の組み合わせでもよい。
・続いて両溶液の少なくとも一部を混合する。
還元工程
上に述べたように還元剤R1とR2は種々な方法で導入される。
実施態様1
a2)+b)+任意にc)、即ち
a2) 8、9,10族から選ばれた少なくとも一つの金属の源を含む溶液を還元剤R1と接触させる工程、
b) 程a2)で得られた溶液を還元剤R1と異なる還元剤R2と接触させることにより異方性金属ナノ粒子を生成する工程、
c) 場合によっては、担体に異方性金属ナノ粒子を担持させる。
・元素周期律表の8、9、10族から選ばれた金属の源と安定化剤を含む二つの水溶液が調製され、
・これに還元剤R2の水溶液が添加され、および還元剤R1が別の溶液に添加され、
・二つの溶液の少なくとも一部が混合される。
a1)+b)、即ち、
a1) 元素周期律表の8、9、10族から選ばれた少なくとも一つの金属の源を含む水溶液で担体を含浸し、ついで該担体を還元剤R1と接触させる工程、
b) および工程a1)で得られた担体を還元剤R1と異なった還元剤R2と接触させることにより異方性金属ナノ粒子を生成する工程
工程a1)で8,9,10族から選ばれた元素で含浸(乾式含浸が好ましい)された担体を調製し、少なくとも一つの還元剤R1を接触させる。
担体、含浸と触媒材料の製造
好ましくは担体は秩序だった構造がない酸化物である。用語「秩序だった構造がない」は特別な構造的な特徴、または特別の形の構造、または中間の構造(即ち空孔の大きさの秩序だった構造)を有しない担体を一般的に意味する。
・元素周期律表の14族からの元素
・アルカリ金属、特にリチウム、ナトリウム、カリウム、および/またはアルカリ土類、好ましくはマグネシウム、カルシウム、ストロンチウム、バリウム、および/または
・ハロゲン
・11族からの元素
一般にこれらの元素は担体にナノ粒子を担持した後、含浸により導入される。
得られた生成物
上のように本発明は、該粒子を含む懸濁物と同様に異方性金属ナノ粒子を含む固体の材料を生成する。
得られた生成物の利用
このように本発明の方法により得られた異方性金属ナノ粒子、およびそれらを含む生成物(上に述べた懸濁物や固体材料のようなもの)は、好適に触媒として使用されてよい。
MPa、150-350℃、時間当たりのガスの体積/触媒の体積が100-20000、H2/CO比が1.2から2.5で供給される。工程は固定床やスラリーを用いて実施される。
実施例
本発明のナノ粒子製造方法は以下の実施例で説明される。本発明の方法で直接に得られるナノ粒子からなる触媒の性能は、従来の技術方法で得られる触媒の性能と比較された。これらの実施例は実例で説明されるが、本発明の範囲を限定するのもでない。
実施例1:パラジウムの担持された異方性ナノ粒子の合成(本発明に相当する触媒A、a2)を実行する)
最初に、濃度0.3モル/リッターの臭化セチルトリメチルアンモニウム水溶液25mlを、濃度5×10−4モル/リッターのNa2PdCl4.3H2Oの水溶液50mlに加える。および濃度0.01モル/リッターの水素化ホウ素ナトリウム水溶液6mlを攪拌しながら滴下して加える。10分間攪拌後、調製されたナノ粒子の溶液を2時間静置する。
実施例2:担持された白金の異方性ナノ粒子の合成(触媒B、本発明に相当しない)
最初に、濃度0.3モル/リッターの臭化セチルトリメチルアンモニウム水溶液25mlを、濃度5×10−4モル/リッターのPt(NH3)4(OH)2の水溶液50mlに加える。および濃度0.01モル/リッターの水素化ホウ素ナトリウム水溶液の12mlを攪拌しながら滴下して加える。10分間攪拌後、調製されたナノ粒子の溶液B1を2時間静置する。
実施例3:コバルトの担持された異方性ナノ粒子の合成(触媒C,a2)を実施する本発明に相当する)
濃度0.3モル/リッターの臭化セチルトリメチルアンモニウム水溶液25mlを、濃度5×10−4モル/リッターのCo(NO3)2の水溶液50mlに加える。および濃度0.01モル/リッターの水素化ホウ素ナトリウム水溶液12mlを攪拌しながら滴下して加える。10分間攪拌後、溶液C1が得られる。およびこの溶液に、濃度10−3mol/lのCo(NO3)2の溶液50ml、濃度0.08モル/リッターの臭化セチルトリメチルアンモニウム水溶液50ml、濃度0.08mol/lのアスコルビン酸の溶液5mlと0.5NのNaOH溶液2mlを含む溶液C2を加える。得られた溶液は2時間後に黒くなる。
実施例4:アルミナに担持されたパラジウムの等方性ナノ粒子の合成(触媒D,本発明に相当しない)
Pdの等方性ナノ粒子を含むアルミナに担持されたPd触媒が、前駆体Pd(acac)2を含むトルエン溶液の過剰量の含浸により調製される。触媒は120℃で一晩乾燥し、350℃、2時間で焼成する。
実施例5:アルミナに担持された白金の等方性ナノ粒子の合成(触媒E、本発明に相当しない)
白金の等方性ナノ粒子を含むアルミナに担持された白金触媒が、前駆体Pt(acac)2を含むトルエン溶液の過剰量の含浸により調製される。触媒は120℃で一晩乾燥し、350℃、2時間で焼成する。
実施例6:アルミナに担持されたコバルトの等方性ナノ粒子の合成(触媒F、本発明に相当しない)
コバルトの等方性ナノ粒子を含むアルミナに担持されたコバルトベースの触媒が、Co(NO3)2の溶液で乾式含浸により調製され、120℃で一晩乾燥し、200℃で焼成する。
実施例7:パラジウムの担持された異方性ナノ粒子の合成(触媒G,a1)を実行する本発明に相当する)
最初に、硝酸パラジウムの溶液の50mlは、パラジウム7.8重量%を含む硝酸パラジウム1.3gを希釈して調製した。次に水酸化ナトリウムの溶液50mlは、1NのNaOH溶液7.5mlを希釈して調製した。およびパラジウムの硝酸溶液はNaOH溶液に加えられる。溶液のpHは13である。およびこの溶液でアルミナを浸漬する。得られた固体G1は120℃で一晩乾燥し、200℃で焼成し、および150℃で2時間水素で還元する。
実施例8:パラジウムの担持された異方性ナノ粒子の合成(触媒H,従来技術)
最初に、濃度0.3モル/リッターの臭化セチルトリメチルアンモニウム水溶液25mlを、濃度5×10−4モル/リッターのK2PdCl4の水溶液50mlに加える。および濃度0.01モル/リッターの水素化ホウ素ナトリウムの水溶液12mlを攪拌しながら滴下して加える。10分間攪拌後、調製されたナノ粒子の溶液H1を2時間静置する。
実施例9:担持された白金の異方性ナノ粒子の合成(触媒I,本発明のa2)を実施する)
最初に、濃度0.3モル/リッターの臭化セチルトリメチルアンモニウム水溶液25mlを、濃度5×10−4モル/リッターのK2PtCl4.3H2Oの水溶液50mlに加える。および濃度0.01モル/リッターの水素化ホウ素ナトリウム水溶液6mlを攪拌しながら滴下して加える。10分間攪拌後、調製されたナノ粒子の溶液Aを2時間静置する。
実施例10:1,3−ブタジエンの水素化の触媒テスト
1,3−ブタジエンの水素化は2MPaの水素の一定の圧力、17℃に調節された温度で、完全に攪拌できる「Grignard」型のバッチ式反応槽で液相(n−ヘプタン)中で実施される。反応生成物はガスクロマトグラフィーで分析する。分当たり、金属のg当たりの水素のモルで表わされる触媒活性は、圧力降下を測定することにより決定される。これらの触媒活性を表1に示す。1−ブテンの選択率は、1,3−ブタジエンの80%転換率で測定される。テストの前に、触媒A,B,G,H,Iは、50℃で水素で前処理される。触媒Dは200℃で水素で前処理される。触媒Eは550℃で水素で前処理される。
実施例11:接触的合成ガス転換テスト
合成ガスの転換反応は、2MPaの水素の一定の圧力と220℃の温度で連続的固定床反応器で実施される。時間当たり空間速度は約1500h−1に保たれ、H2/COモル比は2に保たれる。
実施例12:石油留分の転換の触媒テスト(接触改質)
接触改質反応は、以下の性質の石油留分について連続的固定床反応器で水素(H2/供給のモル比=5)の存在下に実施される。
・リサーチ オクタン価:60
・パラフィン含有量:51%
・ナフテン含有量:36%
・芳香族含有量:13%
実験条件は以下である。
・500℃の温度
・触媒に対する供給流速が3kg/kg
テストの間、温度はオクタン価を一定に保つように徐々に調節される。触媒テストの前に触媒Bは100℃で水素中で処理され、触媒Eは550℃で水素中で処理される。操作10時間後に得られた触媒の性能を表3に示す。
実施例13:C10からC14のパラフィンの接触脱水素化のテスト
C10からC14のパラフィンの脱水素化のテストは450℃で、0.29MPaの圧力、炭化水素に対する水素のモル比が6で、HSVが20h−1で回転床反応器で実施される。水の2000ppmの補充はテストの間を通じて供給される。
実施例14:接触選択的一酸化炭素の酸化テスト
接触選択的一酸化炭素の酸化反応は、70℃から130℃の範囲の温度で、大気圧で回転床反応器で実施される。CO:H2:O2:Heの反応混合物は一酸化炭素を2重量%、H2を50重量%を含み、CO/O2比が3である。触媒活性を表5に示す。
実施例15:水素貯蔵性能テスト
水素貯蔵性能テストは、20℃から1000℃の間の温度と1から50ロッドの範囲の圧力に亘って水素の吸着の動力学の測定可能なRubotherm社の圧力熱天秤を使用して実施された。テストした触媒は測定るつぼに置かれ、および反応器は、真空にしてパージし、水素で追い出し、および水素圧力下に置かれる。熱サイクルは、水素の吸着動力学(水素化)と水素の脱着動力学(分解)を決定するために実施される。
Claims (36)
- 元素周期律表の8、9,10族から選ばれた少なくとも一つの金属の源(ソース)に接触する、二つの異なった還元剤を用いる工程を含む、異方性(anisotropic)金属ナノ粒子の製法であり、該製法は少なくとも以下から構成される。
a)以下の工程の一つ。
a1)元素周期律表の8族、9属、10族から選ばれた少なくとも一つの金属の源を含む水溶液で担体を含浸し、ついで該担体を還元剤R1と接触させる。または
a2)元素周期律表の8族、9属、10族から選ばれた少なくとも一つの金属の源を含む水溶液を還元剤R1と接触させる。
b)工程a)で得られた溶液または担体をR1と異なる還元剤R2と接触させる異方性金属ナノ粒子を生成する工程。
c)工程a)が工程a2)である場合は、場合によっては担体上に異方性金属ナノ粒子を担持する。 - 工程a1)+b)またはa2)+b)が、該二つの還元剤を単一の工程で一緒に導入して、実施される請求項1に記載の製法。
- 工程b)は、金属ナノ粒子の種を生成した後に還元剤R2を導入することによる「2工程」方法において、工程a)の後に実施される請求項1に記載の製法。
- 金属が、ニッケル、コバルト、鉄、ルテニウム、白金、パラジウム、イリジウムから選ばれる請求項1〜3の何れかに記載の製法。
- 金属がコバルト、ニッケル、パラジウム、白金からなるクループから選ばれる請求項4に記載の製法。
- 還元剤R1とR2が、以下により構成されているグループから選ばれる請求項1〜5の何れかに記載の製法。
・無機還元剤として水素、ヒドラジン、ヒドロキシルアミン、水素化アルカリ、水素化ホウ素
・有機還元剤としてカルボン酸、アルコール、ポリオール、アルデヒド、ケトンおよびそれらのイオン - 塩基が工程b)中に加えられる請求項1〜6の何れかに記載の製法。
- 無機塩が工程b)中に加えられる請求項1〜7の何れかに記載の製法。
- 無機塩がアルカリのハロゲン化物、アルカリ土類のハロゲン化物からなるグループから選ばれる請求項8に記載の製法。
- R1またはR2と接触している溶液の少なくとも一つに安定化剤が加えられる請求項1〜9の何れかに記載の製法。
- 安定化剤が界面活性剤または錯化剤である請求項10に記載の製法。
- 以下に記述する手順を行う請求項10または11に記載の製法。
・安定化剤と金属の源を別々に溶解し、
・続いて、溶解した安定化剤の少なくとも一部と溶解した金属の源の少なくとも一部とを混合する。 - 得られた触媒が担体を含み、該担体は、秩序だった構造がない酸化物である請求項1〜12の何れかに記載の製法。
- 担体がアルミナとシリカからなるグループより選ばれる請求項13に記載の製法。
- 工程b)またはc)の後に、以下から選ばれる少なくとも一つの元素が含浸により担体に導入される請求項1〜14の何れかに記載の製法。
・元素周期律表の13族からの元素
・元素周期律表の14族からの元素
・アルカリ金属、好ましくはリチウム、ナトリウム、またはカリウム、および/またはアルカリ土類金属、好ましくはマグネシウム、カルシウム、ストロンチウムまたはバリウム、および/または、
・ハロゲン
・元素周期律表の11族からの元素 - 異方性金属ナノ粒子の平均の大きさが10から500nmの範囲にある1〜15請求項の何れかに記載の製法。
- 工程b)中に形状係数Fが0.7以下の異方性金属ナノ粒子が形成される請求項1〜16の何れかに記載の製法。
- 金属ナノ粒子の少なくとも50%が異方性金属ナノ粒子の形状である請求項1〜17の何れかに記載の製法。
- 工程a1)+b)またはc)の終りで得られる異方性金属ナノ粒子を含む担体が液体から
分離され、120℃またはそれ以下の温度で乾燥される請求項1〜18の何れかに記載の製法。 - 担体が600℃以下の温度で水素中活性化処理を受ける(undergo)請求項19に記載の製法。
- 工程b)の終わりに得られる異方性金属ナノ粒子が該液体から分離され、場合によっては乾燥される請求項1〜18の何れかに記載の製法。
- 得られた固体状の異方性金属ナノ粒子が600℃以下の温度で水素中活性化処理される
請求項に記載21の製法。 - 製法の工程a2)+b)の終わり得られる懸濁物が600℃以下の温度で水素中活性化処理される請求項1〜18の何れかに記載の製法。
- 得られる異方性金属ナノ粒子が懸濁物に取り込まれている請求項22に記載の製法。
- 懸濁物が600℃以下の温度で水素中活性化処理される請求項24に記載の製法。
- 請求項19または20に記載の製法により得られた担体と異方性金属ナノ粒子からなる固体物質の触媒としての用途。
- 請求項1から18の何れか、または請求項21,24または25に記載の製法より工程a2)+b)の終わりに得られる懸濁物の触媒としての用途。
- 請求項22または請求項23に記載の製法により得られる固体状の異方性金属ナノ粒子の触媒としての用途。
- 請求項1〜25の何れかに記載の製法により得られる物質を用いる分子の分離または吸着の方法。
- 請求項1〜28の何れかに記載の触媒を用いる接触炭化水素改質方法。
- 請求項1〜28の何れかに記載の触媒を用いる全または選択的水素化の方法。
- 請求項1〜28の何れかに記載の触媒を用いる脱水素環化の方法。
- 請求項1〜28の何れかに記載の触媒を用いる炭化水素の脱水素化の方法。
- 請求項1〜28の何れかに記載の触媒を用いるフィシャー−トロプシュ合成方法。
- 請求項1〜28の何れかに記載の触媒を用いる一酸化炭素の全酸化または選択的酸化の方法。
- 請求項1〜28の何れかに記載の触媒を用いるガス貯蔵の方法。
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FR0511523 | 2005-11-14 | ||
PCT/FR2006/002512 WO2007057553A1 (fr) | 2005-11-14 | 2006-11-14 | Procede de synthese en presence de reducteur d'un catalyseur a base de nanoparticules metalliques anisotropes |
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Publication number | Publication date |
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DE602006019632D1 (de) | 2011-02-24 |
US8030242B2 (en) | 2011-10-04 |
EP1951460B1 (fr) | 2011-01-12 |
CN101309768A (zh) | 2008-11-19 |
FR2893262A1 (fr) | 2007-05-18 |
WO2007057553A1 (fr) | 2007-05-24 |
ZA200803802B (en) | 2009-02-25 |
JP5563221B2 (ja) | 2014-07-30 |
CN101309768B (zh) | 2012-09-05 |
EP1951460A1 (fr) | 2008-08-06 |
US20090226357A1 (en) | 2009-09-10 |
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