JPWO2015115410A1 - 水素化反応方法 - Google Patents
水素化反応方法 Download PDFInfo
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- JPWO2015115410A1 JPWO2015115410A1 JP2015559942A JP2015559942A JPWO2015115410A1 JP WO2015115410 A1 JPWO2015115410 A1 JP WO2015115410A1 JP 2015559942 A JP2015559942 A JP 2015559942A JP 2015559942 A JP2015559942 A JP 2015559942A JP WO2015115410 A1 JPWO2015115410 A1 JP WO2015115410A1
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- Prior art keywords
- compound
- reaction
- hydrogen
- hydrogenated
- reduced
- Prior art date
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Images
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- C07C209/30—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of nitrogen-to-oxygen or nitrogen-to-nitrogen bonds
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- B01J23/64—Platinum group metals with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/652—Chromium, molybdenum or tungsten
- B01J23/6525—Molybdenum
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- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
- C01B3/06—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of inorganic compounds containing electro-positively bound hydrogen, e.g. water, acids, bases, ammonia, with inorganic reducing agents
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Abstract
Description
工程1: 水素含有化合物(A)と還元型化合物(B)とを反応させることにより水素を発生させる工程、および、
工程2: 上記水素により被水素化化合物(C)を還元して水素化化合物(c)を製造する工程を含むことを特徴とする方法。
[水素含有化合物(A)]
本発明において「水素含有化合物(A)」は、その化学構造中に水素原子を含む、H2以外の化合物をいうものとする。水素含有化合物(A)としては、還元型化合物(B)により還元され、反応に寄与する水素を生じさせるものであればいかなる化合物でも使用できる。水素含有化合物(A)としては、例えば、プロトン性化合物を用いることができる。
本発明において「還元型化合物(B)」は、水素含有化合物(A)を還元し、反応に寄与する水素を発生させることができるものであればよく、少なくとも反応に用いられる程度安定して維持できるものである。例えば当該還元型化合物(B)が金属、低酸化状態の金属酸化物を用いることができる。
水素含有化合物(A)と還元型化合物(B)とを反応させる温度は50℃以上、700℃以下、好ましくは100℃以上、500℃以下であり、50℃未満であれば、水素の発生速度が十分でないおそれがあり得るために好ましくなく、700℃を超える場合には還元型化合物(B)の粒子の焼結により、繰り返し利用すると酸化還元速度が低下するおそれがあり得るので好ましくない。
本発明の水素化反応方法は、水素含有化合物(A)と還元型化合物(B)との反応により発生する水素を用いて、被水素化化合物(C)を水素化化合物(c)へと転化する方法である。
被水素化化合物(C)は、水素により水素化または水素化分解する化合物であればよく、特に限定されない。例えば、一酸化炭素;二酸化炭素;ベンゼン、フェノール、スチレン、ナフタレンなどの芳香族炭化水素化合物;フラン、フルフラールなどのヘテロアリール化合物;シクロヘキセンなどの環状不飽和炭化水素化合物;エチレン、アセチレン、1−デセンなどの鎖状不飽和炭化水素化合物;ニトロベンゼンなどのニトロ化合物;アゾ化合物、ニトリル化合物、オキシム化合物、アミド化合物などの含窒素化合物;アセトン、ヒドロキシアセトン、ジヒドロキシアセトン、シクロヘキサノンなどのケトン類;クロトンアルデヒドなどのアルデヒド類;酢酸や乳酸などのオキソ酸またはカルボン酸;ペンタノールなどのアルコール類;合成炭化水素油;ラウリン酸メチルなどの植物油脂;セルロース、セロビオース、スクロースなどの多糖類;グルコース、フルクトース、キシロース、エリスリトールなどの単糖類;ソルビトールやマンニトールなどの糖アルコール;グリセリンなどのポリオールなどが挙げられる。好ましくは、バイオマス由来の植物油脂、セルロース、グルコースなどの糖類、ソルビトールなどの糖アルコール、グリセリンなどのポリオールなどである。植物由来のバイオマスは、その成長過程で光合成によって二酸化炭素を吸収するため、再生可能な炭素資源であり、脱化石資源という観点で持続可能な化学原料になりうる点で、社会的インパクトが大きく工業的意義も高い。
上記水素化反応においては、水素化反応または水素化分解反応をより一層促進するために水素化触媒(D)を用いてもよい。用いられる水素化触媒(D)は、被水素化化合物(C)を水素化または水素化分解することができる触媒機能を有する金属元素であれば何れのものであっても使用することができる。例えば、周期律表第6族〜10族の金属元素が好ましく、さらに、バナジウム(V)、クロム(Cr)、マンガン(Mn)、鉄(Fe)、コバルト(Co)、ニッケル(Ni)、銅(Cu)、亜鉛(Zn)、モリブデン(Mo)、ルテニウム(Ru)、ロジウム(Rh)、パラジウム(Pd)、銀(Ag)、タングステン(W)、レニウム(Re)、オスミウム(Os)、イリジウム(Ir)、白金(Pt)および金(Au)からなる群から選ばれる少なくとも一種の金属元素を含むことが好ましい。さらに好ましくは、コバルト(Co)、ニッケル(Ni)、銅(Cu)、ロジウム(Rh)、パラジウム(Pd)、イリジウム(Ir)、白金(Pt)である。上記金属元素は金属だけでなく、これらの酸化物および硫化物であってもよく、2種以上混合して用いることもできる。
・含浸法 − 触媒成分前駆体を溶媒に溶解して高比表面積の担体に担持する方法;
・イオン交換法 − 金属化合物溶液にイオン交換能をもつ担体を添加し、イオン結合により金属を担持する方法;
・金属コロイド法 − 高分子や界面活性剤などを該当する金属塩溶液に添加し、その後還元を行い、均一な金属コロイドを得る方法
なお、含浸法としては、平衡吸着法、蒸発乾固法、ポアフィリング法がある。また、一般的に、含浸法とイオン交換法では、金属を担体に担持した後、洗浄・乾燥・焼成・還元を経て反応に供される。
被水素化化合物(C)を水素化または水素化分解する温度は、対象となる反応に合わせて適宜設定すればよいが、50℃以上、600℃以下で行うことが適当である。ただし、反応温度が低すぎると、反応の転化率が低くなるため好ましくなく、逆に高すぎると、副生成物が多くなるなど品質低下が起こったり、触媒寿命が短くなったりするため好ましくない。多くの反応においては、好ましくは、100℃以上、300℃以下、より好ましくは120℃以上、250℃以下であるが、これには限定されない。
本発明の水素化反応の形式は、特に限定されないが、回分式(バッチ式)、半回分式、連続流通式のいずれでも実施できる。上記水素化反応は、水素含有化合物(A)、被水素化化合物(C)がそれぞれ気相であっても液相であってもよく、還元型化合物(B)および水素化触媒(D)を含む反応系全体は、気液固三相系、気固二相系、液固二相系のいずれであってもよく、特に限定されない。以下、各反応形式につき説明する。
本発明の水素化反応方法を連続流通式で実施する場合、還元型化合物(B)を滞留させた反応器に水素含有化合物(A)を通して反応させて水素を発生させ、次に、被水素化化合物(C)を導入し、発生した水素と共に水素化触媒(D)を滞留させた反応器に通すことによって水素化反応を行う(図1を参照)。水素化触媒(D)は固定床、移動床、流動床として使用することができ、単一の反応器でも、連続した2つ以上の反応器を用いることもできる。
本発明の水素化反応方法を回分式で実施する場合には、少なくとも水素含有化合物(A)、還元型化合物(B)および被水素化化合物(C)を反応器に仕込み、加熱・攪拌することによって反応させることができる(図2を参照)。水素化触媒(D)は固定床、移動床、流動床として使用することができ、単一の反応器でも、連続した2つ以上の反応器を用いることもできる。
酸化鉄の粉体を用いて還元し鉄粉を得た。次いで、50mL容のステンレス製オートクレーブに、ニトロベンゼン(0.4922g,4mmol)、鉄粉(平均粒径約60−80nm,0.6701g,12mmol)および水(20mL)を加え、蓋を閉めた。このオートクレーブを窒素ガスでパージした後、マグネティックスターラーで混合物を撹拌しながら、ヒーターを用いてオートクレーブ内部を120℃で加熱した。その後20時間、120℃に保持しながら撹拌を続けた後、加熱を停止し室温中で放冷した。室温まで冷却したオートクレーブ中から反応溶液を取り出し、溶液中の各種生成物をガスクロマトグラフィーにより分析した結果、ニトロベンゼンが水素化されたアニリンの生成が確認された。
50mL容のステンレス製オートクレーブに、表1に示す被水素化化合物、還元型化合物として粒径6〜9μmの亜鉛粉末(0.395g,6mmolもしくは0.789g,12mmol)または粒径60〜80nmの鉄粉末(0.391g,6mmol)、水素含有化合物として水(3mL)とエタノール(17mL)との混合物または水(20mL)、および場合によって表1に示す水素化触媒を加え、蓋を閉めた。当該オートクレーブ内部の気相を窒素ガスで置換し、内圧を0.5MPaとした。マグネティックスターラーで混合物を攪拌しながら、ヒーターを用いてオートクレーブ内部を180℃に加熱し、20時間反応させた。但し、実施例21のみ、内部温度を165℃、反応時間を5時間とした。次に、加熱を停止し、室温まで放冷した。オートクレーブ中から反応液を取り出し、高速液体クロマトグラフィーで分析し、被水素化化合物の水素化により生成する水素化化合物の同定と収率の算出を行った。結果を表1に示す。
100mL容のハステロイ製オートクレーブに、被水素化化合物としてフェノール(0.376g,4mmol)、還元型化合物として粒径60〜80nmの鉄粉末(1.564g,24mmol)、水素含有化合物として水(40mL)、および水素化触媒として活性炭担持5%パラジウム触媒(0.020g)を加え、蓋を閉めた。当該オートクレーブ内部の気相を窒素ガスで置換し、内圧を1.0MPaとした。攪拌翼で混合物を攪拌しながら、ヒーターを用いてオートクレーブ内部を230℃に加熱し、4時間反応させた。次に、加熱を停止し、室温まで放冷した。オートクレーブ中から反応液を取り出し、ガスクロマトグラフィーで分析し、被水素化化合物の水素化により生成する水素化化合物の同定と収率の算出を行った。結果を表2に示す。
100mL容のハステロイ製オートクレーブに、被水素化化合物としてラウリン酸メチル(0.870g,4mmol)、還元型化合物として粒径60〜80nmの鉄粉末(1.564g,24mmol)、水素含有化合物として水(1mL)、溶媒としてテトラデカン(40mL)との混合物、および水素化触媒としてルテニウム−スズ−モリブデン触媒(0.0431g)を加え、蓋を閉めた。当該オートクレーブ内部の気相を窒素ガスで置換し、内圧を0.1MPaとした。攪拌翼で混合物を攪拌しながら、ヒーターを用いてオートクレーブ内部を270℃に加熱し、24時間反応させた。次に、加熱を停止し、室温まで放冷した。オートクレーブ中から反応液を取り出し、ガスクロマトグラフィーで分析し、被水素化化合物の水素化により生成する水素化化合物の同定と収率の算出を行った。結果を表2に示す。
1−2: 還元型化合物(B)
1−3: 水素含有化合物(A)導入用ポンプ
1−4: 被水素化化合物(C)の水素化反応器
1−5: 水素化触媒(D)
1−6: 被水素化化合物(C)導入用ポンプ
2−1: 撹拌機
2−2: 水素含有化合物(A)導入路
2−3: 被水素化化合物(C)導入路
2−4: 水素化化合物排出路
2−5: 還元型化合物(B)
2−6: 水素化触媒(D)
Claims (8)
- 水素化化合物を製造するための方法であって、
工程1: 水素含有化合物(A)と還元型化合物(B)とを反応させることにより水素を発生させる工程、および、
工程2: 上記水素により被水素化化合物(C)を還元して水素化化合物(c)を製造する工程を含むことを特徴とする方法。 - 上記工程1と上記工程2とをワンポットで行う請求項1に記載の方法。
- 上記水素含有化合物(A)がプロトン性化合物である請求項1または2に記載の方法。
- 上記水素含有化合物(A)が、プロトン性溶媒、有機酸および無機酸からなる群より選択される少なくとも一種である請求項1または2に記載の方法。
- 上記水素含有化合物(A)がプロトン性溶媒である請求項1または2に記載の方法。
- 上記還元型化合物(B)が、Mg、Al、Si、Ti、V、Cr、Mn、Fe、Co、Ni、Cu、Zn、Ge、Zr、Nb、Mo、In、Sn、WおよびCeからなる群から選ばれる少なくとも一つの金属である請求項1〜5のいずれかに記載の方法。
- 当該被水素化化合物(C)が、植物油脂、セルロース、スクロース、グルコース、フルクトース、キシロース、ソルビトール、乳酸、フルフラール、フェノールおよびグリセリンからなる群から選ばれる少なくとも一種である請求項1〜6のいずれかに記載の方法。
- 上記工程2において、さらに水素化触媒(D)を添加する請求項1〜7のいずれかに記載の方法。
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Citations (17)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS61167443A (ja) * | 1984-10-02 | 1986-07-29 | Masahiro Suzuki | マグネシウム−水系を用いた有機無機物質の還元に関する方法 |
JPH03202152A (ja) * | 1989-12-28 | 1991-09-03 | Japan Synthetic Rubber Co Ltd | 水素化触媒 |
JP2003512344A (ja) * | 1999-10-20 | 2003-04-02 | サウディ ベーシック インダストリーズ コーポレイション | アルデヒドを対応するアルコールに転化する液相触媒水素化プロセス |
JP2004505879A (ja) * | 2000-08-14 | 2004-02-26 | ザ ユニバーシティ オブ ブリティッシュ コロンビア | 水分解反応による水素の発生 |
JP2004123517A (ja) * | 2002-09-11 | 2004-04-22 | Masao Watanabe | 摩擦腐食反応を利用した水素ガス製造方法 |
JP2004196581A (ja) * | 2002-12-18 | 2004-07-15 | National Institute Of Advanced Industrial & Technology | 水素製造方法及びそれに用いる触媒 |
JP2004525053A (ja) * | 2000-12-21 | 2004-08-19 | ロディア・シミ | 水素発生システム及び水素化脱ハロゲン方法 |
JP2005537327A (ja) * | 2002-09-04 | 2005-12-08 | ビーエーエスエフ アクチェンゲゼルシャフト | 光学活性な2−アミノ−、2−クロロ−、2−ヒドロキシ−または2−アルコキシ−1−アルコールの製造方法 |
JP2006347923A (ja) * | 2005-06-14 | 2006-12-28 | Idemitsu Kosan Co Ltd | n−パラフィンの製造方法 |
JP2007031169A (ja) * | 2005-07-22 | 2007-02-08 | National Institute For Materials Science | 水素の製造方法及び二酸化炭素の固定化方法 |
JP2007045756A (ja) * | 2005-08-10 | 2007-02-22 | New Japan Chem Co Ltd | 隔膜型水素化触媒を用いた水素化方法、水素化反応装置及び隔膜型水素化触媒 |
JP2008285444A (ja) * | 2007-05-18 | 2008-11-27 | Osaka Prefecture Univ | 還元方法およびその還元方法に用いられる還元触媒 |
WO2010016462A1 (ja) * | 2008-08-04 | 2010-02-11 | チッソ株式会社 | グリセリンからのグリコール及び1-プロパノールの製造方法 |
WO2012023546A1 (ja) * | 2010-08-18 | 2012-02-23 | シオノケミカル株式会社 | 水素または重水素の製造方法およびそれを利用した有機化合物の水素化または重水素化 |
JP2012527427A (ja) * | 2009-05-20 | 2012-11-08 | ビーエーエスエフ ソシエタス・ヨーロピア | 銅含有不均一触媒上で、脂肪酸トリグリセリドの水素化を行うことによって脂肪アルコールを製造する方法 |
CN102807483A (zh) * | 2012-08-17 | 2012-12-05 | 中国科学技术大学 | 一种由糠醛或糠醇制备环戊酮和/或环戊醇的方法 |
WO2013121997A1 (ja) * | 2012-02-17 | 2013-08-22 | シオノケミカル株式会社 | 水素または重水素の製造方法、水素化または重水素化有機化合物の製造方法、有機化合物の水素化または重水素化方法、ハロゲンを有する有機化合物の脱ハロゲン化方法、メカノケミカル反応用ボ-ル |
Family Cites Families (14)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4547356A (en) * | 1980-08-05 | 1985-10-15 | Unique Energy Systems, Inc. | Method of generating hydrogen and using the generated hydrogen |
US6440385B1 (en) | 2000-08-14 | 2002-08-27 | The University Of British Columbia | Hydrogen generation from water split reaction |
AR035455A1 (es) * | 2001-04-23 | 2004-05-26 | Hoffmann La Roche | Derivados triciclicos de alquilhidroxamato , procesos para su elaboracion, composiciones farmaceuticas que los contienen, y el uso de dichos compuestos en la preparacion de medicamentos |
US6902664B2 (en) | 2002-11-08 | 2005-06-07 | Chevron U.S.A. Inc. | Extremely low acidity USY and homogeneous, amorphous silica-alumina hydrocracking catalyst and process |
US8158841B2 (en) | 2004-03-25 | 2012-04-17 | Japan Oil, Gas And Metals National Corporation | Hydrotreating method |
JP4219839B2 (ja) | 2004-03-25 | 2009-02-04 | 独立行政法人石油天然ガス・金属鉱物資源機構 | 水素化処理方法 |
WO2007100052A1 (ja) | 2006-03-01 | 2007-09-07 | National University Corporation Hokkaido University | セルロースの加水分解および/または加水分解物の還元用触媒およびセルロースから糖アルコールの製造方法 |
US20080274017A1 (en) | 2007-05-04 | 2008-11-06 | Boykin Jack W | System for the production of synthetic fuels |
JP2009275029A (ja) | 2008-04-16 | 2009-11-26 | Univ Of Tsukuba | グリセリンの還元方法、および触媒 |
JP5182635B2 (ja) | 2008-10-01 | 2013-04-17 | Jfeエンジニアリング株式会社 | 高級炭化水素油製造装置および製造方法 |
JP2011148909A (ja) | 2010-01-21 | 2011-08-04 | Tokyo Univ Of Agriculture & Technology | バイオ炭化水素、バイオ炭化水素の製造方法、およびバイオ炭化水素製造装置 |
JP5522683B2 (ja) | 2010-07-07 | 2014-06-18 | 独立行政法人産業技術総合研究所 | 炭化水素の製造方法 |
JP5736251B2 (ja) | 2011-06-29 | 2015-06-17 | 株式会社ダイセル | エリスリトールの水素化分解物の製造方法 |
US8410319B2 (en) * | 2011-07-28 | 2013-04-02 | Uop Llc | Continuous catalytic generation of polyols from cellulose with recycle |
-
2015
- 2015-01-27 EP EP15744062.9A patent/EP3101000B1/en active Active
- 2015-01-27 US US15/111,263 patent/US10106488B2/en active Active
- 2015-01-27 JP JP2015559942A patent/JP6259839B2/ja active Active
- 2015-01-27 WO PCT/JP2015/052161 patent/WO2015115410A1/ja active Application Filing
Patent Citations (17)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS61167443A (ja) * | 1984-10-02 | 1986-07-29 | Masahiro Suzuki | マグネシウム−水系を用いた有機無機物質の還元に関する方法 |
JPH03202152A (ja) * | 1989-12-28 | 1991-09-03 | Japan Synthetic Rubber Co Ltd | 水素化触媒 |
JP2003512344A (ja) * | 1999-10-20 | 2003-04-02 | サウディ ベーシック インダストリーズ コーポレイション | アルデヒドを対応するアルコールに転化する液相触媒水素化プロセス |
JP2004505879A (ja) * | 2000-08-14 | 2004-02-26 | ザ ユニバーシティ オブ ブリティッシュ コロンビア | 水分解反応による水素の発生 |
JP2004525053A (ja) * | 2000-12-21 | 2004-08-19 | ロディア・シミ | 水素発生システム及び水素化脱ハロゲン方法 |
JP2005537327A (ja) * | 2002-09-04 | 2005-12-08 | ビーエーエスエフ アクチェンゲゼルシャフト | 光学活性な2−アミノ−、2−クロロ−、2−ヒドロキシ−または2−アルコキシ−1−アルコールの製造方法 |
JP2004123517A (ja) * | 2002-09-11 | 2004-04-22 | Masao Watanabe | 摩擦腐食反応を利用した水素ガス製造方法 |
JP2004196581A (ja) * | 2002-12-18 | 2004-07-15 | National Institute Of Advanced Industrial & Technology | 水素製造方法及びそれに用いる触媒 |
JP2006347923A (ja) * | 2005-06-14 | 2006-12-28 | Idemitsu Kosan Co Ltd | n−パラフィンの製造方法 |
JP2007031169A (ja) * | 2005-07-22 | 2007-02-08 | National Institute For Materials Science | 水素の製造方法及び二酸化炭素の固定化方法 |
JP2007045756A (ja) * | 2005-08-10 | 2007-02-22 | New Japan Chem Co Ltd | 隔膜型水素化触媒を用いた水素化方法、水素化反応装置及び隔膜型水素化触媒 |
JP2008285444A (ja) * | 2007-05-18 | 2008-11-27 | Osaka Prefecture Univ | 還元方法およびその還元方法に用いられる還元触媒 |
WO2010016462A1 (ja) * | 2008-08-04 | 2010-02-11 | チッソ株式会社 | グリセリンからのグリコール及び1-プロパノールの製造方法 |
JP2012527427A (ja) * | 2009-05-20 | 2012-11-08 | ビーエーエスエフ ソシエタス・ヨーロピア | 銅含有不均一触媒上で、脂肪酸トリグリセリドの水素化を行うことによって脂肪アルコールを製造する方法 |
WO2012023546A1 (ja) * | 2010-08-18 | 2012-02-23 | シオノケミカル株式会社 | 水素または重水素の製造方法およびそれを利用した有機化合物の水素化または重水素化 |
WO2013121997A1 (ja) * | 2012-02-17 | 2013-08-22 | シオノケミカル株式会社 | 水素または重水素の製造方法、水素化または重水素化有機化合物の製造方法、有機化合物の水素化または重水素化方法、ハロゲンを有する有機化合物の脱ハロゲン化方法、メカノケミカル反応用ボ-ル |
CN102807483A (zh) * | 2012-08-17 | 2012-12-05 | 中国科学技术大学 | 一种由糠醛或糠醇制备环戊酮和/或环戊醇的方法 |
Non-Patent Citations (1)
Title |
---|
RUPPERT A. M. ET AL: "Hydrogenolysis Goes Bio: From Carbohydrates and Sugar Alcohols to Platform Chemicals", ANGEWANDTE CHEMIE INTERNATIONAL EDITION, vol. Volume 51, Issue 11, JPN6015016866, 2012, pages 2564 - 2601, XP002696570, ISSN: 0003651259 * |
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