JP4116891B2 - Catalyst for reduction reaction, production method thereof, and selective hydrogenation method - Google Patents
Catalyst for reduction reaction, production method thereof, and selective hydrogenation method Download PDFInfo
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- JP4116891B2 JP4116891B2 JP2003026134A JP2003026134A JP4116891B2 JP 4116891 B2 JP4116891 B2 JP 4116891B2 JP 2003026134 A JP2003026134 A JP 2003026134A JP 2003026134 A JP2003026134 A JP 2003026134A JP 4116891 B2 JP4116891 B2 JP 4116891B2
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- 238000005984 hydrogenation reaction Methods 0.000 title claims description 61
- 238000006722 reduction reaction Methods 0.000 title claims description 44
- 238000000034 method Methods 0.000 title claims description 22
- 238000004519 manufacturing process Methods 0.000 title claims description 14
- 238000006243 chemical reaction Methods 0.000 claims description 102
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical group [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 45
- 230000007704 transition Effects 0.000 claims description 30
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 25
- 150000002500 ions Chemical class 0.000 claims description 22
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- 238000006467 substitution reaction Methods 0.000 claims 5
- 230000009467 reduction Effects 0.000 description 37
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- 239000000126 substance Substances 0.000 description 14
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- 229940125782 compound 2 Drugs 0.000 description 7
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- 230000003197 catalytic effect Effects 0.000 description 5
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- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 5
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- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 2
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Images
Classifications
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Indole Compounds (AREA)
- Catalysts (AREA)
Description
【０００１】
【発明の属する技術分野】
本発明は、パラジウム等の遷移元素からなる触媒物質を担持させた還元反応用触媒及びその製造方法、並びに選択的水素添加方法に関する。
【０００２】
【従来の技術】
従来、化学品や医薬品等の有機化合物を合成する際、あるいは石油の還元脱硫を行う際に、水素化（還元）触媒が使用されている。この触媒としては、主にパラジウムブラック（Ｐｄ微粉末）やＰｄ−Ｃ（粉状活性炭にＰｄ微粉末を添着させたもの）等の粉体が用いられ、反応対象物（反応基質）を溶媒に溶解させた溶液に粉末の触媒を投入して反応を進行させている。
一方、還元触媒は、水素添加反応と加水素分解反応のいずれにも作用し、これらの反応条件が同一であるために、このうち一方の反応のみを反応基質に対して選択的に行わせることは難しい。そこで、本発明者らは、ベンジルオキシアルケンの選択的水素添加方法として、電解による方法を報告している（例えば、特許文献１、２参照）。この方法では、陰極として用いるパラジウム薄膜で反応系を２槽に区切り、そのうち１槽で水を電気分解して水素を発生させる。水素は、水素吸蔵金属であるパラジウム薄膜に吸蔵され、反対面から他の槽中に透過する。この槽の反応液には反応基質であるベンジルオキシアルケンが溶解しており、ここで、反応基質中のアルケンの不飽和基のみが選択的に水素添加され、一方で加水素分解反応（例えばベンジルオキシアルケンからのベンジル基の脱離等）が抑制された水素添加反応が進行する。
【０００３】
【特許文献１】
特開２００２−１４５８１８号公報
【特許文献２】
特開２００１−３１６３１５号公報
【０００４】
【発明が解決しようとする課題】
しかしながら、上記した粉末触媒の場合、反応後の溶液から触媒を濾過して回収する作業を要し、又、触媒の耐久性も低く、さらには、触媒が粉末であるために発火性が高いという問題があった。
一方、上記した選択的水素添加方法の場合、電気分解のための各種装置（電源、電解セル等）を必要とし、実用的でないという問題があった。
【０００５】
本発明は上記の課題を解決するためになされたものであり、取り扱い性、安全性、耐久性に優れ、又、水素添加反応を選択的に行うことができる還元反応用触媒及びその製造方法、並びに選択的水素添加方法の提供を目的とする。
【０００６】
【課題を解決するための手段】
上記した目的を達成するために、本発明の還元反応用触媒は、合成繊維からなる不織布（但し、グラフト重合された合成繊維を除く）である担体に遷移元素イオンを含む溶液を含浸後、該担体を室温で水素ガス中に保持して前記遷移元素イオンを還元することにより得られ、複数の不飽和結合を有する反応対象物の１置換二重結合部又は２置換二重結合部を選択的水素添加することを特徴とする。
【０００８】
又、前記遷移元素は、パラジウムであることが好ましい。
【０００９】
本発明の還元反応用触媒の製造方法は、合成繊維からなる不織布（但し、グラフト重合された合成繊維を除く）である担体に遷移元素イオンを含む溶液を含浸させる工程と、含浸後の担体を室温で水素ガス中に保持して前記遷移元素イオンを還元する工程とを有し、複数の不飽和結合を有する反応対象物の１置換二重結合部又は２置換二重結合部を選択的水素添加することを特徴とする。
【００１１】
又、本発明の還元触媒の製造方法において、前記遷移元素は、パラジウムであることが好ましい。
【００１２】
本発明の選択的水素添加方法は、前記還元反応用触媒を、複数の不飽和結合を有する反応対象物を含む溶液中に水素ガスの存在下で浸漬し、該反応対象物の１置換二重結合部又は２置換二重結合部を選択的水素添加することを特徴とする。
【００１３】
【発明の実施の形態】
以下、本発明に係る還元反応用触媒及びその製造方法、並びに選択的水素添加方法の実施の形態について説明する。
【００１４】
図１は、本発明の還元反応用触媒の構成を模式的に示す断面図である。この図において、還元触媒１０は、シート状の担体２に遷移元素からなる触媒物質４が担持されて構成されている。この実施形態では、担体２は合成樹脂の不織布からなり、多数の樹脂繊維２ａが網目状に絡み合い、各繊維間に空隙が形成されている。そして、担体２の内部の各繊維の表面全体に触媒物質（パラジウムブラック）４が担持されており、担体２の内部の空隙にも触媒物質が存在している。なお、本発明において、パラジウムブラックとは、微粉末ではないが、従来のパラジウムブラック（黒色微粉末パラジウム）と同様に黒色であり同様な触媒活性を有するものをいう。
【００１５】
上記パラジウムブラックは、担体の表面にアモルファス状で粒状に析出し、その粒径は通常０．１〜３μｍ、好ましくは０．３〜２μｍである。
【００１６】
担体２は、遷移元素イオンを含む溶液が含浸しやすいよう、不織布を用いることができる。又、担体の形状も特定限定されず、シート状、チューブ状、塊状、棒状、球状とすることができるが、取り扱いが容易で表面積の大きいシート状が好ましい。特に、後述するように触媒反応を有機溶媒中で進行させる場合には、溶媒との親和性のよい合成樹脂を用いると空隙に溶液が侵入しやすくなり、反応が促進されるので好ましい。合成樹脂としては、ポリプロピレン、ポリエチレン、ポリイミド等を用いることができる。空隙の大きさ、密度等も特に限定ない。
【００１７】
触媒物質４は、詳しくは後述するが、担体に遷移元素イオンを含む溶液を含浸させた後、還元することにより担体に担持される。又、触媒物質４は遷移元素からなる還元触媒であって、水素添加反応の触媒作用を有するものである。触媒物質４としては、３A〜７A族、８族及び１B族の元素を用いることができるが、好ましくは、パラジウム、白金、ロジウム、イリジウム、ルテニウム、レニウム等を用いるとよく、さらに好ましくはパラジウムを用いるとよい。特に、上記したパラジウムブラックとするのが好ましい。触媒物質の担体への担持量は特に限定されず、対象となる反応に応じて選択できるが、通常１×１０−３〜１×１０３ｍｇ／ｃｍ３、好ましくは１×１０−１〜１×１０２ｍｇ／ｃｍ３、より好ましくは０．５〜５ｍｇ／ｃｍ３である。
【００１８】
このように、本発明の還元反応用触媒は、多数の空隙を有する担体の内部に遷移元素イオンを含む溶液を含浸させることにより、担体の内部に触媒物質（遷移元素）が担持されるので、有効表面積の大きく反応性に優れた触媒となる。その結果として、従来の粉末触媒に比べて反応に必要な触媒物質の量を低減することもできる。又、触媒物質は担体の空隙内に存在するので、担体の最表面に触媒物質を大量に担持させる必要がない。つまり、担体の最表面のみに触媒物質を担持させると、外部との接触等によって触媒物質が脱落し易くなる。特に、触媒の表面積を増大させるためにデンドライト（針）状に触媒物質を析出させると、触媒物質が容易に脱落して触媒性能が低下し、触媒の耐久性に劣ることになる。本発明では、担体の内部にある空隙の周りに触媒物質が担持されており、この部分は外部と接触しずらいので、触媒物質の脱落等が生じにくく耐久性が向上する。又、バルクの担体に触媒物質が固定（担持）されているので、反応後に触媒を反応系から分離しやすく、従来の粉状触媒に比べて取り扱いも容易になる。
【００１９】
このように、本発明の還元反応用触媒は触媒物質の脱落が生じにくいものであるが、触媒物質が脱落したとしてもそれを生成物に混入させないようにすることもできる。つまり、図２に示すように、還元触媒１０を捕集布２０で包み込むことで、脱落した触媒物質を捕集布２０内に留めておくことができる。捕集布２０としては例えば網、不織布等を用いることができ、還元触媒１０の担体として不織布を用いた場合には、それより目の細かい（空隙の径が小さい）不織布等を用いることができる。
【００２０】
次に、本実施形態の還元反応用触媒の製造方法について図３を参照して説明する。まず、上記した多数の空隙を有する担体に、遷移元素イオンを含む溶液（例えば塩化パラジウム溶液）を滴下して含浸させる（図３（ａ））。含浸方法としては、上記した滴下の他、例えば担体を溶液に浸漬してもよい。
【００２１】
上記溶液における溶媒としては、例えば水、メタノール、テトラヒドロフラン、アセトニトリル、酢酸、ジメチルスルホキシド、Ｎ，Ｎ−ジメチルホルムアミド、ヘキサメチルホスホアミド等の水溶性有機溶媒、あるいは無水酢酸、酢酸エチル、塩化メチレン、ベンゼン、プロピレンカーボネート、ニトロメタン、ヘキサメチルホスホアミド等の非水溶性有機溶媒を挙げることができ、これらを単独又は二種類以上組み合わせて用いることができる。
【００２２】
遷移元素イオンとしては、通常は二価、三価、四価のものが挙げられる。例えばＰｄイオンの場合、溶媒に溶解しやすい塩化パラジウム、硫酸パラジウム、硝酸パラジウム等のパラジウム塩に起因する二価のものを好適に用いることができる。又、遷移元素イオンを含む溶液は、通常水素イオン濃度が０．３〜５ｍｏｌ／Ｌ、好ましくは酸濃度が１〜２ｍｏｌ／Ｌの酸溶液に遷移元素の塩（上記パラジウム塩等）を溶解させると、容易に調整できる。
【００２３】
溶液中の遷移元素イオンの濃度は、通常１×１０−６ｍｏｌ／Ｌ〜過飽和状態まで、好ましくは１×１０−４ｍｏｌ／Ｌ〜１×１０−１ｍｏｌ／Ｌとすることができる。
【００２４】
次いで、含浸後の担体を密閉室内に吊り下げ、室内に水素ガスを導入した後で室を密閉し、水素ガス中に担体を保持する（図３（ｂ））。保持時間は担体の形状等にもよるが、通常数分〜数時間程度でよい。これにより、含浸した溶液中の遷移元素イオン（例えばＰｄイオン）が遷移元素（例えばＰｄ０）に還元されて担体表面に析出し、還元触媒が得られる（図３（ｃ））。室内の水素ガスの圧力としては、通常１．０１３×１０２〜１．０１３×１０８Ｐａ、好ましくは１．０１３×１０５〜１．０１３×１０６Ｐａ、さらに好ましくは１．０１３×１０５〜２．０２６×１０５Ｐａとすることができる。
【００２５】
次に、室内の水素ガスを不活性ガス（Ａｒ等）で置換する（図３（ｄ））。そして、得られた還元触媒を室外に取り出し、適宜洗浄を行う。洗浄は、例えば触媒を水洗した後、有機溶媒（メタノール等）で洗浄して行うことができる。さらに、適宜触媒を減圧乾燥させてもよい。このようにして還元触媒が製造される（図３（ｅ））。
【００２６】
このように、本発明の製造方法によれば、担体が多数の空隙を有していて液体を吸収しやすいため、担体の内部に遷移元素イオンを含む溶液を含浸させることができ、担体の内部に触媒物質（遷移元素）が担持されるので、有効表面積の大きく反応性に優れた触媒を製造することができる。
【００２７】
又、本発明の製造方法によれば、担体に上記溶液を含浸させて水素ガス中に保持するだけで触媒を製造することができるので、製造が簡便となる。又、担持量の調整は、溶液の濃度や含浸量を調整するだけでよいので、担持量の調整を簡便かつ正確に行うことができる。
【００２８】
次に、本発明の還元反応用触媒を用いて、選択的水素添加を行う方法について説明する。本発明の方法は、反応対象物を含む溶液中に水素ガスの存在下で還元反応用触媒を浸漬するものである。そして、反応が終了すれば、溶液から還元反応用触媒を取り出して適宜洗浄乾燥すれば、使用によって触媒活性が低下しないので、触媒として繰り返し使用することができる。本発明の方法によれば、溶液中に水素ガスを導入して還元触媒を浸漬するだけでよく、従来のような特別な電解装置を必要としない。
【００２９】
ここで、選択的水素添加とは、不飽和結合を有する反応対象物に水素添加をする際に、所定の水素添加以外の望まない反応を生じさせないか、又は抑制させることをいう。又、選択的水素添加は、反応対象物が複数の不飽和結合を有する場合に、所定位置の水素添加を選択的に生じさせるものである（以下、「タイプ２」と称する）。
【００３２】
又、上記タイプ２の反応に用いる反応対象物としては、ａ）炭素−炭素１置換二重結合、炭素−炭素２置換二重結合から選ばれた少なくとも１つを有する化合物を例示することができる。
【００３３】
本発明の方法において、反応対象物が液体であればそのまま用いることができるが、反応対象物を溶媒に溶かしてもよい。この溶媒としては、反応温度で液体であれば何でもよく、脂肪族炭化水素類、芳香族炭化水素類、アルコール類、フェノール類、等の種々の有機溶媒を用いることができる。これら溶媒は、反応基質の種類、反応温度あるいは目的とする反応時間等によって適宜選択され、単独でも二種以上を組み合わせて用いてもよい。なお、反応基質の水素添加反応が優先されるように、水素添加反応を起こす不飽和結合を有する化合物からなる溶媒でないことが好ましい。特に好ましくは、芳香族炭化水素類、アルキル置換芳香族炭化水素類、ハロゲン置換芳香族炭化水素類、アルコキシ置換芳香族炭化水素類等の非プロトン性の芳香族炭化水素類を用いると、加水素分解反応をほぼ完全に生じさせずに水素添加反応を生じさせることができる。
【００３４】
本発明の方法において、還元触媒の量としては、担体を除く正味の触媒物質の量が反応基質（反応対象物）に対し、１×１０−５〜１００重量％、好ましくは１×１０−２〜１００重量％、より好ましくは５×１０−１〜５重量％とすることができる。
【００３５】
本発明の方法において、反応系に存在させる水素ガスの圧力は、１．０１３×１０４〜１．０１３×１０９Ｐａ、好ましくは５．０６５×１０４〜１．０１３×１０６Ｐａ、より好ましくは１．０１３×１０５〜２．０２６×１０５Ｐａとすることができる。
【００３６】
本発明の方法において、反応温度は、−２００〜１０００℃、好ましくは０〜１００℃、より好ましくは１０〜３０℃とすることができる。
【００３７】
本発明の方法において、反応時間は、１分〜１０００時間、好ましくは３０分〜２４０時間、より好ましくは３０分〜７２時間とすることができる。
【００３８】
なお、本発明の還元触媒を用いれば、上記した反応の他、従来の黒色粉末状パラジウムブラックを用いたのと同様の接触還元操作を行うことにより、ニトロ化合物を還元して対応するアミンを製造したり、ニトリルを還元して対応する第一アミンを製造することもできる。
【００３９】
次に、実施例及び比較例を挙げて本発明をさらに詳細に説明するが、本発明はこれらに限定されるものではない。
【００４０】
【実施例】
Ａ．選択的水素添加の比較実験
実施例１、比較例１〜４
１．還元触媒の作製
ポリプロピレン製の不織布（ダイワボウ社製、型版ＲＰＸ−１０１、目付４９．７ｇ／ｍ２、厚み１．２ｍｍ）を５×２ｃｍに切り出し（重さ５．０ｍｇ）、さらに折り畳んで縦横２．５×１ｃｍ、厚み０．５ｃｍとした。そして、塩化パラジウム１５０ｍｇを１ｍｏｌ／Ｌの塩酸１０ｍＬに溶解し、濃度８．５×１０−２ｍｏｌ／Ｌとした塩化パラジウム塩酸溶液０．１１ｍＬを、この不織布に滴下して含浸させた。次に、含浸後の不織布を密閉室に吊るし、０．１ＭＰａ（常圧）の水素ガスを導入し、室温で１８０分放置して不織布にパラジウムを担持させた。担持後の不織布を水及びアセトンで充分に洗浄し、乾燥して溶媒を完全に取り除いて還元触媒を作製した。触媒担持量は１．０ｍｇ（担体を含む全体の重量は約６．０ｍｇ）であった。これを実施例１とした。
【００４１】
比較として、粉末のパラジウムブラック（和光純薬工業株式会社製）を用意した。これを比較例１とする。又、粉末のＰｄ−Ｃ（粉状活性炭にＰｄ微粉末を添着させたもの、川研ファインケミカル株式会社製、Ｐｄ担持量５％、Ｐｄ活性０．２％）を用意した。これを比較例２とする。さらに、塩化パラジウムを蟻酸により還元する公知の方法で粉末のパラジウムブラックを得た。これを比較例３とする。又、パラジウム箔を比較例４とする。
【００４５】
３．選択的水素添加反応（タイプ２：所定位置の不飽和結合の選択的水素添加）
上記したタイプ２の選択的水素添加反応として、水素添加し得る二重結合を２つ有する化合物２
【化３】
得られた結果を表２に示す。
【００４６】
【表２】
表２から明らかなように、実施例１の場合、反応が４時間経過した時点で１置換二重結合部の選択的水素添加を１００％の収率で行うことができたとともに、反応開始から２４時間経過しても３置換二重結合部の水素添加が生じず、１置換二重結合への水素添加の選択性がより優れたものとなった。一方、比較例１〜３の場合、反応が１時間経過した時点で、１置換二重結合部のみならず３置換二重結合部の水素添加も進行してしまい、３置換二重結合部を還元することなく１置換二重結合部のみ部分水素添加を行うことができなかった。又、比較例４の場合は、触媒反応が全く生じなかった。以上のことから、本発明の還元触媒を用いると所定位置への選択的水素添加を高収率で行えるとともに、望まない位置での水素添加が進行しないことが明らかである。
【００６３】
３．選択的水素添加反応（タイプ２：所定位置の不飽和結合の選択的水素添加）
上記したタイプ２の選択的水素添加反応として、水素添加し得る二重結合を２つ以上有する種々の化合物を用意した。
【００６４】
（１）実施例２７〜３７
前記化合物２を用意した。ここで、式Ａ、Ｂ、Ｃは前記化合物２において説明した反応基質及び生成物である。又、反応基質を溶解させるための溶媒は以下の表５のとおりである。
得られた結果を表５に示す。ここで、表中の数字は式Ａ〜Ｃの各化合物の反応液中での存在割合を示し、ｈｒは反応時間を示す。
【００６５】
【表５】
表５から明らかなように、各実施例２７〜３７の場合、１置換二重結合部の選択的水素添加を所定の収率で行うことができた。特に、実施例２７、２８の場合、反応が４時間経過した時点で１置換二重結合部の選択的水素添加を１００％の収率で行うことができるとともに、反応後２４時間経過しても３置換二重結合部の水素添加が生じず、１置換二重結合部への水素添加の反応選択性がより優れたものとなった。
【００６７】
（２）実施例３８〜４７、比較例８
上記したタイプ２の選択的水素添加反応として、水素添加し得る二重結合を２つ有する化合物１２
【化１３】
得られた結果を表６に示す。ここで、表中の数字は式Ａ〜Ｃの各化合物の反応液中での存在割合を示し、ｈｒは反応時間を示す。
【００６８】
【表６】
表６から明らかなように、各実施例３８〜４７の場合、エステルに結合している２置換二重結合部の選択的水素添加を所定の収率で行うことができた。特に、実施例３８、３９の場合、反応が２４時間経過した時点で２置換二重結合部の選択的水素添加を１００％の収率で行うことができるとともに、反応後４８時間経過しても側鎖３置換二重結合部の水素添加が生じず、２置換二重結合部への水素添加の反応選択性がより優れたものとなった。一方、比較例８の場合、Ｂ式の生成物は得られず、望まないＣ式の生成物が生じた。
【００７０】
（３）実施例１２４
化合物１３
【化１４】
【００７１】
（４）実施例１２５
化合物１４
【化１５】
【００７２】
（５）実施例１２６
化合物１５
【化１６】
【００７３】
（６）実施例１２７
化合物１６
【化１７】
【００７５】
（８）実施例１２９
前記化合物２を用意した。溶媒はメタノールを用い、この実施例のみ反応温度を−３０℃（２４３Ｋ）とした。ここで、式Ａ〜Ｃは前記化合物２において説明したとおりである。得られた結果を表７に示す。ここで、表中の数字は式Ａ〜Ｃの各化合物の反応液中での存在割合を示し、ｈｒは反応時間を示す。
【００７６】
【表７】
表７から明らかなように、この実施例では、１置換二重結合部の選択的水素添加を所定の収率で行うことができた。特に、反応後３０分では１置換二重結合部の水素添加のみ生じ、３置換二重結合部の水素添加は全く生じなかった。
【００７８】
Ｃ．触媒の耐久性評価
１．実験条件
上記実施例１と同じ還元触媒を用い、化合物１８
【化１９】
【００７９】
次に、化合物２をトルエン溶媒中の濃度が７．０×１０−３ｍｏｌ／Ｌとなるよう溶解した溶液に、２％ ｗ／ｗとなるように上記触媒を浸漬し、水素雰囲気で４時間攪拌して反応させた。反応後、溶液から触媒を取り出し、溶媒留去後の残渣（生成物）の重量を測定し、さらに残渣をＮＭＲ（核磁気共鳴法）測定して生成物の構造を特定した。その結果、化合物２における式Ｂの生成物（末端の１置換二重結合が水素添加された部分水素化生成物）が１００％の収率で得られた。この収率は、未使用の還元触媒を用いた場合の値と同じであり、本発明の還元触媒４ｍｇが８４ｍｍｏｌ（１２．５ｇ）の反応基質に触媒作用してもなお活性を維持していることを示している。このとき、turnoverと称される触媒の耐久性指標を求めると、２．１×１０２ｍｏｌ／ｇ以上（触媒１ｇ当り、反応基質を２．１×１０２ｍｏｌ以上反応させることができる値）となった。
【００８０】
【発明の効果】
以上の説明で明らかなように、本発明の還元触媒は、触媒物質が担体の空隙の周りに担持されているので、触媒の有効表面積が増大し、反応性に優れている。その結果として、従来の粉末触媒に比べて反応に必要な触媒物質の量を低減することもできる。又、触媒物質は担体の空隙内に存在し、外部と接触しずらいため、触媒物質の物理的接触による脱落等が生じにくく耐久性が向上する。又、反応後に触媒を反応系から分離しやすく、従来の粉状触媒に比べて取り扱いも容易になる。
【００８１】
本発明の製造方法によれば、担体が液体を吸収しやすいため、担体の内部に遷移元素イオンを含む溶液を確実に含浸させることができ、担体の内部に触媒物質が担持され有効表面積の大きく反応性に優れた触媒を製造することができる。又、担体に上記溶液を含浸させて水素ガス中に保持するだけで触媒を製造することができる。さらに、担持量の調整は、溶液の濃度や含浸量を調整するだけでよいので、担持量の調整を簡便かつ正確に行うことができる。
【００８２】
本発明の選択的水素添加方法によれば、不飽和結合を有する反応対象物を含む溶液中に水素ガスの存在下で還元触媒を浸漬するだけで、水素添加反応を選択的に行うことができる。
【図面の簡単な説明】
【図１】 本発明の還元触媒の構成を模式的に示す断面図である。
【図２】 還元触媒を捕集布で包んだ状態を示す図である。
【図３】 本発明の還元触媒の製造方法を示す工程図である。
【符号の説明】
２ 担体
２ａ 樹脂繊維
４ 触媒物質（遷移元素）
１０ 還元触媒[0001]
BACKGROUND OF THE INVENTION
The present invention is a reduction in which a catalytic material composed of a transition element such as palladium is supported.For reactionThe present invention relates to a catalyst, a production method thereof, and a selective hydrogenation method.
[0002]
[Prior art]
Conventionally, hydrogenation (reduction) catalysts have been used when synthesizing organic compounds such as chemicals and pharmaceuticals, or when performing reductive desulfurization of petroleum. As this catalyst, powders such as palladium black (Pd fine powder) and Pd-C (powdered activated carbon added with Pd fine powder) are mainly used, and the reaction object (reaction substrate) is used as a solvent. A powdered catalyst is added to the dissolved solution to proceed the reaction.
On the other hand, the reduction catalyst acts on both the hydrogenation reaction and the hydrogenolysis reaction, and since these reaction conditions are the same, only one of these reactions can be selectively performed on the reaction substrate. Is difficult. Therefore, the present inventors have reported a method by electrolysis as a selective hydrogenation method of benzyloxyalkene (for example, see Patent Documents 1 and 2). In this method, the reaction system is divided into two tanks with a palladium thin film used as a cathode, and water is electrolyzed in one tank to generate hydrogen. Hydrogen is stored in the palladium thin film which is a hydrogen storage metal and permeates into the other tank from the opposite surface. The reaction solution in this tank dissolves the reaction substrate benzyloxyalkene, where only the unsaturated group of the alkene in the reaction substrate is selectively hydrogenated, while the hydrogenolysis reaction (for example benzyl). The hydrogenation reaction in which the elimination of the benzyl group from the oxyalkene and the like is suppressed proceeds.
[0003]
[Patent Document 1]
JP 2002-145818 A
[Patent Document 2]
JP 2001-316315 A
[0004]
[Problems to be solved by the invention]
However, in the case of the above-mentioned powder catalyst, it is necessary to filter and recover the catalyst from the solution after the reaction, and the durability of the catalyst is low, and furthermore, the catalyst is powder, so that it is highly ignitable. There was a problem.
On the other hand, in the case of the selective hydrogenation method described above, various devices for electrolysis (power supply, electrolysis cell, etc.) are required, which is not practical.
[0005]
The present invention has been made in order to solve the above problems, and is excellent in handling, safety, durability, and reduction capable of selectively performing a hydrogenation reaction.For reactionAn object is to provide a catalyst, a production method thereof, and a selective hydrogenation method.
[0006]
[Means for Solving the Problems]
In order to achieve the above object, the reduction of the present inventionFor reactionThe catalystNon-woven fabric made of synthetic fibers (excluding graft-polymerized synthetic fibers)After impregnating the carrier with a solution containing transition element ions,At room temperatureObtained by reducing the transition element ions held in hydrogen gas., Selectively hydrogenating a 1-substituted or 2-substituted double bond of a reaction object having a plurality of unsaturated bondsIt is characterized by that.
[0008]
The transition element is preferably palladium.
[0009]
Reduction of the present inventionFor reactionThe method for producing the catalyst is as follows:Non-woven fabric made of synthetic fibers (excluding graft-polymerized synthetic fibers)A step of impregnating the carrier with a solution containing transition element ions, and a carrier after the impregnation.At room temperatureHolding in hydrogen gas and reducing the transition element ions,Selective hydrogenation of 1-substituted or 2-substituted double bonds of reaction objects having multiple unsaturated bondsIt is characterized by doing.
[0011]
In the method for producing a reduction catalyst of the present invention, the transition element is preferably palladium.
[0012]
The selective hydrogenation method of the present invention comprises the reductionFor reactionCatalyst,pluralImmersion in the presence of hydrogen gas in a solution containing a reaction object having an unsaturated bondAnd selectively hydrogenating the 1-substituted or 2-substituted double bond of the reaction productIt is characterized by doing.
[0013]
DETAILED DESCRIPTION OF THE INVENTION
Hereinafter, reduction according to the present inventionFor reactionEmbodiments of the catalyst, its production method, and the selective hydrogenation method will be described.
[0014]
FIG. 1 shows the reduction of the present invention.For reactionIt is sectional drawing which shows the structure of a catalyst typically. In this figure, the
[0015]
The palladium black is deposited in an amorphous and granular form on the surface of the carrier, and its particle size is usually 0.1 to 3 μm, preferably 0.3 to 2 μm.
[0016]
The carrier 2 is easily impregnated with a solution containing transition element ions., Non-wovenCan be used. Further, the shape of the carrier is not particularly limited, and can be a sheet shape, a tube shape, a lump shape, a rod shape, or a spherical shape, but a sheet shape that is easy to handle and has a large surface area is preferable..In particular, when the catalytic reaction proceeds in an organic solvent as will be described later, it is preferable to use a synthetic resin having a good affinity with the solvent because the solution easily enters the voids and promotes the reaction. As the synthetic resin, polypropylene, polyethylene, polyimide, or the like can be used. There are no particular limitations on the size and density of the voids.
[0017]
As will be described in detail later, the
[0018]
Thus, the reduction of the present inventionFor reactionThe catalyst has a large effective surface area and excellent reactivity because the catalyst substance (transition element) is supported inside the carrier by impregnating the inside of the carrier having a large number of voids with a solution containing transition element ions. It becomes. As a result, the amount of catalyst material required for the reaction can be reduced as compared with conventional powder catalysts. Further, since the catalyst material is present in the voids of the support, it is not necessary to load a large amount of the catalyst material on the outermost surface of the support. That is, when the catalyst material is supported only on the outermost surface of the carrier, the catalyst material is easily dropped due to contact with the outside. In particular, if the catalyst material is deposited in the shape of a dendrite (needle) in order to increase the surface area of the catalyst, the catalyst material will easily fall off, resulting in poor catalyst performance and poor catalyst durability. In the present invention, the catalyst material is supported around the voids inside the carrier, and this portion is difficult to contact with the outside, so that the catalyst material is less likely to fall off and the durability is improved. In addition, since the catalyst substance is fixed (supported) on the bulk carrier, the catalyst can be easily separated from the reaction system after the reaction, and the handling becomes easier as compared with the conventional powdery catalyst.
[0019]
Thus, the reduction of the present inventionFor reactionThe catalyst is less likely to cause the catalyst material to fall off, but even if the catalyst material falls off, it can be prevented from being mixed into the product. That is, as shown in FIG. 2, by wrapping the
[0020]
Next, the reduction of this embodimentFor reactionA method for producing the catalyst will be described with reference to FIG. First, a solution containing transition element ions (for example, palladium chloride solution) is dropped and impregnated into the above-described carrier having a large number of voids (FIG. 3A). As the impregnation method, in addition to the above-described dropping, for example, a carrier may be immersed in the solution.
[0021]
Examples of the solvent in the above solution include water-soluble organic solvents such as water, methanol, tetrahydrofuran, acetonitrile, acetic acid, dimethyl sulfoxide, N, N-dimethylformamide, and hexamethylphosphoamide, or acetic anhydride, ethyl acetate, methylene chloride, and benzene. , Propylene carbonate, nitromethane, hexamethylphosphoamide and the like water-insoluble organic solvents, and these can be used alone or in combination of two or more.
[0022]
Examples of transition element ions usually include divalent, trivalent, and tetravalent ions. For example, in the case of Pd ions, divalent ones resulting from palladium salts such as palladium chloride, palladium sulfate, palladium nitrate and the like that are easily dissolved in a solvent can be suitably used. The solution containing transition element ions usually dissolves the salt of the transition element (such as the above palladium salt) in an acid solution having a hydrogen ion concentration of 0.3 to 5 mol / L, preferably an acid concentration of 1 to 2 mol / L. And can be adjusted easily.
[0023]
The concentration of transition element ions in the solution is usually 1 × 10-6mol / L to supersaturated state, preferably 1 × 10-4mol / L to 1 × 10-1mol / L.
[0024]
Next, the impregnated carrier is suspended in a sealed chamber, hydrogen gas is introduced into the chamber, the chamber is sealed, and the carrier is held in the hydrogen gas (FIG. 3B). Although the holding time depends on the shape of the carrier and the like, it is usually from several minutes to several hours. As a result, transition element ions (for example, Pd ions) in the impregnated solution become transition elements (for example, Pd ions).0) To be deposited on the surface of the carrier to obtain a reduction catalyst (FIG. 3 (c)). The pressure of hydrogen gas in the room is usually 1.013 × 102~ 1.013 × 108Pa, preferably 1.013 × 105~ 1.013 × 106Pa, more preferably 1.013 × 105~ 2.026 × 105Pa can be used.
[0025]
Next, the hydrogen gas in the room is replaced with an inert gas (Ar or the like) (FIG. 3D). Then, the obtained reduction catalyst is taken out of the room and washed appropriately. The washing can be performed, for example, by washing the catalyst with water and then washing with an organic solvent (such as methanol). Furthermore, the catalyst may be dried under reduced pressure as appropriate. Thus, a reduction catalyst is manufactured (FIG. 3 (e)).
[0026]
As described above, according to the production method of the present invention, since the carrier has a large number of voids and easily absorbs the liquid, the inside of the carrier can be impregnated with the solution containing transition element ions. Since the catalyst substance (transition element) is supported on the catalyst, a catalyst having a large effective surface area and excellent reactivity can be produced.
[0027]
In addition, according to the production method of the present invention, the catalyst can be produced simply by impregnating the above-mentioned solution into a carrier and holding it in hydrogen gas, so that the production becomes simple. Moreover, since the adjustment of the carrying amount only needs to be carried out by adjusting the concentration and impregnation amount of the solution, the carrying amount can be adjusted easily and accurately.
[0028]
Next, the reduction of the present inventionFor reactionA method for performing selective hydrogenation using a catalyst will be described. The method of the present invention is a reduction in the presence of hydrogen gas in a solution containing a reaction object.For reactionThe catalyst is immersed. When the reaction is complete, the solution is reduced.For reactionIf the catalyst is taken out and washed and dried as appropriate, the catalyst activity does not decrease by use, so that it can be used repeatedly as a catalyst. According to the method of the present invention, it is only necessary to introduce hydrogen gas into the solution and immerse the reduction catalyst, and no special electrolysis apparatus as in the prior art is required.
[0029]
Here, the selective hydrogenation means that an unwanted reaction other than a predetermined hydrogenation is not caused or suppressed when hydrogenating a reaction target having an unsaturated bond. Selective hydrogenationIsIn the case where the reaction object has a plurality of unsaturated bonds, hydrogenation at a predetermined position is selectively caused (hereinafter referred to as “type 2”).
[0032]
Moreover, the reaction object used for the above type 2 reaction includes a) a carbon-carbon 1-substituted double bond and a carbon-carbon 2-substituted double bond.FromCompound having at least one selectedTheIt can be illustrated.
[0033]
In the method of the present invention, if the reaction object is a liquid, it can be used as it is, but the reaction object may be dissolved in a solvent. Any solvent can be used as long as it is liquid at the reaction temperature, and various organic solvents such as aliphatic hydrocarbons, aromatic hydrocarbons, alcohols, and phenols can be used. These solvents are appropriately selected depending on the type of reaction substrate, reaction temperature, target reaction time, and the like, and may be used alone or in combination of two or more. In order to give priority to the hydrogenation reaction of the reaction substrate, the solvent is preferably not a solvent composed of a compound having an unsaturated bond that causes the hydrogenation reaction. Particularly preferably, when aprotic aromatic hydrocarbons such as aromatic hydrocarbons, alkyl-substituted aromatic hydrocarbons, halogen-substituted aromatic hydrocarbons, alkoxy-substituted aromatic hydrocarbons are used, hydrogenation is performed. The hydrogenation reaction can occur without causing the decomposition reaction almost completely.
[0034]
In the method of the present invention, as the amount of the reduction catalyst, the amount of the net catalyst material excluding the carrier is 1 × 10 5 with respect to the reaction substrate (reaction target).-5~ 100% by weight, preferably 1 x 10-2To 100% by weight, more preferably 5 × 10-1It can be made into 5 weight%.
[0035]
In the method of the present invention, the hydrogen gas pressure present in the reaction system is 1.013 × 10 6.4~ 1.013 × 109Pa, preferably 5.065 × 104~ 1.013 × 106Pa, more preferably 1.013 × 105~ 2.026 × 105Pa can be used.
[0036]
In the method of the present invention, the reaction temperature can be -200 to 1000 ° C, preferably 0 to 100 ° C, more preferably 10 to 30 ° C.
[0037]
In the method of the present invention, the reaction time can be 1 minute to 1000 hours, preferably 30 minutes to 240 hours, more preferably 30 minutes to 72 hours.
[0038]
If the reduction catalyst of the present invention is used, a corresponding amine is produced by reducing the nitro compound by performing the same catalytic reduction operation as that using the conventional black powdery palladium black in addition to the above reaction. Or the nitrile can be reduced to produce the corresponding primary amine.
[0039]
Next, although an Example and a comparative example are given and this invention is demonstrated further in detail, this invention is not limited to these.
[0040]
【Example】
A. Comparative experiment of selective hydrogenation
Example 1 and Comparative Examples 1 to 4
1. Preparation of reduction catalyst
Nonwoven fabric made of polypropylene (Daiwabo Co., Ltd., template RPX-101, basis weight 49.7 g / m2, Thickness 1.2 mm) was cut into 5 × 2 cm (weight 5.0 mg) and further folded to 2.5 × 1 cm in length and width and 0.5 cm in thickness. Then, 150 mg of palladium chloride was dissolved in 10 mL of 1 mol / L hydrochloric acid, and the concentration was 8.5 × 10.-20.11 mL of a mol / L palladium chloride hydrochloric acid solution was dropped into the nonwoven fabric and impregnated. Next, the impregnated non-woven fabric was suspended in a sealed chamber, hydrogen gas of 0.1 MPa (normal pressure) was introduced, and allowed to stand at room temperature for 180 minutes to support palladium on the non-woven fabric. The supported nonwoven fabric was thoroughly washed with water and acetone, dried to completely remove the solvent, thereby producing a reduction catalyst. The amount of the catalyst supported was 1.0 mg (the total weight including the support was about 6.0 mg). This was designated Example 1.
[0041]
For comparison, powdered palladium black (manufactured by Wako Pure Chemical Industries, Ltd.) was prepared. This is referred to as Comparative Example 1. Also, powdered Pd-C (powdered activated carbon with Pd fine powder impregnated, manufactured by Kawaken Fine Chemical Co., Ltd., 5% Pd loading, 0.2% Pd activity) was prepared. This is referred to as Comparative Example 2. Further, powdered palladium black was obtained by a known method of reducing palladium chloride with formic acid. This is referred to as Comparative Example 3. Further, a palladium foil is referred to as Comparative Example 4.
[0045]
3. Selective hydrogenation reaction (Type 2: Selective hydrogenation of unsaturated bond at a predetermined position)
Compound 2 having two double bonds capable of hydrogenation as the selective hydrogenation reaction of type 2 described above
[Chemical Formula 3]
The obtained results are shown in Table 2.
[0046]
[Table 2]
As is clear from Table 2, in the case of Example 1, when the reaction was performed for 4 hours, selective hydrogenation of the 1-substituted double bond portion could be performed in a yield of 100%, and from the start of the reaction. Even after 24 hours, hydrogenation of the 3-substituted double bond did not occur, and the selectivity of hydrogenation to the 1-substituted double bond became more excellent. On the other hand, in the case of Comparative Examples 1 to 3, when the reaction has passed for 1 hour, hydrogenation of not only the 1-substituted double bond portion but also the 3-substituted double bond portion has progressed. Partial hydrogenation could not be performed only on the 1-substituted double bond part without reduction. In the case of Comparative Example 4, no catalytic reaction occurred. From the above, it is clear that when the reduction catalyst of the present invention is used, selective hydrogenation at a predetermined position can be performed in a high yield and hydrogenation at an undesired position does not proceed.
[0063]
3. Selective hydrogenation reaction (Type 2: Selective hydrogenation of unsaturated bond at a predetermined position)
As the type 2 selective hydrogenation reaction, various compounds having two or more double bonds capable of hydrogenation were prepared.
[0064]
(1) Examples 27-37
The compound 2 was prepared. Here, the formulas A, B, and C are the reaction substrates and products described in the compound 2. Further, the solvents for dissolving the reaction substrate are as shown in Table 5 below.
The results obtained are shown in Table 5. Here, the numbers in the table indicate the abundance ratios of the compounds of formulas A to C in the reaction solution, and hr indicates the reaction time.
[0065]
[Table 5]
As is clear from Table 5, in each of Examples 27 to 37, selective hydrogenation of the 1-substituted double bond portion could be performed in a predetermined yield. In particular, in the case of Examples 27 and 28, the selective hydrogenation of the 1-substituted double bond portion can be performed at a yield of 100% when the reaction has passed for 4 hours, and even after 24 hours have passed after the reaction. Hydrogenation of the 3-substituted double bond portion did not occur, and the reaction selectivity of hydrogenation to the 1-substituted double bond portion became more excellent.
[0067]
(2) Examples 38 to 47, Comparative Example 8
Embedded image
The results obtained are shown in Table 6. Here, the numbers in the table indicate the abundance ratios of the compounds of formulas A to C in the reaction solution, and hr indicates the reaction time.
[0068]
[Table 6]
As is clear from Table 6, in each of Examples 38 to 47, the selective hydrogenation of the disubstituted double bond bonded to the ester could be carried out in a predetermined yield. In particular, in the case of Examples 38 and 39, the selective hydrogenation of the 2-substituted double bond portion can be performed at a yield of 100% when the reaction has passed for 24 hours, and even after 48 hours have passed after the reaction. Hydrogenation of the side chain 3-substituted double bond portion did not occur, and the reaction selectivity of hydrogenation to the 2-substituted double bond portion became more excellent. On the other hand, in the case of Comparative Example 8, a product of formula B was not obtained, and an undesired product of formula C was produced.
[0070]
(3) Examples124
Compound 13
Embedded image
[0071]
(4) Examples125
Compound 14
Embedded image
[0072]
(5) Examples126
Compound 15
Embedded image
[0073]
(6) Examples127
Compound 16
Embedded image
[0075]
(8) Examples129
The compound 2 was prepared. Methanol was used as the solvent, and only in this example, the reaction temperature was −30 ° C. (243 K). Here, Formulas A to C are as described in Compound 2 above. The results obtained are shown in Table 7. Here, the numbers in the table indicate the abundance ratios of the compounds of formulas A to C in the reaction solution, and hr indicates the reaction time.
[0076]
[Table 7]
As is apparent from Table 7, in this example, the selective hydrogenation of the monosubstituted double bond portion could be performed in a predetermined yield. In particular, 30 minutes after the reaction, only hydrogenation of the 1-substituted double bond portion occurred, and no hydrogenation of the 3-substituted double bond portion occurred.
[0078]
C. Catalyst durability evaluation
1. Experimental conditions
Using the same reduction catalyst as in Example 1 above, Compound 18
Embedded image
[0079]
Next, the concentration of Compound 2 in the toluene solvent is 7.0 × 10-3The catalyst was immersed in the solution dissolved so as to be mol / L so as to be 2% w / w, and the reaction was performed by stirring in a hydrogen atmosphere for 4 hours. After the reaction, the catalyst was taken out from the solution, the weight of the residue (product) after evaporation of the solvent was measured, and the residue was measured by NMR (nuclear magnetic resonance method) to identify the structure of the product. As a result, the product of formula B in compound 2 (partially hydrogenated product in which the terminal monosubstituted double bond was hydrogenated) was obtained in a yield of 100%. This yield is the same as that when an unused reduction catalyst is used, and the activity is still maintained even when 4 mg of the reduction catalyst of the present invention catalyzes 84 mmol (12.5 g) of the reaction substrate. It is shown that. At this time, when the durability index of the catalyst called turnover is obtained, 2.1 × 102mol / g or more (2.1 × 10 reaction substrate per gram of catalyst)2It was a value capable of reacting more than mol).
[0080]
【The invention's effect】
As is apparent from the above description, the reduction catalyst of the present invention is excellent in reactivity because the catalytic material is supported around the voids of the carrier, so that the effective surface area of the catalyst is increased. As a result, the amount of catalyst material required for the reaction can be reduced as compared with conventional powder catalysts. Further, since the catalyst substance is present in the voids of the carrier and is difficult to come into contact with the outside, the catalyst substance is unlikely to fall off due to physical contact, and durability is improved. In addition, the catalyst can be easily separated from the reaction system after the reaction, and handling becomes easier as compared with the conventional powdery catalyst.
[0081]
According to the production method of the present invention, since the carrier easily absorbs the liquid, the solution containing the transition element ions can be surely impregnated inside the carrier, and the catalyst substance is carried inside the carrier and the effective surface area is increased. A catalyst having excellent reactivity can be produced. In addition, the catalyst can be produced simply by impregnating the support with the above solution and holding it in hydrogen gas. Further, the adjustment of the supported amount can be performed simply and accurately because the concentration of the solution and the amount of impregnation need only be adjusted.
[0082]
According to the selective hydrogenation method of the present invention, the hydrogenation reaction can be selectively performed only by immersing the reduction catalyst in the presence of hydrogen gas in a solution containing a reaction target having an unsaturated bond. .
[Brief description of the drawings]
FIG. 1 is a cross-sectional view schematically showing the configuration of a reduction catalyst of the present invention.
FIG. 2 is a diagram showing a state in which a reduction catalyst is wrapped with a collection cloth.
FIG. 3 is a process diagram showing a method for producing a reduction catalyst of the present invention.
[Explanation of symbols]
2 Carrier
2a Resin fiber
4 Catalytic substances (transition elements)
10 Reduction catalyst
Claims (5)
含浸後の担体を室温で水素ガス中に保持して前記遷移元素イオンを還元する工程と
を有し、複数の不飽和結合を有する反応対象物の１置換二重結合部又は２置換二重結合部を選択的水素添加することを特徴とする還元反応用触媒の製造方法。A step of impregnating a carrier which is a non-woven fabric made of synthetic fibers (excluding graft-polymerized synthetic fibers) with a solution containing transition element ions;
Holding the impregnated support in hydrogen gas at room temperature to reduce the transition element ions, and a 1-substitution double bond portion or a 2-substitution double bond of a reaction object having a plurality of unsaturated bonds A method for producing a catalyst for reduction reaction , wherein a part is selectively hydrogenated .
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| JP4116891B2 true JP4116891B2 (en) | 2008-07-09 |
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Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS58146446A (en) * | 1982-02-25 | 1983-09-01 | Asahi Chem Ind Co Ltd | Fixed bed catalyst |
| US5326825A (en) * | 1992-11-27 | 1994-07-05 | Naesman Jan H | Process for the preparation of a graft copolymer bound catalyst |
| FI105274B (en) * | 1996-03-15 | 2000-07-14 | Upm Kymmene Oy | Method for hydrogenation of non-hormone-containing unsaturated plant steroids and regeneration of spent catalyst |
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2003
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