JP2004130216A - Desulfurizing agent for hydrocarbon-containing gas and method for producing hydrogen for fuel cell - Google Patents
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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
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Abstract
Description
【０００１】
【発明の属する技術】
本発明は、炭化水素含有ガス用脱硫剤及び燃料電池用水素の製造方法に関する。さらに詳しくは、本発明は、予め還元処理を施すことなく、燃料電池用燃料などとして用いられる炭化水素含有ガスの脱硫処理に使用し得る脱硫剤、及び該脱硫剤を用いて脱硫処理された炭化水素含有ガスを改質して、燃料電池用水素を効率よく、かつ経済的に有利に製造する方法に関するものである。
【０００２】
【従来の技術】
近年、環境問題から新エネルギー技術が脚光を浴びており、この新エネルギー技術の一つとして燃料電池が注目されている。燃料電池は、水素と酸素を電気化学的に反応させることにより、化学エネルギーを電気エネルギーに変換するものであって、エネルギーの利用効率が高いという特徴を有しており、民生用、産業用あるいは自動車用などとして、実用化研究が積極的になされている。
この燃料電池には、使用する電解質の種類に応じて、リン酸型、溶融炭酸塩型、固体酸化物型、固体高分子型などのタイプが知られている。一方、水素源としては、メタノール、メタンを主体とする液化天然ガス、この天然ガスを主成分とする都市ガス、天然ガスを原料とするジメチルエーテルなどの合成液体燃料、さらには石油系のＬＰＧ、ナフサ、灯油などの石油系炭化水素の使用が研究されている。
これらのガス状又は液状炭化水素を用いて水素を製造する場合、一般に、該炭化水素を改質触媒の存在下に部分酸化改質、オートサーマル改質又は水蒸気改質などで処理する方法が用いられている。
ＬＰＧや都市ガスなどを改質して燃料電池用水素を製造する場合、改質触媒の被毒を抑制するためには、ガス中の硫黄分を０．１ｐｐｍ以下に低減させることが要求される。また、プロピレンやブテンなどは、石油化学製品の原料として使用する場合、やはり触媒の被毒を防ぐためには、硫黄分を０．１ｐｐｍ以下に低減させることが要求される。
前記ＬＰＧ中には、硫黄化合物として、一般にメチルメルカプタンや硫化カルボニル（ＣＯＳ）などに加えて、付臭剤として添加されたジメチルサルファイド（ＤＭＳ）、ｔ−ブチルメルカプタン（ＴＢＭ）、メチルエチルサルファイド（ＭＥＳ）などが含まれている。このようなＬＰＧなどの燃料ガス中の硫黄分を吸着除去するための各種吸着剤、例えばゼオライト系や遷移金属系の吸着剤などが知られている。
【０００３】
しかしながら、ゼオライト系吸着剤は、吸着容量が不十分であるし、一方遷移金属系吸着剤においては、脱硫性能を発揮させるには、前処理として還元処理が必要であり、また、還元処理後に空気が混入した場合には、脱硫性能が低下するなどの問題があり、必ずしも十分に満足し得るものではなかった。
一方、疎水性ゼオライトにＡｇ、Ｃｕ、Ｚｎ、Ｆｅ、Ｃｏ、Ｎｉなどをイオン交換により担持させた脱硫剤（例えば特許文献１参照）や、Ｙ型ゼオライト、β型ゼオライト又はＸ型ゼオライトにＡｇ又はＣｕを担持した脱硫剤（例えば、特許文献２参照）が開示されている。しかしながら、これらの脱硫剤は、メルカプタン類やサルファイド類を室温において効率的に吸着除去し得るものの、硫化カルボニルをほとんど吸着しないことがわかった。
また、銅−亜鉛系脱硫剤が開示されている（例えば、特許文献３参照）。しかしながら、この脱硫剤においては、１５０℃以上の温度ではＣＯＳを含む各種硫黄化合物を吸着除去できるが、１００℃以下の低い温度では、硫黄化合物に対する吸着性能が低い。さらに、アルミナなどの多孔質担体に銅を担持した脱硫剤が開示されている（例えば、特許文献４参照）。この脱硫剤は１００℃以下の温度でも使用できるとしているが、その吸着性能については十分に満足し得るものではない。また、銅−亜鉛−酸化アルミニウム系の脱硫剤が開示されている（例えば、特許文献５参照）。しかしながら、この脱硫剤においては、前処理として水素による還元処理が必要となる。
【０００４】
【特許文献１】
特開２００１−２８６７５３号公報
【特許文献２】
特開２００１−３０５１２３号公報
【特許文献３】
特開平２−３０２４９６号公報（第２頁）
【特許文献４】
特開２００１−１２３１８８号公報（第３頁）
【特許文献５】
特開平１１−１３９８０３号公報
【０００５】
【発明が解決しようとする課題】
本発明は、このような状況下で、予め還元処理を施すことなく、炭化水素含有ガスの脱硫処理に使用することができ、かつ該炭化水素含有ガス中の硫黄分を、室温においても低濃度まで効率よく除去し得る炭化水素含有ガス用脱硫剤、及び上記脱硫剤を用いて脱硫処理した炭化水素含有ガスを改質して、燃料電池用水素を効率よく、経済的に有利に製造する方法を提供するものである。
【０００６】
【課題を解決するための手段】
本発明者らは、前記目的を達成するために鋭意研究を重ねた結果、担体に、酸化ニッケル、又は酸化ニッケルと酸化銅を担持してなる脱硫剤が、炭化水素含有ガス用脱硫剤として、その目的に適合し得ること、そして、この脱硫剤を用いて脱硫処理した炭化水素含有ガスに、部分酸化改質、オートサーマル改質、水蒸気改質などの改質処理を施すことにより、効率よく、経済的に有利に燃料電池用水素が得られることを見出した。本発明は、かかる知見に基づいて完成したものである。
【０００７】
すなわち、本発明は、
（１）担体上に酸化ニッケル、又は酸化ニッケルと酸化銅を担持してなる脱硫剤であって、予め還元処理を施すことなく、炭化水素含有ガスの脱硫処理に使用することを特徴とする炭化水素含有ガス用脱硫剤、
（２）脱硫剤全量に基づき、酸化ニッケル含有量が５〜９０質量％、酸化銅含有量が０〜８５質量％及び酸化ニッケルと酸化銅の合計含有量が６０〜９０質量％である上記（１）の炭化水素含有ガス用脱硫剤、
（３）担体が、シリカ、アルミナ、シリカ−アルミナ、チタニア、ジルコニア、マグネシア、珪藻土、白土、粘土及び酸化亜鉛の中から選ばれる少なくとも一種の無機多孔質担体である上記（１）又は（２）の炭化水素含有ガス用脱硫剤、
（４）炭化水素含有ガスが、ＬＰＧ、天然ガス、都市ガス又はジメチルエーテルである上記（１）、（２）又は（３）の炭化水素含有ガス用脱硫剤、
（５）担体上に酸化ニッケル、又は酸化ニッケルと酸化銅を担持してなる脱硫剤を、これに予め還元処理を施すことなく用いて炭化水素含有ガスの脱硫処理を行うことを特徴とする炭化水素含有ガスの脱硫方法、
（６）炭化水素含有ガスが、ＬＰＧ、天然ガス、都市ガス又はジメチルエーテルである上記（５）の脱硫方法。
（７）−２０〜１００℃の温度で行う上記（５）又は（６）の脱硫方法、
（８）上記（１）〜（４）のいずれかの脱硫剤を用いて、炭化水素含有ガスを脱硫処理したのち、改質することを特徴とする燃料電池用水素の製造方法、
（９）改質が、部分酸化改質、オートサーマル改質又は水蒸気改質である上記（８）の燃料電池用水素の製造方法、
（１０）部分酸化改質触媒、オートサーマル改質触媒又は水蒸気改質触媒が、ルテニウム系又はニッケル系触媒である上記（９）の燃料電池用水素の製造方法、及び
（１１）触媒に用いられる担体が、酸化マンガン、酸化セリウム及びジルコニアの中から選ばれる少なくとも一種を含むものである上記（１０）の燃料電池用水素の製造方法、
を提供するものである。
【０００８】
【発明の実施の形態】
本発明の炭化水素含有ガス用脱硫剤は、担体上に酸化ニッケル、又は酸化ニッケルと酸化銅を担持してなり、かつ予め還元処理を施すことなく、炭化水素含有ガスの脱硫処理に用いられる。
当該脱硫剤における担体としては、無機多孔質担体が好ましく、例えばシリカ、アルミナ、シリカ−アルミナ、チタニア、ジルコニア、マグネシア、珪藻土、白土、粘土及び酸化亜鉛などを挙げることができる。これらは単独で用いてもよく、二種以上を組み合わせて用いてもよい。これらの中で、特にシリカ−アルミナが好適である。
【０００９】
これらの担体上に担持される酸化ニッケルの担持量は、脱硫剤全量に基づき、５〜９０質量％の範囲が好ましい。この量が５質量％未満では十分な脱硫性能が発揮されないおそれがあり、一方９０質量％を超えると担体の割合が少なくなって、脱硫剤の機械的強度や脱硫性能が低下する原因となる。脱硫性能及び機械的強度などを考慮すると、この酸化ニッケルのより好ましい担持量は、１０〜８５質量％の範囲である。また、酸化銅の担持量は、脱硫剤全量に基づき、０〜８５質量％の範囲が好ましい。この量が８５質量％を超えると脱硫剤の機械的強度や脱硫性能が低下する場合がある。該酸化銅のより好ましい担持量は、０〜８０質量％の範囲である。また、酸化ニッケルと酸化銅の合計担持量は、脱硫性能及び機械的強度のバランスなどの点から、脱硫剤全量に基づき、６０〜９０質量％の範囲が好ましく、特に６５〜８５質量％の範囲が好ましい。
【００１０】
該担体に酸化ニッケル、又は酸化ニッケルと酸化銅を担持させる方法については特に制限はなく、含浸法、共沈法、混練法などの公知の任意の方法を採用することができる。本発明の好ましい脱硫剤である、シリカ−アルミナ担体上に酸化ニッケル、又は酸化ニッケルと酸化銅を担持させてなる脱硫剤は、例えば以下に示すような共沈法によって製造することができる。
この共沈法においては、まずニッケル源及びアルミニウム源、必要に応じ銅源を含む酸性水溶液又は酸性水性分散液と、ケイ素源及び無機塩基を含む塩基性水溶液を調製する。前者の酸性水溶液又は酸性水分散液に用いられるニッケル源としては、例えば塩化ニッケル、硝酸ニッケル、硫酸ニッケル、酢酸ニッケル及びこれらの水和物などが挙げられる。また銅源としては、例えば塩化銅、硝酸銅、硫酸銅、酢酸銅及びこれらの水和物が挙げられる。更にアルミニウム源としては、硝酸アルミニウム、擬ベーマイト、ベーマイトアルミナ、バイヤライト、ジブサイトなどのアルミナ水和物や、γ−アルミナなどが挙げられる。
【００１１】
一方、塩基性水溶液に用いられるケイ素源としては、アルカリ水溶液に可溶であって、焼成によりシリカになるものであればよく、特に制限されず、例えばオルトケイ酸、メタケイ酸及びそれらのナトリウム塩やカリウム塩、水ガラスなどが挙げられる。また、無機塩基としては、アルカリ金属の炭酸塩や水酸化物などが挙げられる。
次に、このようにして調製した酸性の水溶液又は水分散液と塩基性水溶液を、それぞれ５０〜９０℃程度に加温して、両者を混合し、さらに５０〜９０℃程度の温度に保持して反応を完結させる。
次に、生成した固形物を充分に洗浄したのち固液分離するか、あるいは生成した固形物を固液分離したのち充分に洗浄し、次いで、この固形物を公知の方法により８０〜１５０℃程度の温度で乾燥処理する。このようにして得られた乾燥処理物を、好ましくは２００〜４００℃の範囲の温度において焼成することにより、シリカ−アルミナ担体上に酸化ニッケル、又は酸化ニッケルと酸化銅が担持された脱硫剤が得られる。
【００１２】
本発明の脱硫方法は、上記脱硫剤を、これに予め還元処理を施すことなく用いて炭化水素含有ガスの脱硫処理を行うものである。本発明の脱硫剤は、予め還元処理することなく、炭化水素含有ガスの脱硫処理に用いられる。上記炭化水素含有ガスとしては、例えばＬＰＧ、天然ガス、ジメチルエーテル、都市ガス、あるいはエタン、エチレン、プロパン、プロピレン、ブタンなどの中から選ばれる少なくとも一種を含むガスなどが挙げられるが、これらの中で市場での流通の面でＬＰＧ、天然ガス、都市ガス又はジメチルエーテルの脱硫処理に、本発明の脱硫剤を用いるのが好ましい。
本発明の脱硫剤が適用される炭化水素含有ガス中の硫黄化合物の濃度としては、０．００１〜１０，０００容量ｐｐｍが好ましく、特に０．１〜１００容量ｐｐｍが好ましい。また、脱硫条件としては、通常温度は−２０〜１００℃、好ましくは−１０〜８０℃の範囲で選ばれ、ＧＨＳＶ（ガス時空間速度）は１００〜１００，０００ｈ−１の範囲で選ばれる。
【００１３】
本発明の脱硫剤は、以下に示す効果を奏する。
（１）炭化水素含有ガス中の硫黄分を、室温においても低濃度まで効率よく除去することができる。
（２）予め還元処理を施すことなく、炭化水素含有ガスの脱硫処理に使用し得るので、脱硫コストの低減を図ることができる。
（３）燃料電池システムに組み込んだ場合、脱硫剤を交換するたびに、還元処理を施す必要がなく、例えば予め別の場所で還元処理を行った脱硫剤を交換する際にも、空気の流入を気にすることがないため、利便性が高い。また、仮に停止時に空気が混入しても、還元処理した遷移金属系脱硫剤のような、急激な発熱や酸化による脱硫剤の劣化のおそれがない。
【００１４】
次に、本発明の燃料電池用水素の製造方法においては、前述の本発明の脱硫剤を用いて、炭化水素含有ガス中の硫黄化合物を脱硫処理したのち、脱硫処理炭化水素含有ガスを改質することにより、水素を製造する。
この際、改質方法として、部分酸化改質、オートサーマル改質、水蒸気改質などの方法を用いることができる。この改質方法においては、脱硫処理炭化水素含有ガス中の硫黄化合物の濃度は、各改質触媒の寿命の点から、０．１容量ｐｐｍ以下が好ましく、特に０．０５容量ｐｐｍ以下が好ましい。
前記部分酸化改質は、炭化水素の部分酸化反応により、水素を製造する方法であって、部分酸化改質触媒の存在下、通常、反応圧力常圧〜５ＭＰａ、反応温度４００〜１１００℃、ＧＨＳＶ１０００〜１００，０００ｈ−１、酸素（Ｏ２）／炭素比０．２〜０．８の条件で改質反応が行われる。
【００１５】
また、オートサーマル改質は、部分酸化改質と水蒸気改質とを組み合わせた方法であって、オートサーマル改質触媒の存在下、通常、反応圧力常圧〜５ＭＰａ、反応温度４００〜１１００℃、酸素（Ｏ２）／炭素比０．１〜１、スチーム／炭素比０．１〜１０、ＧＨＳＶ１０００〜１００，０００ｈ−１の条件で改質反応が行われる。
さらに、水蒸気改質は、炭化水素に水蒸気を接触させて、水素を製造する方法であって、水蒸気改質触媒の存在下、通常、反応圧力常圧〜３ＭＰａ、反応温度２００〜９００℃、スチーム／炭素比１．５〜１０、ＧＨＳＶ１０００〜１００，０００ｈ−１の条件で改質反応が行われる。
【００１６】
本発明においては、前記の部分酸化改質触媒、オートサーマル改質触媒、水蒸気改質触媒としては、従来公知の各触媒の中から適宜選択して用いることができるが、特にルテニウム系及びニッケル系触媒が好適である。また、これらの触媒の担体としては、酸化マンガン、酸化セリウム及びジルコニアの中から選ばれる少なくとも一種を含む担体を好ましく挙げることができる。該担体は、これらの金属酸化物のみからなる担体であってもよく、アルミナなどの他の耐火性多孔質無機酸化物に、上記金属酸化物を含有させてなる担体であってもよい。
【００１７】
【実施例】
次に、本発明を実施例により、さらに詳細に説明するが、本発明は、これらの例によってなんら限定されるものではない。
実施例１
硫酸ニッケル・６水和物［和光純薬（株）製、特級］３６０．１ｇ及び硫酸銅・５水和物［和光純薬（株）製、特級］８５．２ｇを８０℃に加温したイオン交換水４Ｌに溶解し、これに擬ベーマイト［触媒化成工業（株）製、「Ｃ−ＡＰ」、Ａｌ２Ｏ３として６７質量％］７．２ｇを混合した（調製液Ａ）。
一方、８０℃に加温したイオン交換水４Ｌに炭酸ナトリウム３００．０ｇを溶解し、これに水ガラス［日本化学工業（株）製、「Ｊ−１号」、Ｓｉ濃度２９質量％］９３．６ｇを加えた（調製液Ｂ）。
次に、前記調製液Ａと調製液Ｂをそれぞれ温度８０℃に保ちながら混合し、１時間攪拌したのち、イオン交換水６０Ｌを用いて沈殿ケーキを洗浄、ろ取し、送風乾燥機にて１２０℃で１２時間乾燥した。その後、３５０℃で３時間焼成処理して、ＣｕＯ１６質量％、ＮｉＯ６４質量％及びＳｉＯ２・Ａｌ２Ｏ３２０質量％を含む脱硫剤Ａ［ＣｕＯ（１６）ＮｉＯ（６４）／ＳｉＡｌ（２０）と示す。］を得た。
【００１８】
実施例２
実施例１において、硫酸ニッケル・６水和物４２７．６ｇ及び硫酸銅・５水和物２１．３ｇを用いた以外は、実施例１と同様にして、ＣｕＯ４質量％、ＮｉＯ７６質量％及びＳｉＯ２・Ａｌ２Ｏ３２０質量％を含む脱硫剤Ｂ［ＣｕＯ（４）ＮｉＯ（７６）／ＳｉＡｌ（２０）と示す。］を得た。
実施例３
実施例１において、硫酸ニッケル・６水和物２２５．１ｇ及び硫酸銅・５水和物２１３．０ｇを用いた以外は、実施例１と同様にして、ＣｕＯ４０質量％、ＮｉＯ４０質量％及びＳｉＯ２・Ａｌ２Ｏ３２０質量％を含む脱硫剤Ｃ［ＣｕＯ（４０）ＮｉＯ（４０）／ＳｉＡｌ（２０）と示す。］を得た。
【００１９】
実施例４
実施例１において、硫酸ニッケル・６水和物４４４．５ｇ及び硫酸銅・５水和物５．３ｇを用いた以外は、実施例１と同様にして、ＣｕＯ１質量％、ＮｉＯ７９質量％及びＳｉＯ２・Ａｌ２Ｏ３２０質量％を含む脱硫剤Ｄ［ＣｕＯ（１）ＮｉＯ（７９）／ＳｉＡｌ（２０）と示す。］を得た。
実施例５
実施例１において、硫酸ニッケル・６水和物４５０．１ｇを用い、かつ硫酸銅・５水和物を用いることなしに、実施例１と同様にして、ＮｉＯ８０質量％及びＳｉＯ２・Ａｌ２Ｏ３２０質量％を含む脱硫剤Ｅ［ＮｉＯ（８０）／ＳｉＡｌ（２０）と示す。］を得た。
【００２０】
比較例１
硫酸銅・５水和物［和光純薬（株）製、特級］４２６．０ｇを８０℃に加温したイオン交換水４Ｌに溶解し、これに擬ベーマイト［触媒化成工業（株）製、「Ｃ−ＡＰ」、Ａｌ２Ｏ３として６７質量％］７．２ｇを混合した（調製液Ａ）。
一方、８０℃に加温したイオン交換水４Ｌに炭酸ナトリウム３００．０ｇを溶解し、これに水ガラス［日本化学工業（株）製、「Ｊ−１号」、Ｓｉ濃度２９質量％］９３．６ｇを加えた（調製液Ｂ）。
次に、前記調製液Ａと調製液Ｂをそれぞれ温度８０℃に保ちながら混合し、１時間攪拌したのち、イオン交換水６０Ｌを用いて沈殿ケーキを洗浄、ろ取し、送風乾燥機にて１２０℃で１２時間乾燥した。その後、３５０℃で３時間焼成処理して、ＣｕＯ８０質量％、及びＳｉＯ２・Ａｌ２Ｏ３２０質量％を含む脱硫剤Ｆ［ＣｕＯ（８０）／ＳｉＡｌ（２０）と示す。］を得た。
【００２１】
比較例２
ズードケミー触媒社製の脱硫剤「Ｇ１３２Ｂ」［ＣｕＯ３２質量％及びＺｎＯ６８質量％を含む。ＣｕＯ（３２）／ＺｎＯ（６８）と示す。］を比較例２の触媒として用いた。
比較例３
ズードケミー触媒社製の脱硫剤「Ｔ２５５２」［Ａｇ５質量％及びＡｌ２Ｏ３９５質量％を含む。Ａｇ（５）／Ａｌ２Ｏ３（９５）と示す。］を比較例３の触媒として用いた。
【００２２】
比較例４
脱硫剤Ａを反応管に１．０ｃｍ３充填し、１００％水素ガスを１００ｃｍ３／ｍｉｎで流通させ、３００℃で３時間還元処理したのち、反応管上下部に設置したバルブを開放し、空気が反応管内に入るようにして、３時間放置したものを、比較例４の触媒として用いた。
試験例１
実施例１〜５及び比較例１〜４の各脱硫剤を０．５〜１ｍｍに成型し、脱硫剤１ｃｍ３を内径９ｍｍの脱硫管に充填した。脱硫剤温度を２０℃とし、ＣＯＳ、ジメチルサルファイド（ＤＭＳ）、ｔ−ブチルメルカブタン（ＴＢＭ）及びジメチルジサルファイド（ＤＭＤＳ）を各１０ｖｏｌｐｐｍ（合計４０ｖｏｌｐｐｍ）含むプロパンガスを、常圧、ＧＨＳＶ（ガス時空間速度）３０，０００ｈ−１の条件で流通させた。
脱硫管出口ガスの各硫黄化合物濃度をＳＣＤ（化学発光イオウ検出器：ＳｕｌｆｕｒＣｈｅｍｉｌｕｍｉｎｅｓｃｅｎｃｅ Ｄｅｔｅｃｔｏｒ）ガスクロマトグラフィーにより、１時間毎に測定した。第１表に各硫黄化合物濃度が０．１ｖｏｌｐｐｍを超える時間を示した。
比較例５
脱硫剤Ａを０．５〜１ｍｍに成型し、脱硫剤１ｃｍ３を内径９ｍｍの脱硫管に充填した後、比較例４と同様に３００℃で３時間還元処理した。その後、還元処理した脱硫剤を空気に触れさせることなく試験例１と同様に試験した。結果を第１表に示す。
【００２３】
【表１】
第１表から明らかなように、本発明の脱硫剤（実施例１〜５）は、未還元処理で高性能を示すことが分かる。
また、実施例１の脱硫剤を還元処理した後に空気に接触させることで、大幅な性能低下が見られた（比較例４）。[0001]
[Technology to which the Invention belongs]
The present invention relates to a desulfurizing agent for a hydrocarbon-containing gas and a method for producing hydrogen for a fuel cell. More specifically, the present invention relates to a desulfurizing agent that can be used for desulfurizing a hydrocarbon-containing gas used as a fuel for a fuel cell or the like without performing a reducing process in advance, and a desulfurizing process performed using the desulfurizing agent. The present invention relates to a method for efficiently and economically producing hydrogen for fuel cells by reforming a hydrogen-containing gas.
[0002]
[Prior art]
In recent years, new energy technologies have been spotlighted due to environmental problems, and fuel cells have attracted attention as one of the new energy technologies. Fuel cells convert chemical energy into electric energy by electrochemically reacting hydrogen and oxygen, and have the characteristic of high energy use efficiency. Practical research is being actively conducted for use in automobiles and the like.
Known types of fuel cells include a phosphoric acid type, a molten carbonate type, a solid oxide type, and a solid polymer type, depending on the type of electrolyte used. On the other hand, as a hydrogen source, liquefied natural gas mainly composed of methanol and methane, city gas mainly composed of natural gas, synthetic liquid fuel such as dimethyl ether using natural gas as a raw material, petroleum-based LPG and naphtha The use of petroleum hydrocarbons such as kerosene has been studied.
When producing hydrogen using these gaseous or liquid hydrocarbons, generally, a method of treating the hydrocarbons by partial oxidation reforming, autothermal reforming or steam reforming in the presence of a reforming catalyst is used. Have been.
When producing hydrogen for fuel cells by reforming LPG or city gas, it is required to reduce the sulfur content in the gas to 0.1 ppm or less in order to suppress the poisoning of the reforming catalyst. . Further, when propylene, butene, or the like is used as a raw material for petrochemical products, it is necessary to reduce the sulfur content to 0.1 ppm or less in order to prevent poisoning of the catalyst.
In the LPG, dimethyl sulfide (DMS), t-butyl mercaptan (TBM), and methyl ethyl sulfide (MES) added as odorants, in addition to sulfur compounds, such as methyl mercaptan and carbonyl sulfide (COS), are generally added. ) Etc. are included. Various adsorbents for adsorbing and removing sulfur in fuel gas such as LPG, for example, zeolite-based and transition metal-based adsorbents are known.
[0003]
However, zeolite-based adsorbents have insufficient adsorption capacity, while transition metal-based adsorbents require a reduction treatment as a pretreatment in order to exhibit desulfurization performance, and air after the reduction treatment. In the case where is mixed, there is a problem such as a decrease in desulfurization performance, and it was not always satisfactory.
On the other hand, a desulfurizing agent in which Ag, Cu, Zn, Fe, Co, Ni, etc. are supported on a hydrophobic zeolite by ion exchange (for example, see Patent Literature 1), or a Y-type zeolite, a β-type zeolite, or an X-type zeolite with Ag or A desulfurizing agent supporting Cu (for example, see Patent Document 2) is disclosed. However, it has been found that these desulfurizing agents can efficiently adsorb and remove mercaptans and sulfides at room temperature, but hardly adsorb carbonyl sulfide.
Further, a copper-zinc-based desulfurizing agent is disclosed (for example, see Patent Document 3). However, this desulfurizing agent can adsorb and remove various sulfur compounds including COS at a temperature of 150 ° C. or higher, but has low adsorption performance for sulfur compounds at a low temperature of 100 ° C. or lower. Furthermore, a desulfurizing agent in which copper is supported on a porous carrier such as alumina is disclosed (for example, see Patent Document 4). Although it is stated that this desulfurizing agent can be used at a temperature of 100 ° C. or less, its adsorption performance is not sufficiently satisfactory. Further, a copper-zinc-aluminum oxide-based desulfurizing agent is disclosed (for example, see Patent Document 5). However, this desulfurizing agent requires a reduction treatment with hydrogen as a pretreatment.
[0004]
[Patent Document 1]
Japanese Patent Application Laid-Open No. 2001-286753 [Patent Document 2]
JP 2001-305123 A [Patent Document 3]
JP-A-2-302496 (page 2)
[Patent Document 4]
JP 2001-123188 A (page 3)
[Patent Document 5]
JP-A-11-139803
[Problems to be solved by the invention]
Under such circumstances, the present invention can be used for desulfurizing a hydrocarbon-containing gas without performing a reduction treatment in advance, and the sulfur content in the hydrocarbon-containing gas can be reduced even at room temperature. And a method for reforming a hydrocarbon-containing gas desulfurized using the desulfurizing agent to efficiently and economically produce hydrogen for fuel cells. Is provided.
[0006]
[Means for Solving the Problems]
The present inventors have conducted intensive studies in order to achieve the above object, and as a result, a carrier, a nickel oxide, or a desulfurizing agent carrying nickel oxide and copper oxide, as a desulfurizing agent for hydrocarbon-containing gas, Efficient by being able to meet the purpose, and by subjecting the hydrocarbon-containing gas desulfurized using this desulfurizing agent to reforming treatment such as partial oxidation reforming, autothermal reforming, and steam reforming, It has been found that hydrogen for fuel cells can be obtained economically advantageously. The present invention has been completed based on such findings.
[0007]
That is, the present invention
(1) A desulfurizing agent comprising nickel oxide or nickel oxide and copper oxide supported on a carrier, wherein the desulfurizing agent is used for desulfurizing a hydrocarbon-containing gas without performing a reduction treatment in advance. Desulfurizing agent for hydrogen-containing gas,
(2) Based on the total amount of the desulfurizing agent, the nickel oxide content is 5 to 90% by mass, the copper oxide content is 0 to 85% by mass, and the total content of nickel oxide and copper oxide is 60 to 90% by mass ( 1) desulfurizing agent for hydrocarbon-containing gas,
(3) The above (1) or (2), wherein the carrier is at least one inorganic porous carrier selected from silica, alumina, silica-alumina, titania, zirconia, magnesia, diatomaceous earth, clay, clay and zinc oxide. Desulfurizing agent for hydrocarbon-containing gas,
(4) The desulfurizing agent for hydrocarbon-containing gas according to (1), (2) or (3), wherein the hydrocarbon-containing gas is LPG, natural gas, city gas, or dimethyl ether.
(5) A desulfurization treatment of a hydrocarbon-containing gas using a desulfurization agent comprising nickel oxide or nickel oxide and copper oxide supported on a carrier without performing a reduction treatment in advance. Hydrogen-containing gas desulfurization method,
(6) The desulfurization method according to (5), wherein the hydrocarbon-containing gas is LPG, natural gas, city gas, or dimethyl ether.
(7) The desulfurization method according to the above (5) or (6), which is performed at a temperature of -20 to 100 ° C.
(8) A method for producing hydrogen for a fuel cell, comprising subjecting a hydrocarbon-containing gas to desulfurization treatment using any of the desulfurizing agents (1) to (4) above, followed by reforming.
(9) The method for producing hydrogen for a fuel cell according to (8) above, wherein the reforming is partial oxidation reforming, autothermal reforming, or steam reforming.
(10) The method for producing hydrogen for a fuel cell according to the above (9), wherein the partial oxidation reforming catalyst, the autothermal reforming catalyst or the steam reforming catalyst is a ruthenium-based or nickel-based catalyst, and (11) a catalyst. The method for producing hydrogen for a fuel cell according to the above (10), wherein the carrier contains at least one selected from manganese oxide, cerium oxide and zirconia;
Is provided.
[0008]
BEST MODE FOR CARRYING OUT THE INVENTION
The desulfurizing agent for a hydrocarbon-containing gas of the present invention comprises nickel oxide or nickel oxide and copper oxide supported on a carrier, and is used for desulfurizing a hydrocarbon-containing gas without performing a reduction treatment in advance.
As the carrier in the desulfurizing agent, an inorganic porous carrier is preferable, and examples thereof include silica, alumina, silica-alumina, titania, zirconia, magnesia, diatomaceous earth, clay, clay and zinc oxide. These may be used alone or in combination of two or more. Of these, silica-alumina is particularly preferred.
[0009]
The amount of nickel oxide supported on these carriers is preferably in the range of 5 to 90% by mass based on the total amount of the desulfurizing agent. If the amount is less than 5% by mass, sufficient desulfurization performance may not be exhibited. On the other hand, if it exceeds 90% by mass, the ratio of the carrier is reduced, and the mechanical strength and desulfurization performance of the desulfurizing agent are reduced. In consideration of desulfurization performance, mechanical strength, and the like, the more preferable amount of nickel oxide to be supported is in the range of 10 to 85% by mass. Further, the supported amount of copper oxide is preferably in the range of 0 to 85% by mass based on the total amount of the desulfurizing agent. If this amount exceeds 85% by mass, the mechanical strength and desulfurization performance of the desulfurizing agent may decrease. The more preferable loading amount of the copper oxide is in the range of 0 to 80% by mass. In addition, the total loading of nickel oxide and copper oxide is preferably in the range of 60 to 90% by mass, and more preferably in the range of 65 to 85% by mass, based on the total amount of the desulfurizing agent from the viewpoint of the balance between the desulfurization performance and the mechanical strength. Is preferred.
[0010]
The method of supporting nickel oxide or nickel oxide and copper oxide on the carrier is not particularly limited, and any known method such as an impregnation method, a coprecipitation method, and a kneading method can be employed. The desulfurizing agent, which is a preferred desulfurizing agent of the present invention, in which nickel oxide or nickel oxide and copper oxide are supported on a silica-alumina carrier, can be produced, for example, by a coprecipitation method as described below.
In this coprecipitation method, first, an acidic aqueous solution or acidic aqueous dispersion containing a nickel source and an aluminum source, and if necessary, a copper source, and a basic aqueous solution containing a silicon source and an inorganic base are prepared. Examples of the nickel source used in the former acidic aqueous solution or acidic aqueous dispersion include nickel chloride, nickel nitrate, nickel sulfate, nickel acetate and hydrates thereof. Examples of the copper source include copper chloride, copper nitrate, copper sulfate, copper acetate and hydrates thereof. Further, examples of the aluminum source include aluminum hydrates such as aluminum nitrate, pseudoboehmite, boehmite alumina, bayerite, and gibbsite, and γ-alumina.
[0011]
On the other hand, the silicon source used in the basic aqueous solution is not particularly limited as long as it is soluble in an alkaline aqueous solution and can be converted into silica by firing, and examples thereof include orthosilicic acid, metasilicic acid, and sodium salts thereof. Potassium salts, water glass and the like can be mentioned. Examples of the inorganic base include alkali metal carbonates and hydroxides.
Next, the acidic aqueous solution or aqueous dispersion thus prepared and the basic aqueous solution are each heated to about 50 to 90 ° C., mixed with each other, and further maintained at a temperature of about 50 to 90 ° C. To complete the reaction.
Next, the produced solid is sufficiently washed and then subjected to solid-liquid separation, or the produced solid is subjected to solid-liquid separation and sufficiently washed, and then the solid is subjected to a known method at about 80 to 150 ° C. Drying at the temperature of By drying the thus obtained dried product, preferably at a temperature in the range of 200 to 400 ° C., a desulfurizing agent in which nickel oxide or nickel oxide and copper oxide are supported on a silica-alumina carrier is obtained. can get.
[0012]
In the desulfurization method of the present invention, a desulfurization treatment of a hydrocarbon-containing gas is performed using the desulfurization agent without subjecting the desulfurization agent to a reduction treatment in advance. The desulfurizing agent of the present invention is used for desulfurizing a hydrocarbon-containing gas without prior reduction. Examples of the hydrocarbon-containing gas include LPG, natural gas, dimethyl ether, city gas, and a gas containing at least one selected from ethane, ethylene, propane, propylene, butane, and the like. From the viewpoint of market distribution, it is preferable to use the desulfurizing agent of the present invention for desulfurizing LPG, natural gas, city gas, or dimethyl ether.
The concentration of the sulfur compound in the hydrocarbon-containing gas to which the desulfurizing agent of the present invention is applied is preferably 0.001 to 10,000 ppm by volume, and particularly preferably 0.1 to 100 ppm by volume. As desulfurization conditions, the temperature is usually selected in the range of -20 to 100C, preferably -10 to 80C, and the GHSV (gas hourly space velocity) is selected in the range of 100 to 100,000h- 1 .
[0013]
The desulfurizing agent of the present invention has the following effects.
(1) The sulfur content in the hydrocarbon-containing gas can be efficiently removed to a low concentration even at room temperature.
(2) Since the gas can be used for desulfurizing a hydrocarbon-containing gas without performing a reduction treatment in advance, the cost of desulfurization can be reduced.
(3) When incorporated in a fuel cell system, it is not necessary to perform a reduction process each time the desulfurizing agent is replaced. For example, when replacing a desulfurizing agent that has been subjected to a reduction process in another place, the inflow of air It is convenient because you don't have to worry about it. Even if air is mixed in at the time of shutdown, there is no fear that the desulfurizing agent is deteriorated due to rapid heat generation or oxidation, such as a transition metal desulfurizing agent subjected to a reduction treatment.
[0014]
Next, in the method for producing hydrogen for a fuel cell of the present invention, after the sulfur compound in the hydrocarbon-containing gas is desulfurized using the desulfurizing agent of the present invention, the desulfurized hydrocarbon-containing gas is reformed. By doing so, hydrogen is produced.
At this time, a method such as partial oxidation reforming, autothermal reforming, and steam reforming can be used as the reforming method. In this reforming method, the concentration of the sulfur compound in the desulfurized hydrocarbon-containing gas is preferably 0.1 ppm by volume or less, particularly preferably 0.05 ppm by volume or less, from the viewpoint of the life of each reforming catalyst.
The partial oxidation reforming is a method for producing hydrogen by a partial oxidation reaction of hydrocarbons. In the presence of a partial oxidation reforming catalyst, usually, the reaction pressure is normal pressure to 5 MPa, the reaction temperature is 400 to 1100 ° C., and the GHSV1000 The reforming reaction is performed under the conditions of 100,000 h −1 and an oxygen (O 2 ) / carbon ratio of 0.2 to 0.8.
[0015]
Autothermal reforming is a method in which partial oxidation reforming and steam reforming are combined, and usually in the presence of an autothermal reforming catalyst, usually at a reaction pressure of normal pressure to 5 MPa, a reaction temperature of 400 to 1100 ° C, The reforming reaction is performed under the conditions of an oxygen (O 2 ) / carbon ratio of 0.1 to 1, a steam / carbon ratio of 0.1 to 10, and a GHSV of 1000 to 100,000 h −1 .
Further, steam reforming is a method for producing hydrogen by bringing steam into contact with a hydrocarbon, and usually in the presence of a steam reforming catalyst, at a reaction pressure of normal pressure to 3 MPa, a reaction temperature of 200 to 900 ° C., and steam. The reforming reaction is carried out under the conditions of a / carbon ratio of 1.5 to 10 and a GHSV of 1000 to 100,000 h -1 .
[0016]
In the present invention, the partial oxidation reforming catalyst, the autothermal reforming catalyst, and the steam reforming catalyst can be appropriately selected from conventionally known catalysts. Particularly, ruthenium-based and nickel-based catalysts can be used. Catalysts are preferred. Further, as a carrier of these catalysts, a carrier containing at least one selected from manganese oxide, cerium oxide and zirconia can be preferably exemplified. The carrier may be a carrier composed of only these metal oxides, or a carrier in which the above-mentioned metal oxide is contained in another refractory porous inorganic oxide such as alumina.
[0017]
【Example】
Next, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples.
Example 1
360.1 g of nickel sulfate hexahydrate [manufactured by Wako Pure Chemical Industries, Ltd.] and 85.2 g of copper sulfate pentahydrate [manufactured by Wako Pure Chemical Industries, Ltd.] were heated to 80 ° C. was dissolved in deionized water 4L, which pseudoboehmite [catalysts & Chemicals Industries Co., Ltd., "C-AP", 67 wt% as Al 2 O 3] were mixed 7.2 g (preparation a).
On the other hand, 300.0 g of sodium carbonate was dissolved in 4 L of ion-exchanged water heated to 80 ° C., and water glass [“J-1”, manufactured by Nippon Chemical Industry Co., Ltd., Si concentration 29% by mass] 6 g was added (Preparation solution B).
Next, the prepared liquid A and the prepared liquid B were mixed while keeping the temperature at 80 ° C., respectively, and stirred for 1 hour. Then, the precipitated cake was washed and filtered with 60 L of ion-exchanged water, and dried with a blow dryer. Dry at 12 ° C. for 12 hours. Then, it is calcined at 350 ° C. for 3 hours to obtain a desulfurizing agent A [CuO (16) NiO (64) / SiAl (20) containing 16% by mass of CuO, 64% by mass of NiO and 20% by mass of SiO 2 .Al 2 O 3. Show. ] Was obtained.
[0018]
Example 2
In the same manner as in Example 1, except that 427.6 g of nickel sulfate hexahydrate and 21.3 g of copper sulfate pentahydrate were used, 4% by mass of CuO, 76% by mass of NiO, and SiO 2 A desulfurizing agent B containing 20% by mass of Al 2 O 3 [shown as CuO (4) NiO (76) / SiAl (20). ] Was obtained.
Example 3
In the same manner as in Example 1, except that 225.1 g of nickel sulfate hexahydrate and 213.0 g of copper sulfate pentahydrate were used, 40 mass% of CuO, 40 mass% of NiO and SiO 2 were used. A desulfurizing agent C containing 20% by mass of Al 2 O 3 [shown as CuO (40) NiO (40) / SiAl (20). ] Was obtained.
[0019]
Example 4
In the same manner as in Example 1, except that 444.5 g of nickel sulfate hexahydrate and 5.3 g of copper sulfate pentahydrate were used, 1% by mass of CuO, 79% by mass of NiO, and SiO 2 A desulfurizing agent D containing 20% by mass of Al 2 O 3 [shown as CuO (1) NiO (79) / SiAl (20). ] Was obtained.
Example 5
In Example 1, NiO 80% by mass and SiO 2 .Al 2 O were used in the same manner as in Example 1 except that 450.1 g of nickel sulfate hexahydrate was used and copper sulfate pentahydrate was not used. 3 Desulfurizing agent E containing 20% by mass [NiO (80) / SiAl (20). ] Was obtained.
[0020]
Comparative Example 1
426.0 g of copper sulfate pentahydrate (manufactured by Wako Pure Chemical Industries, Ltd., special grade) was dissolved in 4 L of ion-exchanged water heated to 80 ° C., and pseudo-boehmite [manufactured by Catalyst Chemical Industry Co., Ltd., “ C-AP ", were mixed 67 mass%] 7.2 g as Al 2 O 3 (preparation a).
On the other hand, 300.0 g of sodium carbonate was dissolved in 4 L of ion-exchanged water heated to 80 ° C., and water glass [“J-1”, manufactured by Nippon Chemical Industry Co., Ltd., Si concentration 29% by mass] 6 g was added (Preparation solution B).
Next, the prepared liquid A and the prepared liquid B were mixed while keeping the temperature at 80 ° C., respectively, and stirred for 1 hour. Then, the precipitated cake was washed and filtered with 60 L of ion-exchanged water, and dried with a blow dryer. Dry at 12 ° C. for 12 hours. Then, it is calcined at 350 ° C. for 3 hours, and is indicated as a desulfurizing agent F [CuO (80) / SiAl (20) containing 80% by mass of CuO and 20% by mass of SiO 2 .Al 2 O 3 . ] Was obtained.
[0021]
Comparative Example 2
Desulfurizing agent “G132B” manufactured by Sudo Chemie Catalysts Inc. [Includes 32% by mass of CuO and 68% by mass of ZnO. Indicated as CuO (32) / ZnO (68). ] Was used as the catalyst of Comparative Example 2.
Comparative Example 3
Desulfurizing agent “T2552” manufactured by Sudo Chemie Catalysts Inc. [Includes 5 mass% of Ag and 95 mass% of Al 2 O 3 . Ag (5) / Al 2 O 3 (95). ] Was used as the catalyst of Comparative Example 3.
[0022]
Comparative Example 4
After filling the reaction tube with 1.0 cm 3 of the desulfurizing agent A and flowing 100% hydrogen gas at 100 cm 3 / min, performing a reduction treatment at 300 ° C. for 3 hours, the valves installed at the upper and lower portions of the reaction tube were opened, and air was released. Was left in the reaction tube for 3 hours and used as a catalyst in Comparative Example 4.
Test example 1
Each of the desulfurizing agents of Examples 1 to 5 and Comparative Examples 1 to 4 was molded into 0.5 to 1 mm, and 1 cm 3 of the desulfurizing agent was filled in a desulfurizing tube having an inner diameter of 9 mm. The temperature of the desulfurizing agent was set to 20 ° C., and propane gas containing 10 vol ppm (40 vol ppm in total) of COS, dimethyl sulfide (DMS), t-butyl mercaptan (TBM) and dimethyl disulfide (DMDS) at normal pressure and GHSV (gas time). (Space velocity) 30,000 h -1 .
The concentration of each sulfur compound in the gas at the outlet of the desulfurization tube was measured every hour by SCD (Sulfur Chemiluminescence Detector) gas chromatography. Table 1 shows the time when the concentration of each sulfur compound exceeds 0.1 volppm.
Comparative Example 5
The desulfurizing agent A was molded to a size of 0.5 to 1 mm, and 1 cm 3 of the desulfurizing agent was filled in a desulfurizing tube having an inner diameter of 9 mm. Thereafter, the reduced desulfurizing agent was tested in the same manner as in Test Example 1 without being exposed to air. The results are shown in Table 1.
[0023]
[Table 1]
As is clear from Table 1, it can be seen that the desulfurizing agent of the present invention (Examples 1 to 5) shows high performance in the unreduced treatment.
In addition, by bringing the desulfurizing agent of Example 1 into contact with air after the reduction treatment, a significant decrease in performance was observed (Comparative Example 4).
Claims (11)
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| JP2005281358A (en) * | 2004-03-29 | 2005-10-13 | Mitsubishi Heavy Ind Ltd | Desulfurization agent for hydrocarbonaceous fuel and method for producing the same |
| WO2006120981A1 (en) * | 2005-05-12 | 2006-11-16 | Idemitsu Kosan Co., Ltd. | Liquefied petroleum gas for lp gas fuel cell, method of desulfurizing the same and fuel cell system |
| CN100591418C (en) * | 2007-07-19 | 2010-02-24 | 武汉理工大学 | Nickel base crouse vent gas hydrogenation catalysts and coprecipitation manufacturing method |
| CN106669670A (en) * | 2015-11-11 | 2017-05-17 | 中国石油化工股份有限公司 | Preparation method of flue gas desulfurization agent |
| CN112058043A (en) * | 2020-08-25 | 2020-12-11 | 北京金隅水泥节能科技有限公司 | Desulfurizing agent and preparation method thereof |
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| JP2005281358A (en) * | 2004-03-29 | 2005-10-13 | Mitsubishi Heavy Ind Ltd | Desulfurization agent for hydrocarbonaceous fuel and method for producing the same |
| JP4616569B2 (en) * | 2004-03-29 | 2011-01-19 | 三菱重工業株式会社 | Desulfurization agent for hydrocarbon fuel and method for producing the same |
| WO2006120981A1 (en) * | 2005-05-12 | 2006-11-16 | Idemitsu Kosan Co., Ltd. | Liquefied petroleum gas for lp gas fuel cell, method of desulfurizing the same and fuel cell system |
| CN100591418C (en) * | 2007-07-19 | 2010-02-24 | 武汉理工大学 | Nickel base crouse vent gas hydrogenation catalysts and coprecipitation manufacturing method |
| CN106669670A (en) * | 2015-11-11 | 2017-05-17 | 中国石油化工股份有限公司 | Preparation method of flue gas desulfurization agent |
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| CN112058043A (en) * | 2020-08-25 | 2020-12-11 | 北京金隅水泥节能科技有限公司 | Desulfurizing agent and preparation method thereof |
| CN112058043B (en) * | 2020-08-25 | 2021-07-09 | 北京金隅水泥节能科技有限公司 | Desulfurizing agent and preparation method thereof |
| CN114686275A (en) * | 2022-04-02 | 2022-07-01 | 太原理工大学 | Manganese oxide-zinc oxide porous desulfurizer and preparation method thereof |
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