JP2004255282A - Steam-reforming catalyst for methanol and method for producing hydrogen by steam-reforming methanol by using the catalyst - Google Patents
Steam-reforming catalyst for methanol and method for producing hydrogen by steam-reforming methanol by using the catalyst Download PDFInfo
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Abstract
Description
【０００１】
【発明の属する技術分野】
本発明は、メタノールの水蒸気改質触媒および該触媒の存在下でメタノールを水蒸気改質することを特徴とする水素の製造方法に関する。
【０００２】
【従来の技術】
メタノールの水蒸気改質反応は、次の式（１）、式（２）に示した反応からなると考えられている。
【０００３】
【化１】
上記の反応により、メタノールと水蒸気とから水素を製造することができる。
【０００５】
従来、メタノールの水蒸気改質触媒として、銅系触媒が活性及び選択性に優れていることが広く知られているが、銅系触媒は熱安定性に問題があるといわれている（非特許文献１）。
【０００６】
このように銅系触媒は熱安定性に問題があるといわれてはいるが、高い触媒活性を有することから、銅系触媒の改良に関する報告例はその数が多い。
【０００７】
例えば、銅系触媒として、銅、亜鉛および周期律表第８属の各金属元素を含有する触媒および該触媒を用いたメタノールの水蒸気改質反応に関する報告がなされている。
【０００８】
特許文献１には、酸化銅、酸化亜鉛、酸化ニッケルおよび酸化アルミニウムからなる触媒をプロセスに組み込んだメタノールの水蒸気改質法が報告されている。
【０００９】
特許文献２には、銅、亜鉛、クロムおよび鉄を主成分とする特定の触媒が、低温でのメタノール転化率が高く、高温時に生成ガス中の一酸化炭素濃度が低く抑えられること、さらに耐熱性が高く触媒寿命が延びることが報告されている。
【００１０】
本発明者らは、特許文献３において、銅、亜鉛および貴金属であるパラジウムおよび／または白金を含む特定の触媒およびこれを用いてメタノールと水蒸気とから水素を製造する方法について報告している。
【００１１】
しかしながら、これら公知の触媒は、触媒の活性および耐久性、一酸化炭素の副生率の点で充分満足すべきものとはいえない。
【００１２】
【非特許文献１】
触媒学会編「触媒講座・第９巻」（１９８５年５月１０日発行） 講談社、Ｐ１３２〜１３４
【特許文献１】
特開昭５９−１５２２０５号公報
【特許文献２】
特開昭６０−７７１０４号公報
【特許文献３】
特開２００２−９５９７０号公報
【００１３】
【発明が解決しようとする課題】
本発明は、前記の従来技術に鑑み、触媒の活性および耐久性を損なわずに一酸化炭素の副生を抑制することのできるメタノールの水蒸気改質触媒を提供することを課題とする。また、本発明は、該触媒の存在下でメタノールを水蒸気改質することを特徴とする水素の製造方法を提供することを課題とする。
【００１４】
【課題を解決するための手段】
本発明者らは、前述の課題を解決すべく鋭意検討した結果、特定の金属元素の酸化物を触媒成分として含有する触媒が課題の解決に有効であることを見出し、本発明を完成するに至った。
【００１５】
すなわち、本発明は、
▲１▼ 銅酸化物、亜鉛酸化物、パラジウム酸化物および鉄酸化物を含むメタノールの水蒸気改質触媒、
▲２▼ 前記▲１▼に記載の触媒において、銅酸化物、亜鉛酸化物、パラジウム酸化物および鉄酸化物の各酸化物の合計量に占める鉄酸化物の含有率が０．２〜３０重量％である、メタノールの水蒸気改質触媒、
▲３▼ 前記▲１▼に記載の触媒において、銅酸化物、亜鉛酸化物、パラジウム酸化物および鉄酸化物の各酸化物の合計量に占める鉄酸化物の含有率が０．５〜２５重量％である、メタノールの水蒸気改質触媒、
▲４▼ 前記▲１▼に記載の触媒において、銅酸化物、亜鉛酸化物、パラジウム酸化物および鉄酸化物の各酸化物の合計量に占める鉄酸化物の含有率が１．０〜２２重量％である、メタノールの水蒸気改質触媒、
▲５▼ 前記▲１▼〜▲４▼のいずれか１項に記載の触媒が共沈法により調製されたものである、メタノールの水蒸気改質触媒、
▲６▼ 前記▲１▼〜▲５▼のいずれか１項に記載の触媒の存在下で、メタノールを水蒸気改質することを特徴とする水素の製造方法
である。
【００１６】
【発明の実施の形態】
本発明のメタノールの水蒸気改質触媒（以下単に「触媒」という。）は、銅酸化物、亜鉛酸化物、パラジウム酸化物および鉄酸化物を必須成分として含むことを特徴とする。
【００１７】
これらの各酸化物を必須成分として含む本発明の触媒は、触媒の活性および耐久性を損なわずに一酸化炭素の副生を抑制することができる。
【００１８】
本発明の触媒において、銅酸化物、亜鉛酸化物、パラジウム酸化物、鉄酸化物の各酸化物の合計量に占める鉄酸化物の含有率は、好ましくは０．２〜３０重量％、より好ましくは０．５〜２５重量％、特に好ましくは１．０〜２２重量％である。
【００１９】
本発明の触媒において、銅酸化物、亜鉛酸化物、パラジウム酸化物、鉄酸化物の合計量に占める鉄酸化物の含有率が０．２重量％以上であると一酸化炭素の選択率が小さくなる点で好ましく、３０重量％以下であるとメタノールの転化率が高くなる点で好ましい。
【００２０】
本発明の触媒のなかでも、銅酸化物、亜鉛酸化物、パラジウム酸化物、鉄酸化物の各酸化物の合計量に占める銅酸化物、亜鉛酸化物、パラジウム酸化物、鉄酸化物のそれぞれの含有率が、銅酸化物１５〜４０重量％、亜鉛酸化物４５〜６０重量％、パラジウム酸化物０．５〜３０重量％、鉄酸化物０．２〜３０重量％である触媒は好ましく、銅酸化物１５〜４０重量％、亜鉛酸化物４５〜６０重量％、パラジウム酸化物０．５〜３０重量％、鉄酸化物０．５〜２５重量％である触媒はより好ましく、銅酸化物１５〜４０重量％、亜鉛酸化物４５〜６０重量％、パラジウム酸化物０．５〜３０重量％、鉄酸化物１．０〜２２重量％である触媒は特に好ましい。
【００２１】
本発明の触媒には、本発明の効果を損なわない範囲であれば、金属元素および本発明の触媒において必須成分である各酸化物以外の酸化物を成分として含むことは差し支えない。金属元素としては、例えば、銅、亜鉛、パラジウム、鉄、白金、ジルコニウムが挙げられる。酸化物としては、例えば、酸化珪素、酸化アルミニウム、酸化チタン、酸化ジルコニウム、酸化マグネシウムが挙げられる。
【００２２】
本発明の触媒の製造方法には特に制限はないが、例えば、湿式法を用いて調製することができる。湿式法としては、含浸法および共沈法が挙げられるが、これらのなかでも共沈法は高い活性が得られる点で好ましい。
【００２３】
本発明の触媒の共沈法による製造方法を具体的に示すとすれば、例えば、銅、亜鉛、パラジウム、鉄の各金属元素の酸性塩水溶液を混合した水溶液を塩基性化合物の水溶液と接触させ、析出した析出物を洗浄・回収し、回収した析出物を乾燥した後、焼成する方法が挙げられる。
【００２４】
銅、亜鉛、パラジウム、鉄の各金属元素の酸性塩としては、塩基性化合物と反応させて得られる析出物を乾燥・焼成して各金属元素の酸化物を与えるものであれば特に制限はない。このような酸性塩としては、例えば、硝酸塩、硫酸塩、塩酸塩が挙げられる。
【００２５】
各金属元素の酸性塩と接触させる塩基性化合物としては、例えば、アルカリ金属またはアルカリ土類金属の炭酸塩、重炭酸塩が挙げられる。
【００２６】
銅、亜鉛、パラジウム、鉄の各金属元素の酸性塩水溶液を塩基性化合物の水溶液と接触させる方法としては、接触させて得られる水溶液のｐＨを６〜９の範囲となるように制御できれば特に制限はなく、例えば、塩基性化合物の水溶液と各金属元素の酸性塩の水溶液を同時に混合する方法、塩基性化合物の水溶液に各金属元素の酸性塩水溶液を混合した水溶液を加える方法、各金属元素の酸性塩水溶液を混合した溶液に塩基性化合物の水溶液を加える方法が挙げられる。
【００２７】
銅、亜鉛、パラジウムおよび鉄の各金属元素の酸性塩水溶液と塩基性化合物の水溶液とを接触させる温度は、約１０〜約８０℃の温度範囲であれば特に制限はない。
【００２８】
銅、亜鉛、パラジウム、鉄の各金属元素の酸性塩と塩基性化合物とを反応させて得られる析出物は、通常、室温〜５０℃の温度範囲の水で洗浄し、次いで約１００〜１６０℃の温度範囲で空気または不活性ガス雰囲気下で乾燥させる。
【００２９】
乾燥した後、焼成することにより本発明の触媒を得ることができる。焼成は約２００℃〜４７０℃の温度範囲で行うことができる。焼成温度は４５０℃以下が好ましい。また、焼成温度が３００℃以上であると該析出物の分解が充分行われる点で好ましい。焼成は、通常、空気または不活性ガスの存在下で行う。
【００３０】
焼成後の触媒は、そのままメタノールの水蒸気改質反応に用いることができるが、焼成後の触媒を液相または気相中で水素、一酸化炭素等の還元性ガスで処理した後、メタノールの水蒸気改質反応に用いることもできる。
【００３１】
本発明の触媒は、打錠成型または押し出し成型する他、ムライト、コージェライトなどのセラミック担体、シリカクロス、スポンジ状金属焼結多孔板等の上に担持せしめたハニカム状の形状にして反応に用いることもできる。
【００３２】
本発明における水素の製造方法は、本発明の触媒の存在下にメタノールと水（水蒸気）とを接触させることにより行われる。
【００３３】
メタノールの水蒸気改質反応の反応条件は、メタノールの転化率、生成する水素の収率などの所望値に応じ適宜決定することができる。
【００３４】
通常、メタノールと水の使用割合は、メタノール１モルに対して水０．５〜３０モルとなるように用いられるが、好ましくはメタノール１モルに対して水１〜１０モルである。
【００３５】
反応温度としては、通常、１５０〜６００℃、 好ましくは、反応温度２００〜５００℃である。
【００３６】
反応圧力としては、通常、５０ｋｇ／ｃｍ２Ｇ以下、好ましくは３０ｋｇ／ｃｍ２Ｇ〜常圧である。
【００３７】
触媒に接触させるメタノールと水蒸気を含む混合ガスの空間速度は、５０〜５００，０００ｈｒ−１、好ましくは１００〜１５０，０００ｈｒ−１の範囲である。
【００３８】
なお、本発明における水素の製造方法においては、必要に応じて水素、一酸化炭素、二酸化炭素、窒素、及び空気等のガスを共存させることもできる。
【００３９】
【実施例】
以下、本発明を実施例によりさらに具体的に説明するが、本発明はこれら実施例に限定されるものではない。
【００４０】
（１）触媒の調製
［実施例１］
硝酸パラジウム［Ｐｄ（ＮＯ３）２］水溶液 ６．１２ｇ（Ｐｄ；５ｗｔ％含有）、硝酸銅・三水和物 ［Ｃｕ（ＮＯ３）２・３Ｈ２Ｏ］ ６．９５ｇ、硝酸亜鉛・六水和物［Ｚｎ（ＮＯ３）２・６Ｈ２Ｏ］２６．１０ｇ、硝酸鉄・九水和物［Ｆｅ（ＮＯ３）３・９Ｈ２Ｏ］１２．９１ｇ、硝酸アルミニウム・九水和物［Ａｌ（ＮＯ３）３・９Ｈ２Ｏ］４．７８ｇ、を純水２００ｍｌに溶解し水溶液（Ａ液）を調製した。一方、炭酸ナトリウム・十水和物［Ｎａ２ＣＯ３・１０Ｈ２Ｏ］６４．３０ｇを純水２００ｍｌに溶解し水溶液（Ｂ液）を調整した。水４００ｍｌを入れたフラスコを用意し、室温でフラスコ内の水を攪拌しながら、これにＡ液およびＢ液を同一速度で滴下した。生成したスラリーを１５０分間攪拌した後、スラリー中の析出物を減圧濾過し、蒸留水にて十分に洗浄した。その後、回収した析出物を８０℃に調節した乾燥器中で１２時間乾燥させた後、大気下で温度３５０℃に調整した電気炉内で３時間焼成して酸化物を１３．０ｇ得た。酸化物を打錠成型、粉砕した後、粉砕物１ｍｌを採取した。これを小型反応管に充填し、Ｈ２／Ｎ２＝１／９の混合ガＧＨＳＶ＝６０００ ［ｈｒ−１］、３５０℃にて還元処理を行い、触媒を得た。
【００４１】
［実施例２］
Ａ液として硝酸パラジウム［Ｐｄ（ＮＯ３）２］水溶液 １１．７４ｇ（Ｐｄ；５ｗｔ％含有）、硝酸銅・三水和物 ［Ｃｕ（ＮＯ３）２・３Ｈ２Ｏ］ １２．６９ｇ、硝酸亜鉛・六水和物［Ｚｎ（ＮＯ３）２・６Ｈ２Ｏ］２５．４５ｇ、硝酸鉄・九水和物［Ｆｅ（ＮＯ３）３・９Ｈ２Ｏ］１．０６ｇ、硝酸アルミニウム・九水和物［Ａｌ（ＮＯ３）３・９Ｈ２Ｏ］４．６６ｇ、Ｂ液として炭酸ナトリウム・十水和物［Ｎａ２ＣＯ３・１０Ｈ２Ｏ］５７．６０ｇを含む液をそれぞれ調製し、実施例１と同様な方法を用いて触媒を得た。
【００４２】
［実施例３］
Ａ液として硝酸パラジウム［Ｐｄ（ＮＯ３）２］水溶液 ５２．３７ｇ（Ｐｄ；５ｗｔ％含有）、硝酸銅・三水和物 ［Ｃｕ（ＮＯ３）２・３Ｈ２Ｏ］ ６．０１ｇ、硝酸亜鉛・六水和物［Ｚｎ（ＮＯ３）２・６Ｈ２Ｏ］２１．２５ｇ、硝酸鉄・九水和物［Ｆｅ（ＮＯ３）３・９Ｈ２Ｏ］５．７９ｇ、硝酸アルミニウム・九水和物［Ａｌ（ＮＯ３）３・９Ｈ２Ｏ］４．５９ｇ、Ｂ液として炭酸ナトリウム・十水和物［Ｎａ２ＣＯ３・１０Ｈ２Ｏ］５７．６７ｇを含む液をそれぞれ調製し、実施例１と同様な方法を用いて触媒を得た。
【００４３】
［実施例４］
Ａ液として硝酸パラジウム［Ｐｄ（ＮＯ３）２］水溶液 １１．８６ｇ（Ｐｄ；５ｗｔ％含有）、硝酸銅・三水和物 ［Ｃｕ（ＮＯ３）２・３Ｈ２Ｏ］ １３．８６ｇ、硝酸亜鉛・六水和物［Ｚｎ（ＮＯ３）２・６Ｈ２Ｏ］２１．０２ｇ、硝酸鉄・九水和物［Ｆｅ（ＮＯ３）３・９Ｈ２Ｏ］５．７９ｇ、硝酸アルミニウム・九水和物［Ａｌ（ＮＯ３）３・９Ｈ２Ｏ］４．７０ｇ、Ｂ液として炭酸ナトリウム・十水和物［Ｎａ２ＣＯ３・１０Ｈ２Ｏ］６０．２９ｇを含む液をそれぞれ調製し、実施例１と同様な方法を用いて触媒を得た。
【００４４】
［実施例５］
Ａ液として硝酸パラジウム［Ｐｄ（ＮＯ３）２］水溶液 １１．９９ｇ（Ｐｄ；５ｗｔ％含有）、硝酸銅・三水和物 ［Ｃｕ（ＮＯ３）２・３Ｈ２Ｏ］ １０．５１ｇ、硝酸亜鉛・六水和物［Ｚｎ（ＮＯ３）２・６Ｈ２Ｏ］２１．２７ｇ、硝酸鉄・九水和物［Ｆｅ（ＮＯ３）３・９Ｈ２Ｏ］１１．７１ｇ、硝酸アルミニウム・九水和物［Ａｌ（ＮＯ３）３・９Ｈ２Ｏ］４．７６ｇ、Ｂ液として炭酸ナトリウム・十水和物［Ｎａ２ＣＯ３・１０Ｈ２Ｏ］６３．４５ｇを含む液をそれぞれ調製し、実施例１と同様な方法を用いて触媒を得た。
【００４５】
［実施例６］
Ａ液として硝酸パラジウム［Ｐｄ（ＮＯ３）２］水溶液 １１．８０ｇ（Ｐｄ；５ｗｔ％含有）、硝酸銅・三水和物 ［Ｃｕ（ＮＯ３）２・３Ｈ２Ｏ］ １３．０２ｇ、硝酸亜鉛・六水和物［Ｚｎ（ＮＯ３）２・６Ｈ２Ｏ］２５．４８ｇ、硝酸鉄・九水和物［Ｆｅ（ＮＯ３）３・９Ｈ２Ｏ］０．３６ｇ、硝酸アルミニウム・九水和物［Ａｌ（ＮＯ３）３・９Ｈ２Ｏ］４．７３ｇ、Ｂ液として炭酸ナトリウム・十水和物［Ｎａ２ＣＯ３・１０Ｈ２Ｏ］５７．３０ｇを含む液をそれぞれ調製し、実施例１と同様な方法を用いて触媒を得た。
【００４６】
［実施例７］
Ａ液として硝酸パラジウム［Ｐｄ（ＮＯ３）２］水溶液 ２．３４ｇ（Ｐｄ；５ｗｔ％含有）、硝酸銅・三水和物 ［Ｃｕ（ＮＯ３）２・３Ｈ２Ｏ］ ７．６８ｇ、硝酸亜鉛・六水和物［Ｚｎ（ＮＯ３）２・６Ｈ２Ｏ］２５．０２ｇ、硝酸鉄・九水和物［Ｆｅ（ＮＯ３）３・９Ｈ２Ｏ］１４．５４ｇ、硝酸アルミニウム・九水和物［Ａｌ（ＮＯ３）３・９Ｈ２Ｏ］４．７８ｇ、Ｂ液として炭酸ナトリウム・十水和物［Ｎａ２ＣＯ３・１０Ｈ２Ｏ］６５．３９ｇを含む液をそれぞれ調製し、実施例１と同様な方法を用いて触媒を得た。
【００４７】
［比較例１］
Ａ液として硝酸パラジウム［Ｐｄ（ＮＯ３）２］水溶液 １１．７２ｇ（Ｐｄ；５ｗｔ％含有）、硝酸銅・三水和物 ［Ｃｕ（ＮＯ３）２・３Ｈ２Ｏ］ １３．３０ｇ、硝酸亜鉛・六水和物［Ｚｎ（ＮＯ３）２・６Ｈ２Ｏ］２５．３９ｇ、硝酸アルミニウム・九水和物［Ａｌ（ＮＯ３）３・９Ｈ２Ｏ］４．６５ｇ、Ｂ液として炭酸ナトリウム・十水和物［Ｎａ２ＣＯ３・１０Ｈ２Ｏ］５７．０４ｇを含む液をそれぞれ調製し、実施例１と同様な方法を用いて触媒を得た。
【００４８】
［比較例２］
Ａ液として硝酸パラジウム［Ｐｄ（ＮＯ３）２］水溶液 ５２．３７ｇ（Ｐｄ；５ｗｔ％含有）、硝酸銅・三水和物 ［Ｃｕ（ＮＯ３）２・３Ｈ２Ｏ］ ５．９４ｇ、硝酸亜鉛・六水和物［Ｚｎ（ＮＯ３）２・６Ｈ２Ｏ］２４．９７ｇ、硝酸アルミニウム・九水和物［Ａｌ（ＮＯ３）３・９Ｈ２Ｏ］４．５７ｇ、Ｂ液として炭酸ナトリウム・十水和物［Ｎａ２ＣＯ３・１０Ｈ２Ｏ］５４．４８ｇを含む液をそれぞれ調製し、実施例１と同様な方法を用いて触媒を得た。
【００４９】
［比較例３］
Ａ液として硝酸銅・三水和物 ［Ｃｕ（ＮＯ３）２・３Ｈ２Ｏ］ １５．４２ｇ、硝酸亜鉛・六水和物［Ｚｎ（ＮＯ３）２・６Ｈ２Ｏ］２５．５１ｇ、硝酸アルミニウム・九水和物［Ａｌ（ＮＯ３）３・９Ｈ２Ｏ］４．６７ｇ、Ｂ液として炭酸ナトリウム・十水和物［Ｎａ２ＣＯ３・１０Ｈ２Ｏ］５７．７８ｇを含む液をそれぞれ調製し、実施例１と同様な方法を用いて触媒を得た。
【００５０】
［比較例４］
Ａ液として硝酸銅・三水和物 ［Ｃｕ（ＮＯ３）２・３Ｈ２Ｏ］ １１．７０ｇ、硝酸亜鉛・六水和物［Ｚｎ（ＮＯ３）２・６Ｈ２Ｏ］２５．８４ｇ、硝酸鉄・九水和物［Ｆｅ（ＮＯ３）３・９Ｈ２Ｏ］６．５３ｇ、硝酸アルミニウム・九水和物［Ａｌ（ＮＯ３）３・９Ｈ２Ｏ］４．７３ｇ、Ｂ液として炭酸ナトリウム・十水和物［Ｎａ２ＣＯ３・１０Ｈ２Ｏ］６１．２７ｇを含む液をそれぞれ調製し、実施例１と同様な方法を用いて触媒を得た。
【００５１】
［比較例５］
Ａ液として硝酸銅・三水和物 ［Ｃｕ（ＮＯ３）２・３Ｈ２Ｏ］ ４．１４ｇ、硝酸亜鉛・六水和物［Ｚｎ（ＮＯ３）２・６Ｈ２Ｏ］２６．５ｇ、硝酸鉄・九水和物［Ｆｅ（ＮＯ３）３・９Ｈ２Ｏ］１９．７９ｇ、硝酸アルミニウム・九水和物［Ａｌ（ＮＯ３）３・９Ｈ２Ｏ］４．８５ｇ、Ｂ液として炭酸ナトリウム・十水和物［Ｎａ２ＣＯ３・１０Ｈ２Ｏ］６８．３７ｇを含む液をそれぞれ調製し、実施例１と同様な方法を用いて触媒を得た。
【００５２】
２）活性試験
上記の方法で調製した触媒について、メタノールの水蒸気改質反応の活性を測定した。原料として５９．７重量％のメタノール水溶液Ｈ２Ｏ／ＣＨ３ＯＨ＝１．２（モル／モル）を用い、Ｏ２／ＣＨ３ＯＨ＝０．１（モル／モル）となるように空気を導入した。反応条件として反応温度２５０℃、常圧下にて、前記原料であるメタノール水溶液の供給速度を単位触媒量あたり６０（Ｌ−ｓｏｌｖ．／Ｌ−ｃａｔ・ｈ）にて行った。反応により生成したガスはガスクロマトグラフィーにて成分を測定した。加速劣化試験として反応開始後４８時間のメタノール転化率を求め、生成ガス中の一酸化炭素及び二酸化炭素の成分濃度より一酸化炭素の選択率を算出した。
【００５３】
【化２】
調製した触媒の組成および活性試験の結果を表１に示す。
【００５５】
【表１】
表１
【発明の効果】
本発明によれば、高い触媒活性および耐久性を有し、かつ、一酸化炭素の選択率が低いメタノールの水蒸気改質触媒を提供することができる。また、本発明の水素の製造方法によれば、長期にわたり効率よく水素を製造することが可能である。[0001]
TECHNICAL FIELD OF THE INVENTION
The present invention relates to a steam reforming catalyst for methanol and a method for producing hydrogen, which comprises steam reforming methanol in the presence of the catalyst.
[0002]
[Prior art]
It is considered that the steam reforming reaction of methanol consists of the reactions shown in the following equations (1) and (2).
[0003]
Embedded image
By the above reaction, hydrogen can be produced from methanol and steam.
[0005]
Conventionally, as a steam reforming catalyst for methanol, it is widely known that a copper-based catalyst has excellent activity and selectivity, but it is said that the copper-based catalyst has a problem in thermal stability (Non-patent Document 1).
[0006]
Although it is said that the copper-based catalyst has a problem in thermal stability as described above, there are many reports on improvement of the copper-based catalyst because of its high catalytic activity.
[0007]
For example, there have been reports on catalysts containing copper, zinc, and each metal element belonging to Group 8 of the Periodic Table as a copper-based catalyst, and on steam reforming of methanol using the catalyst.
[0008]
Patent Document 1 reports a steam reforming method for methanol in which a catalyst comprising copper oxide, zinc oxide, nickel oxide, and aluminum oxide is incorporated in a process.
[0009]
Patent Document 2 discloses that a specific catalyst containing copper, zinc, chromium, and iron as its main components has a high conversion rate of methanol at a low temperature and a low carbon monoxide concentration in a generated gas at a high temperature. It is reported that the catalyst life is high and the catalyst life is prolonged.
[0010]
The present inventors report in Patent Document 3 a specific catalyst containing copper, zinc and the noble metals palladium and / or platinum, and a method for producing hydrogen from methanol and steam using the same.
[0011]
However, these known catalysts are not sufficiently satisfactory in terms of the activity and durability of the catalyst and the by-product rate of carbon monoxide.
[0012]
[Non-patent document 1]
The Japan Society of Catalysis, “Catalyst Course, Volume 9” (issued May 10, 1985) Kodansha, P132-134
[Patent Document 1]
JP-A-59-152205 [Patent Document 2]
JP-A-60-77104 [Patent Document 3]
JP-A-2002-95970
[Problems to be solved by the invention]
An object of the present invention is to provide a steam reforming catalyst for methanol that can suppress the by-product of carbon monoxide without impairing the activity and durability of the catalyst in view of the above-mentioned conventional technology. Another object of the present invention is to provide a method for producing hydrogen, which comprises subjecting methanol to steam reforming in the presence of the catalyst.
[0014]
[Means for Solving the Problems]
The present inventors have conducted intensive studies to solve the aforementioned problems, and as a result, have found that a catalyst containing an oxide of a specific metal element as a catalyst component is effective in solving the problems. Reached.
[0015]
That is, the present invention
(1) A steam reforming catalyst for methanol containing copper oxide, zinc oxide, palladium oxide and iron oxide,
(2) In the catalyst according to (1), the content of iron oxide in the total amount of each oxide of copper oxide, zinc oxide, palladium oxide and iron oxide is 0.2 to 30% by weight. %, A steam reforming catalyst for methanol,
(3) In the catalyst according to (1), the content of iron oxide in the total amount of each of copper oxide, zinc oxide, palladium oxide, and iron oxide is 0.5 to 25% by weight. %, A steam reforming catalyst for methanol,
(4) The catalyst according to (1), wherein the content of iron oxide in the total amount of each of the oxides of copper oxide, zinc oxide, palladium oxide and iron oxide is 1.0 to 22% by weight. %, A steam reforming catalyst for methanol,
(5) a methanol steam reforming catalyst, wherein the catalyst according to any one of (1) to (4) is prepared by a coprecipitation method;
(6) A method for producing hydrogen, comprising subjecting methanol to steam reforming in the presence of the catalyst according to any one of (1) to (5).
[0016]
BEST MODE FOR CARRYING OUT THE INVENTION
The methanol steam reforming catalyst of the present invention (hereinafter, simply referred to as “catalyst”) is characterized by containing copper oxide, zinc oxide, palladium oxide and iron oxide as essential components.
[0017]
The catalyst of the present invention containing these oxides as essential components can suppress the by-product of carbon monoxide without impairing the activity and durability of the catalyst.
[0018]
In the catalyst of the present invention, the content of iron oxide in the total amount of each oxide of copper oxide, zinc oxide, palladium oxide and iron oxide is preferably 0.2 to 30% by weight, more preferably Is 0.5 to 25% by weight, particularly preferably 1.0 to 22% by weight.
[0019]
In the catalyst of the present invention, when the content of iron oxide in the total amount of copper oxide, zinc oxide, palladium oxide and iron oxide is 0.2% by weight or more, the selectivity of carbon monoxide is small. When the content is 30% by weight or less, the conversion of methanol is high, which is preferable.
[0020]
Among the catalysts of the present invention, copper oxides, zinc oxides, palladium oxides, copper oxides, zinc oxides, palladium oxides, and iron oxides account for the total amount of each oxide. A catalyst having a content of 15 to 40% by weight of copper oxide, 45 to 60% by weight of zinc oxide, 0.5 to 30% by weight of palladium oxide, and 0.2 to 30% by weight of iron oxide is preferable. A catalyst containing 15 to 40% by weight of an oxide, 45 to 60% by weight of a zinc oxide, 0.5 to 30% by weight of a palladium oxide, and 0.5 to 25% by weight of an iron oxide is more preferable. Catalysts which are 40% by weight, 45-60% by weight of zinc oxide, 0.5-30% by weight of palladium oxide and 1.0-22% by weight of iron oxide are particularly preferred.
[0021]
The catalyst of the present invention may contain metal elements and oxides other than the respective oxides which are essential components in the catalyst of the present invention as long as the effects of the present invention are not impaired. Examples of the metal element include copper, zinc, palladium, iron, platinum, and zirconium. Examples of the oxide include silicon oxide, aluminum oxide, titanium oxide, zirconium oxide, and magnesium oxide.
[0022]
Although the method for producing the catalyst of the present invention is not particularly limited, it can be prepared by, for example, a wet method. Examples of the wet method include an impregnation method and a coprecipitation method. Among them, the coprecipitation method is preferable in that a high activity is obtained.
[0023]
If the production method of the catalyst of the present invention by the coprecipitation method is specifically shown, for example, an aqueous solution obtained by mixing an aqueous solution of an acidic salt of each metal element of copper, zinc, palladium, and iron is brought into contact with an aqueous solution of a basic compound. And a method of washing and recovering the deposited precipitate, drying the recovered precipitate, and firing the dried precipitate.
[0024]
The acidic salt of each metal element of copper, zinc, palladium, and iron is not particularly limited as long as the precipitate obtained by reacting with a basic compound is dried and fired to give an oxide of each metal element. . Examples of such acidic salts include nitrates, sulfates, and hydrochlorides.
[0025]
Examples of the basic compound to be brought into contact with the acid salt of each metal element include carbonates and bicarbonates of alkali metals or alkaline earth metals.
[0026]
The method of contacting an aqueous solution of an acidic salt of each metal element of copper, zinc, palladium, and iron with an aqueous solution of a basic compound is particularly limited as long as the pH of the aqueous solution obtained by the contact can be controlled to be in the range of 6 to 9. For example, a method of simultaneously mixing an aqueous solution of a basic compound and an aqueous solution of an acidic salt of each metal element, a method of adding an aqueous solution obtained by mixing an aqueous solution of an acidic salt of each metal element with an aqueous solution of a basic compound, There is a method in which an aqueous solution of a basic compound is added to a solution obtained by mixing an aqueous solution of an acidic salt.
[0027]
The temperature at which the aqueous solution of the acidic salt of each metal element of copper, zinc, palladium and iron is brought into contact with the aqueous solution of the basic compound is not particularly limited as long as it is in the temperature range of about 10 to about 80 ° C.
[0028]
A precipitate obtained by reacting an acidic salt of each metal element of copper, zinc, palladium and iron with a basic compound is usually washed with water in a temperature range of room temperature to 50 ° C, and then washed at about 100 to 160 ° C. And dried under an air or inert gas atmosphere in the temperature range described above.
[0029]
After drying, the catalyst of the present invention can be obtained by calcining. Firing can be performed in a temperature range of about 200C to 470C. The firing temperature is preferably 450 ° C. or lower. Further, it is preferable that the calcination temperature is 300 ° C. or higher in that the decomposition of the precipitate is sufficiently performed. The calcination is usually performed in the presence of air or an inert gas.
[0030]
The calcined catalyst can be used for the steam reforming reaction of methanol as it is, but after treating the calcined catalyst in a liquid or gaseous phase with a reducing gas such as hydrogen or carbon monoxide, the steam of methanol is removed. It can also be used for a reforming reaction.
[0031]
The catalyst of the present invention is used for the reaction in a honeycomb shape which is supported on a ceramic carrier such as mullite or cordierite, silica cloth, a sponge-like metal sintered porous plate or the like, in addition to tablet molding or extrusion molding. You can also.
[0032]
The method for producing hydrogen in the present invention is performed by bringing methanol into contact with water (steam) in the presence of the catalyst of the present invention.
[0033]
The reaction conditions for the steam reforming reaction of methanol can be appropriately determined according to desired values such as the conversion of methanol and the yield of generated hydrogen.
[0034]
Usually, methanol and water are used at a ratio of 0.5 to 30 mol of water to 1 mol of methanol, but preferably 1 to 10 mol of water to 1 mol of methanol.
[0035]
The reaction temperature is usually from 150 to 600C, preferably from 200 to 500C.
[0036]
The reaction pressure is usually 50 kg / cm 2 G or less, preferably 30 kg / cm 2 G to normal pressure.
[0037]
The space velocity of the mixed gas containing methanol and water vapor brought into contact with the catalyst is in the range of 50 to 500,000 hr -1 , preferably 100 to 150,000 hr -1 .
[0038]
In the method for producing hydrogen according to the present invention, gases such as hydrogen, carbon monoxide, carbon dioxide, nitrogen, and air may be used, if necessary.
[0039]
【Example】
Hereinafter, the present invention will be described more specifically with reference to examples, but the present invention is not limited to these examples.
[0040]
(1) Preparation of catalyst [Example 1]
6.12 g of aqueous solution of palladium nitrate [Pd (NO 3 ) 2 ] (containing 5 wt% of Pd), 6.95 g of copper nitrate trihydrate [Cu (NO 3 ) 2 .3H 2 O], zinc nitrate 6 water dihydrate [Zn (NO 3) 2 · 6H 2 O] 26.10g, iron nitrate nonahydrate [Fe (NO 3) 3 · 9H 2 O] 12.91g, aluminum nitrate nonahydrate [Al (NO 3) 3 · 9H2O] 4.78g, was prepared was dissolved in pure water 200ml aqueous (a solution). On the other hand, an aqueous solution (solution B) was prepared by dissolving 64.30 g of sodium carbonate decahydrate [Na 2 CO 3 .10H 2 O] in 200 ml of pure water. A flask containing 400 ml of water was prepared, and while stirring the water in the flask at room temperature, the solution A and the solution B were dropped at the same rate. After the generated slurry was stirred for 150 minutes, the precipitate in the slurry was filtered under reduced pressure and washed sufficiently with distilled water. Thereafter, the collected precipitate was dried in a dryer adjusted to 80 ° C. for 12 hours, and then calcined in an electric furnace adjusted to a temperature of 350 ° C. in the atmosphere for 3 hours to obtain 13.0 g of an oxide. After the oxide was tableted and pulverized, 1 ml of the pulverized material was collected. This was filled in a small reaction tube and subjected to a reduction treatment at 350 ° C. at a mixed gas GHSV of 6000 [hr −1 ] of H 2 / N 2 = 1/9 to obtain a catalyst.
[0041]
[Example 2]
Palladium nitrate as A solution [Pd (NO 3) 2] solution 11.74g (Pd; 5wt% containing), copper nitrate trihydrate [Cu (NO 3) 2 · 3H 2 O] 12.69g, zinc nitrate 25.45 g of hexahydrate [Zn (NO 3 ) 2 .6H 2 O], 1.06 g of iron nitrate 9-hydrate [Fe (NO 3 ) 3 9H 2 O], aluminum nitrate 9-hydrate things [Al (NO 3) 3 · 9H 2 O] 4.66g, sodium carbonate decahydrate [Na 2 CO 3 · 10H 2 O] 57.60g liquid containing the respectively prepared as solution B, example A catalyst was obtained using the same method as in Example 1.
[0042]
[Example 3]
Palladium nitrate as A solution [Pd (NO 3) 2] solution 52.37g (Pd; 5wt% containing), copper nitrate trihydrate [Cu (NO 3) 2 · 3H 2 O] 6.01g, zinc nitrate Hexahydrate [Zn (NO 3 ) 2 .6H 2 O] 21.25 g, iron nitrate 9-hydrate [Fe (NO 3 ) 3 9H 2 O] 5.79 g, aluminum nitrate 9-hydrate things [Al (NO 3) 3 · 9H 2 O] 4.59g, sodium carbonate decahydrate [Na 2 CO 3 · 10H 2 O] 57.67g liquid containing the respectively prepared as solution B, example A catalyst was obtained using the same method as in Example 1.
[0043]
[Example 4]
Palladium nitrate as A solution [Pd (NO 3) 2] solution 11.86g (Pd; 5wt% containing), copper nitrate trihydrate [Cu (NO 3) 2 · 3H 2 O] 13.86g, zinc nitrate 21.02 g of hexahydrate [Zn (NO 3 ) 2 .6H 2 O], 5.79 g of iron nitrate 9-hydrate [Fe (NO 3 ) 3 .9H 2 O], aluminum nitrate 9-hydrate A liquid containing 4.70 g of the product [Al (NO 3 ) 3 .9H 2 O] and 60.29 g of sodium carbonate decahydrate [Na 2 CO 3 .10H 2 O] as the liquid B was prepared, respectively. A catalyst was obtained using the same method as in Example 1.
[0044]
[Example 5]
Palladium nitrate as A solution [Pd (NO 3) 2] solution 11.99g (Pd; 5wt% containing), copper nitrate trihydrate [Cu (NO 3) 2 · 3H 2 O] 10.51g, zinc nitrate 21.27 g of hexahydrate [Zn (NO 3 ) 2 .6H 2 O], 11.71 g of iron nitrate 9-hydrate [Fe (NO 3 ) 3 .9H 2 O], aluminum nitrate 9-hydrate A liquid containing 4.76 g of the product [Al (NO 3 ) 3 .9H 2 O] and 63.45 g of sodium carbonate decahydrate [Na 2 CO 3 .10H 2 O] as the liquid B was prepared, respectively. A catalyst was obtained using the same method as in Example 1.
[0045]
[Example 6]
Palladium nitrate as A solution [Pd (NO 3) 2] solution 11.80g (Pd; 5wt% containing), copper nitrate trihydrate [Cu (NO 3) 2 · 3H 2 O] 13.02g, zinc nitrate 25.48 g of hexahydrate [Zn (NO 3 ) 2 .6H 2 O], 0.36 g of iron nitrate 9-hydrate [Fe (NO 3 ) 3 9H 2 O], aluminum nitrate 9-hydrate A liquid containing 4.73 g of the product [Al (NO 3 ) 3 .9H 2 O] and 57.30 g of sodium carbonate decahydrate [Na 2 CO 3 .10H 2 O] as the liquid B was prepared, respectively. A catalyst was obtained using the method.
[0046]
[Example 7]
Palladium nitrate as A solution [Pd (NO 3) 2] aqueous solution 2.34g (Pd; 5wt% containing), copper nitrate trihydrate [Cu (NO 3) 2 · 3H 2 O] 7.68g, zinc nitrate 25.02 g of hexahydrate [Zn (NO 3 ) 2 .6H 2 O], 14.54 g of iron nitrate 9-hydrate [Fe (NO 3 ) 3 .9H 2 O], aluminum nitrate 9-hydrate A solution containing 4.78 g of the product [Al (NO 3 ) 3 .9H 2 O] and 65.39 g of sodium carbonate decahydrate [Na 2 CO 3 .10H 2 O] as the B solution was prepared. A catalyst was obtained using the method.
[0047]
[Comparative Example 1]
Palladium nitrate as A solution [Pd (NO 3) 2] solution 11.72g (Pd; 5wt% containing), copper nitrate trihydrate [Cu (NO 3) 2 · 3H 2 O] 13.30g, zinc nitrate 25.39 g of hexahydrate [Zn (NO 3 ) 2 .6H 2 O], 4.65 g of aluminum nitrate nonahydrate [Al (NO 3 ) 3 .9H 2 O], sodium carbonate and dehydrated water as B solution Liquids each containing 57.04 g of the hydrate [Na 2 CO 3 .10H 2 O] were prepared, and a catalyst was obtained in the same manner as in Example 1.
[0048]
[Comparative Example 2]
Palladium nitrate as A solution [Pd (NO 3) 2] solution 52.37g (Pd; 5wt% containing), copper nitrate trihydrate [Cu (NO 3) 2 · 3H 2 O] 5.94g, zinc nitrate 24.97 g of hexahydrate [Zn (NO 3 ) 2 .6H 2 O], 4.57 g of aluminum nitrate 9-hydrate [Al (NO 3 ) 3 .9H 2 O], sodium carbonate as a B liquid Liquids each containing 54.48 g of the hydrate [Na 2 CO 3 .10H 2 O] were prepared, and a catalyst was obtained in the same manner as in Example 1.
[0049]
[Comparative Example 3]
15.42 g of copper nitrate trihydrate [Cu (NO 3 ) 2 .3H 2 O] as a liquid A, 25.51 g of zinc nitrate hexahydrate [Zn (NO 3 ) 2 .6H 2 O], nitric acid aluminum nonahydrate [Al (NO 3) 3 · 9H2O] 4.67g, B solution as sodium carbonate decahydrate [Na 2 CO 3 · 10H2O] 57.78g liquid containing the prepared respectively, performed A catalyst was obtained in the same manner as in Example 1.
[0050]
[Comparative Example 4]
11.70 g of copper nitrate trihydrate [Cu (NO 3 ) 2 .3H 2 O] as a liquid A, 25.84 g of zinc nitrate hexahydrate [Zn (NO 3 ) 2 .6H 2 O], nitric acid iron nonahydrate [Fe (NO 3) 3 · 9H 2 O] 6.53g, aluminum nitrate nonahydrate [Al (NO 3) 3 · 9H2O] 4.73g, sodium carbonate, ten as B solution Liquids containing 61.27 g of hydrate [Na 2 CO 3 .10H 2 O] were respectively prepared, and a catalyst was obtained in the same manner as in Example 1.
[0051]
[Comparative Example 5]
4.14 g of copper nitrate trihydrate [Cu (NO 3 ) 2 .3H 2 O] as a liquid A, 26.5 g of zinc nitrate hexahydrate [Zn (NO 3 ) 2 .6H 2 O], nitric acid iron nonahydrate [Fe (NO 3) 3 · 9H 2 O] 19.79g, aluminum nitrate nonahydrate [Al (NO 3) 3 · 9H2O] 4.85g, sodium carbonate, ten as B solution Liquids each containing 68.37 g of hydrate [Na 2 CO 3 .10H 2 O] were prepared, and a catalyst was obtained in the same manner as in Example 1.
[0052]
2) Activity test The activity of the catalyst prepared by the above method in the steam reforming reaction of methanol was measured. A 59.7% by weight aqueous methanol solution H 2 O / CH 3 OH = 1.2 (mol / mol) was used as a raw material, and air was blown so that O 2 / CH 3 OH = 0.1 (mol / mol). Introduced. The reaction was carried out at a reaction temperature of 250 ° C. and normal pressure at a supply rate of the aqueous methanol solution as the raw material of 60 (L-solv./L-cat·h) per unit catalyst amount. The components of the gas generated by the reaction were measured by gas chromatography. As an accelerated deterioration test, the methanol conversion rate for 48 hours after the start of the reaction was determined, and the selectivity of carbon monoxide was calculated from the component concentrations of carbon monoxide and carbon dioxide in the produced gas.
[0053]
Embedded image
Table 1 shows the composition of the prepared catalyst and the results of the activity test.
[0055]
[Table 1]
Table 1
【The invention's effect】
ADVANTAGE OF THE INVENTION According to this invention, it has a high catalytic activity and durability, and can provide the steam reforming catalyst of methanol with low selectivity of carbon monoxide. Further, according to the method for producing hydrogen of the present invention, hydrogen can be produced efficiently over a long period of time.
Claims (6)
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20180122233A (en) * | 2017-05-02 | 2018-11-12 | 국방과학연구소 | Methanol steam reforming catalysts, preparation method thereof, and methanol reforming apparatus comprising the same |
| JP2019193913A (en) * | 2018-05-01 | 2019-11-07 | 公立大学法人首都大学東京 | Hydrogen manufacturing catalyst |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH09221437A (en) * | 1996-02-15 | 1997-08-26 | Tsushosangyosho Kiso Sangyokyokucho | Production of ethanol |
| JP2003117396A (en) * | 2001-10-11 | 2003-04-22 | Mitsubishi Heavy Ind Ltd | Methanol reforming catalyst and method for producing the same |
| JP2003320254A (en) * | 2002-05-01 | 2003-11-11 | National Institute Of Advanced Industrial & Technology | Catalyst for water gas shift reaction and steam reforming reaction of methanol |
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2003
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH09221437A (en) * | 1996-02-15 | 1997-08-26 | Tsushosangyosho Kiso Sangyokyokucho | Production of ethanol |
| JP2003117396A (en) * | 2001-10-11 | 2003-04-22 | Mitsubishi Heavy Ind Ltd | Methanol reforming catalyst and method for producing the same |
| JP2003320254A (en) * | 2002-05-01 | 2003-11-11 | National Institute Of Advanced Industrial & Technology | Catalyst for water gas shift reaction and steam reforming reaction of methanol |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20180122233A (en) * | 2017-05-02 | 2018-11-12 | 국방과학연구소 | Methanol steam reforming catalysts, preparation method thereof, and methanol reforming apparatus comprising the same |
| KR102039045B1 (en) | 2017-05-02 | 2019-10-31 | 국방과학연구소 | Methanol steam reforming catalysts, preparation method thereof, and methanol reforming apparatus comprising the same |
| JP2019193913A (en) * | 2018-05-01 | 2019-11-07 | 公立大学法人首都大学東京 | Hydrogen manufacturing catalyst |
| JP7257019B2 (en) | 2018-05-01 | 2023-04-13 | 東京都公立大学法人 | Hydrogen production catalyst |
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