JP2010540232A - 水素化および脱水素化反応において使用する焼結耐性触媒ならびにその製造方法 - Google Patents
水素化および脱水素化反応において使用する焼結耐性触媒ならびにその製造方法 Download PDFInfo
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- JP2010540232A JP2010540232A JP2010527353A JP2010527353A JP2010540232A JP 2010540232 A JP2010540232 A JP 2010540232A JP 2010527353 A JP2010527353 A JP 2010527353A JP 2010527353 A JP2010527353 A JP 2010527353A JP 2010540232 A JP2010540232 A JP 2010540232A
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- catalyst
- palladium
- hydrogenation
- nanoparticles
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Abstract
Description
しかしながら、これらの既知の解決策はある程度の焼結を防止できるのみであるため、その構造に起因して焼結を防止する、新しい型の耐熱性触媒の必要性が存在する。
酸化ジルコニウムを含有するシェルの内径は、好ましくは10〜1000nm、非常に好ましくは15〜500nm、とりわけ好ましくは20〜300nmである。
酸化ジルコニウムを含有する層厚は、通常、10〜100nmの範囲であり、好ましくは15〜80nm、特に好ましくは15〜40nmの範囲である。
a)パラジウムナノ粒子の生成
b)生成したパラジウムナノ粒子のSiO2による包み込み
c)Pd/SiO2球への酸化ジルコニウム層の塗布
d)塩基によるSiO2層の洗い流し
の工程を含んでなる触媒の製造方法を提供する。
工程a)におけるパラジウムナノ粒子の生成は、特に好ましくはアルコールに溶解させたパラジウム塩、例えば、PdCl2、H2PdCl4、Pd(NO3)2、トリフルオロ酢酸パラジウム(II)、塩化ビス(アセトニトリル)パラジウム(II)、パラジウム(II)ヘキサフルオロアセチルアセトネートを、パラジウム含有前駆体として使用して行う。
パラジウムナノ粒子の生成−工程a):
マグネットスターラー、コンデンサーおよび加熱装置の備わったフラスコで、106.4mg(2.0mmol)のPdCl2を、6mlのHCl(0.2M)と294mlの蒸留水と混合する。これにより約300mlの2.0mMH2PdCl4溶液が得られる。15ml(30μmolのPd)の2.0mMH2PdCl4溶液を、100mlフラスコ中で31.5mlの水と3.5mlのメタノールと混合する。さらに、300μmol(33.25mg)のPVP40(Sigma−Aldrich)を加え、混合物全体を空気雰囲気中、還流下、3時間加熱する(温度=80℃)。該溶液は、加熱直後、茶色に変わる。パラジウムナノ粒子の沈殿をともなうこの着色溶液を10000rpmで遠心分離する。その後、上澄み液を静かに移す。湿潤パラジウム粒子は、この状態でさらなる合成に使用し得る。図1は、得られたパラジウムナノ粒子の透過電子顕微鏡写真を示す(器具:Tecnai 20 LaB6陰極、カメラ:Tietz F114T 1x1K(FEI/Philips製)、製造業者の指示に従った方法)。平均粒子径は8nmである。
工程a)のパラジウムナノ粒子を、3mlの水に再分散させる(超音波浴:10分)。合成の開始前に、下記の溶液を準備しておかなくてはならない:
a.エタノール−NH3溶液(全10.5ml):0.5mlの濃アンモニア溶液(28〜30%)を10mlのエタノールと混合する。
b.エタノール−TEOS溶液(全7.6ml):0.6mlのテトラエチルオルトケイ酸塩を7mlのエタノールと混合する。
水溶性パラジウムナノ粒子分散体(3ml)をしっかりと(5分間)攪拌する。その後、エタノール−NH3混合物を加える。その後すぐに、エタノール−TEOS混合物を、素早く添加する。反応混合物を室温(20℃)で一晩攪拌する。Pd−SiO2ナノ粒子を遠心分離(10000rpm、25分間)し、それぞれ、遠心分離後の上澄み液を移し、再び遠心分離する前に超音波浴(5分間)を用いて適当な洗浄液により残っている固形物(コロイド)を再分散させることにより、水で2回、無水エタノールで1回洗浄する。最後に、Pd−SiO2ナノ粒子を無水エタノール(40g)にとり、超音波浴(5分、USバス)を用いて再分散させる。このようにして得られるPd−SiO2ナノ粒子を貯蔵し、またはそのまま次工程で使用し得る。図2は、このようにして得られたPd−SiO2ナノ粒子の透過電子顕微鏡写真を示す(器具:Tecnai 20 LaB6陰極、カメラ:Tietz F114T 1x1K(FEI/Philips製)、製造業者の指示に従った方法)。Pd−SiO2ナノ粒子の平均粒子径は、120nmである。
合成の開始前に、Marlipal(登録商標)O13/40溶液(エトキシル化イソトリデカノール;Sasol製)を、11gの水に0.43gのMarlipal(登録商標)を溶解することにより調製する。工程b)で得られたPd−SiO2ナノ粒子(30μmol金属浴)を、40gのエタノールに分散させ、隔壁により閉られた100mlフラスコ内へ無水エタノールを用いて移し、その後30℃まで加熱する。予め調製した水溶性Marlipal(登録商標)溶液0.125ml(125μl)を、30℃に加熱されたPd−SiO2ナノ粒子の攪拌分散体に加える。30分後、0.45mlのジルコニウムn−ブトキシド(ブタノール中80重量%)を加える。4時間攪拌後、分散体の液相を水に置き換える。このために、分散体を遠心分離(10000rpm;15分間)し、上澄み液を移し、上澄み液を取り除いた後の固形物を、25mlの水に再分散させる(超音波浴:5分間)。遠心分離と再分散の一連の作業を3回行う。その後、粒子を2日間、室温で熟成させる。その後、試料を乾燥させ、空気雰囲気中、加熱炉で焼成する。このために、全部で7.5時間にわたって、温度を100℃から900℃に段階的に上げる。
工程c)で得られたPd−SiO2−ZrO2ナノ粒子(30μmol金属浴)を、50mlの1モルNaOH溶液中で、室温で3時間攪拌する。その後、コロイドを遠心分離(10000rpm;30分間)により洗浄し、上澄みを移し50mlの1モルNaOH溶液にとる。分散体を2時間50℃で攪拌し、その後室温で一晩攪拌する。最後に、粒子を、遠心分離/再分散の一連の作業により、5回水で洗浄する。このようにして得られるPd−ZrO2粒子は、もはやSiO2核を有さず、多孔性シェルで焼結バリアを有する。図3aは、透過電子顕微鏡写真を示す(器具:Tecnai 20 LaB6陰極、カメラ:Tietz F114T 1x1K(FEI/Philips製)、製造業者の指示に従った方法)を示し、図3bは、XPS分析(器具:Phoenix(EDAX/Ametek製);製造業者の指示に従った方法)の結果を示す。Pd−ZrO2粒子の平均径は、130nmである。XPS分析から、SiO2がもはやナノ粒子に存在しないことがわかる。
Claims (11)
- 少なくとも1つのナノ粒子パラジウムクラスター、ならびに、酸化ジルコニウムを含有する気体および液体透過性シェルを含んでなる、水素化および脱水素化における使用のための触媒。
- ナノ粒子パラジウムクラスターが、0.1〜100nmの範囲の平均粒度分布(d50)を有し、シェルが、10〜1000nmの範囲の内径を有する酸化ジルコニウムを含有することを特徴とする、請求項1に記載の触媒。
- 酸化ジルコニウムを含有するシェルの層厚が、10〜100nmの範囲にあることを特徴とする、請求項1または2に記載の触媒。
- 請求項1〜3のいずれかに記載の触媒を使用することを特徴とする、触媒存在下、気相中の水素を用いて有機化合物を水素化する方法。
- ニトロ化合物の水素化または移動水素化あるいは脱水素化反応における、請求項1〜3のいずれかに記載の触媒の使用。
- 触媒を、100〜600℃の温度で、液相または気相におけるニトロ化合物の水素化に使用する、請求項5に記載の使用。
- 請求項1〜3のいずれかに記載の触媒を使用することを特徴とする、触媒存在下、気相中の水素を用いてニトロベンゼンをアニリンに転換する方法。
- 請求項1〜3のいずれかに記載の触媒を使用することを特徴とする、触媒存在下、気相中で有機化合物を脱水素化する方法。
- a)0.1〜100μmの範囲の平均粒度分布(d50)を有するパラジウムナノ粒子の生成
b)生成したパラジウムナノ粒子のSiO2による包み込み
c)Pd/SiO2球への酸化ジルコニウム層の塗布
d)塩基によるSiO2層の洗い流し
の工程を含んでなる触媒の製造方法。 - 工程a)におけるパラジウムナノ粒子の生成が、ポリビニルピロリドン、アルコールポリエチレングリコールエーテル、ポリアクリレート、ポリオール、長鎖n−アルキル酸、長鎖n−アルキル酸エステル、長鎖n−アルキルアルコールおよびイオン性界面活性剤からなる群から選択される、少なくとも1つのコロイド安定剤の存在下、液相において、パラジウム含有前駆体の還元により行われることを特徴とする、請求項9に記載の方法。
- 工程c)における酸化ジルコニウム層の塗布が、アルコールポリエチレングリコールエーテル、ポリビニルピロリドン、ポリアクリレート、ポリオール、長鎖n−アルキル酸、長鎖n−アルキル酸エステルおよび長鎖n−アルキルアルコールからなる群から選択される、少なくとも1つのコロイド安定剤の存在下、加水分解性Zr前駆体の加水分解または沈降により行われることを特徴とする、請求項9または10に記載の方法。
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CN112934220B (zh) * | 2021-02-05 | 2022-10-04 | 浙江工业大学上虞研究院有限公司 | 一种中空型钯催化剂微球的制备方法 |
CN112958080B (zh) * | 2021-02-05 | 2022-10-11 | 浙江工业大学上虞研究院有限公司 | 一种介孔型钯催化剂的制备方法 |
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WO2009043496A3 (de) | 2009-06-18 |
US20100204518A1 (en) | 2010-08-12 |
US20130035511A1 (en) | 2013-02-07 |
WO2009043496A2 (de) | 2009-04-09 |
EP2200739A2 (de) | 2010-06-30 |
JP5415425B2 (ja) | 2014-02-12 |
RU2010116815A (ru) | 2011-11-10 |
DE102007047434A1 (de) | 2009-04-09 |
BRPI0817590A2 (pt) | 2015-03-31 |
CN101815575A (zh) | 2010-08-25 |
RU2480278C2 (ru) | 2013-04-27 |
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