JP3943902B2 - Hydrocarbon desulfurization catalyst, desulfurization method, and fuel cell system - Google Patents
Hydrocarbon desulfurization catalyst, desulfurization method, and fuel cell system Download PDFInfo
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- JP3943902B2 JP3943902B2 JP2001344685A JP2001344685A JP3943902B2 JP 3943902 B2 JP3943902 B2 JP 3943902B2 JP 2001344685 A JP2001344685 A JP 2001344685A JP 2001344685 A JP2001344685 A JP 2001344685A JP 3943902 B2 JP3943902 B2 JP 3943902B2
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- catalyst
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- desulfurization
- hydrogen
- fuel cell
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- 239000003054 catalyst Substances 0.000 title claims description 85
- 239000000446 fuel Substances 0.000 title claims description 61
- 238000006477 desulfuration reaction Methods 0.000 title claims description 41
- 230000023556 desulfurization Effects 0.000 title claims description 41
- 238000000034 method Methods 0.000 title claims description 32
- 229930195733 hydrocarbon Natural products 0.000 title claims description 27
- 150000002430 hydrocarbons Chemical class 0.000 title claims description 27
- 239000004215 Carbon black (E152) Substances 0.000 title claims description 25
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- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 68
- 239000001257 hydrogen Substances 0.000 claims description 41
- 229910052739 hydrogen Inorganic materials 0.000 claims description 41
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 39
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 33
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- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 27
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- 239000007789 gas Substances 0.000 description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 18
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 description 18
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- 230000003647 oxidation Effects 0.000 description 12
- 238000007254 oxidation reaction Methods 0.000 description 12
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 10
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Images
Classifications
-
- 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
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
-
- 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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- Fuel Cell (AREA)
- Hydrogen, Water And Hydrids (AREA)
- Catalysts (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Description
【０００１】
【発明の属する技術分野】
本発明は炭化水素用脱硫触媒に関する。また、この触媒を用いた脱硫方法、さらには、この触媒を充填した脱硫装置を備えた燃料電池システムに関する。
【０００２】
【従来の技術】
燃料電池は燃料の燃焼反応による自由エネルギー変化を直接電気エネルギーとして取り出せるため、高い効率が得られるという特徴がある。さらに有害物質を排出しないことも相俟って、様々な用途への展開が図られている。特に固体高分子形燃料電池は、出力密度が高く、コンパクトで、しかも低温で作動するのが特徴である。
【０００３】
一般的に燃料電池用の燃料ガスとしては水素を主成分とするガスが用いられるが、その原料には天然ガス、ＬＰＧ、ナフサ、灯油等の炭化水素およびメタノール、エタノール等のアルコールおよびジメチルエーテル等のエーテルなどが用いられる。これら炭素と水素を含む原料を水蒸気とともに触媒上で高温処理して改質したり、酸素含有気体と部分酸化したり、また水蒸気と酸素含有気体が共存する系において自己熱回収型の改質反応を行うことにより得られる水素を、基本的には燃料電池用の燃料水素としている。
【０００４】
しかし、これらの原料中には水素以外の元素も存在するため、燃料電池への燃料ガス中に炭素由来の不純物が混入することは避けられない。中でも一酸化炭素は燃料電池の電極触媒として使われている白金系貴金属を被毒するため、燃料ガス中に一酸化炭素が存在すると充分な発電特性が得られなくなる。特に低温作動させる燃料電池ほど一酸化炭素吸着は強く、被毒を受けやすい。このため固体高分子形燃料電池を用いたシステムでは燃料ガス中の一酸化炭素の濃度が低減されていることが必要不可欠である。
【０００５】
そこで原料を改質して得られた改質ガス中の一酸化炭素を水蒸気と反応させ、水素と二酸化炭素に転化したり、さらに微量残存した一酸化炭素を選択酸化で除去する方法が採られる。
最終的に一酸化炭素が十分低い濃度になるまで除去された燃料水素は燃料電池の陰極に導入され、ここでは電極触媒上でプロトンと電子に変換される。生成したプロトンは電解質中を陽極側へ移動し、外部回路を通ってきた電子とともに酸素と反応し、水を生成する。電子が外部回路を通ることにより電気を発生する。
【０００６】
これら燃料電池用燃料水素を製造するまでの原料改質、一酸化炭素除去の各工程さらに陰極の電極に用いられる触媒は貴金属または銅などが還元状態で使われることが多く、このような状態では多量の硫黄が共存した場合、触媒毒となり、水素製造工程または電池そのものの触媒活性を低下させ、効率が低下する。
従って、燃料中に含まれる硫黄分を十分に除去することが水素製造工程に用いられている触媒さらには電極触媒を本来の性能で使用するために必要不可欠であると考えられる。
基本的に硫黄を除去する、いわゆる脱硫工程は水素製造工程の一番最初に行われる。その直後の改質工程に用いる触媒が十分機能するレベルまで硫黄濃度を低減する必要があるが、それは通常０．１質量ｐｐｍ以下である。
【０００７】
これまでは燃料電池用原料の硫黄分を除去する方法としては、脱硫触媒によって難脱硫性有機硫黄化合物を水素化脱硫して、一度吸着除去し易い硫化水素に変換し、適当な吸着剤で処理する方法が適していると思われていた。しかし一般的な水素化脱硫触媒では水素圧力を高くして用いられるが、燃料電池システムに用いる場合は、大気圧か、高くても１ＭＰａにとどめた技術開発が進んでいるので、通常の脱硫触媒系では対応できないのが現状である。
【０００８】
そこで低圧系でも十分に脱硫機能を発現する吸着剤に関する発明が提案され、これまでも様々な触媒系が紹介されている。たとえば特開平１−１８８４０４号、特開平１−１８８４０５号にはニッケル系脱硫剤で脱硫した灯油を水蒸気改質し、水素を製造する方法が報告されている。しかし、この場合、良好な条件で脱硫の可能な温度範囲は１５０〜３００℃であり、プロセス上の制約があった。脱硫の後段にある水蒸気改質装置の入口温度は４００〜５００℃であり、脱硫温度もこの温度に近い方がプロセス上好ましい。また特開平２−３０２３０２号、特開平２−３０２３０３号には銅−亜鉛系脱硫剤が開示されている。しかし、この触媒は比較的高温で用いても炭素析出は少ないが、脱硫活性がニッケルに比べて低いため、天然ガス、ＬＰＧ、ナフサ等の軽質炭化水素の脱硫は行えるが、灯油の脱硫に対しては不十分である。
また特開平１−１４３１５５号に脱硫作用を行わせるために活性炭あるいは薬液を用いる方法が示されている。しかし、この触媒は起動時常温で脱硫に効果があることが示されているが、原料は常温でのガス体に限定され、ナフサ、灯油の類への効果はない。
【０００９】
【発明が解決しようとする課題】
上記したように、燃料電池用燃料水素を製造するまでの原料改質、一酸化炭素除去の各工程さらに陰極の電極に用いられる触媒は貴金属または銅などが還元状態で使われることが多く、このような状態では硫黄が共存した場合、触媒毒となり、水素製造工程または電池そのものの触媒活性を低下させ、効率が低下する。従って、燃料中に含まれる硫黄分を十分に除去することが水素製造工程に用いられている触媒さらには電極触媒を本来の性能で使用するために必要不可欠である。しかも低圧条件下で、難脱硫性物質を効果的に脱硫する必要がある。
本発明はこのような難しい条件をクリアする触媒およびそれを基盤技術とした燃料電池システムを提供するものである。
【００１０】
【課題を解決するための手段】
本発明者は鋭意研究により、原料中に含まれる硫黄化合物を効率的に脱硫する触媒を見出し、本発明を完成するに至ったものである。
すなわち、本発明は、表面積が６００ｍ2／ｇ以上の活性炭を少なくとも５０質量％以上含む担体に酸化ニッケルおよび酸化亜鉛を担持してなる触媒であって、触媒に対する酸化ニッケルおよび酸化亜鉛の担持量がそれぞれ１〜４９質量％であり、かつ酸化ニッケルと酸化亜鉛の担持量の和が５〜５０質量％であることを特徴とする炭化水素用脱硫触媒に関する。
【００１１】
また本発明は、前記の炭化水素用脱硫触媒を用いて、硫黄を含有する炭化水素原料を常圧〜１ＭＰａの圧力下、室温〜４５０℃の反応温度にて脱硫処理することにより、該炭化水素原料の硫黄濃度を０．１質量ｐｐｍ以下に脱硫する方法に関する。
さらに本発明は、前記の炭化水素用脱硫触媒が充填された、硫黄を含有する炭化水素原料を脱硫する脱硫装置と、該脱硫装置により脱硫された炭化水素原料を、水素を主成分とする燃料ガスに改質する改質装置を少なくとも有する燃料電池システムに関する。
【００１２】
【発明の実施の形態】
以下に本発明について詳述する。
本発明は、表面積が６００ｍ2／ｇ以上の活性炭を少なくとも５０質量％以上含む担体に酸化ニッケルおよび酸化亜鉛を担持してなる触媒であって、触媒に対する酸化ニッケルおよび酸化亜鉛の担持量がそれぞれ１〜４９質量％であり、かつ酸化ニッケルと酸化亜鉛の担持量の和が５〜５０質量％であることを特徴とする炭化水素用脱硫触媒に関するものである。
【００１３】
活性炭の種類は特に限定するものではなく、例えば石炭系活性炭、ヤシ殻系活性炭、木質系活性炭などを用いることができる。活性炭の形状も特に限定するものではなく、例えば粉末炭、破砕炭、顆粒炭、円柱状炭、球状炭などを用いることができる。活性炭の粒径も特に限定するものではなく、通常、１μｍ〜１０ｍｍのものを用いることができる。活性炭のかさ密度も特に限定するものではなく、通常０．１〜０．８ｇ／ｃｍ3のものを用いることができる。
【００１４】
活性炭の表面積は６００ｍ2／ｇ以上であることが好ましく、８００ｍ2／ｇ以上であることがより好ましい。活性炭の表面積が６００ｍ2／ｇ未満であると、金属の分散性が低下し、脱硫活性が劣化する。上限は特に限定されないが、通常３５００ｍ2／ｇ以下であることが好ましく、３０００ｍ2／ｇ以下であることがより好ましい。ここで表面積とは、窒素吸着法により測定したＢＥＴ表面積をいう。
【００１５】
担体中の活性炭の量は、５０質量％以上あることが好ましく、特に好ましくは７０質量％以上である。５０質量％未満であると、担体の表面積が低下し、脱硫活性が低下する。上限は１００質量％である。なお、担体中には活性炭以外にバインダー等を含むことができる。
【００１６】
担体の形状、大きさ、成型方法は特に限定するものではない。また成型時には適度なバインダーを添加して成形性を高めてもよい。バインダーとしては、特に限定するものではないが、アルミナ、シリカ、チタニア、ジルコニア、もしくはそれらの複合酸化物などを用いることができる。担体におけるバインダーの添加量は５０質量％以下が好ましく、より好ましくは３０質量％以下である。下限はバインダーとしての機能が発揮される限り特に限定されるものではなく、通常１質量％以上であり、好ましくは５質量％以上である。
【００１７】
酸化ニッケルおよび酸化亜鉛を担体に担持する方法に関しては特に制限はなく、通常の含浸法、イオン交換法など公知の方法を用いることができる。例えば含浸法においては、ニッケルおよび亜鉛の金属塩あるいは金属錯体を、水、エタノールもしくはアセトンなどの溶媒、特に好ましくは水に溶解させ、担体に含浸させる。しかるのち、乾燥、焼成等の処理を行って酸化ニッケルおよび酸化亜鉛を形成させることにより、酸化ニッケルおよび酸化亜鉛を担持した触媒を得ることができる。
【００１８】
ニッケルおよび亜鉛の金属塩あるいは金属錯体は、溶媒に溶解するものあれば、特に制限はなく、各種の塩化物、硝酸塩、硫酸塩、有機酸塩等があげられ、具体的には硝酸ニッケル、酢酸ニッケル、硝酸亜鉛、酢酸亜鉛などを用いることができる。
【００１９】
乾燥方法は特に限定されるものではなく、例えば、空気中での乾燥、減圧下での脱気乾燥等を用いることができる。乾燥温度としては、通常、室温〜１５０℃で行うことができるが、５０〜１４０℃が好ましく、８０〜１２０℃が特に好ましい。
また焼成方法も特に限定されるものではなく、通常、窒素雰囲気で行うことが望ましい。焼成温度としては２５０〜４５０℃が好ましく、３００〜４００℃がより好ましい。また焼成時間としては０．１〜１０時間が好ましく、０．５〜５時間がより好ましい。
【００２０】
酸化ニッケルおよび酸化亜鉛を担持する順序については特に制限はなく、同時に担持させても良く、また酸化亜鉛を担持させた後酸化ニッケルを担持させても良いし、酸化ニッケルを担持させた後酸化亜鉛を担持させても良いが、酸化ニッケルおよび酸化亜鉛を同時に担持させるか、酸化亜鉛を担持させた後酸化ニッケルを担持させるのが好ましい。
【００２１】
酸化ニッケルおよび酸化亜鉛の触媒に対する担持量はそれぞれ１〜４９質量％であり、５〜４５質量％が好ましく、特に１０〜４０質量％が好ましい。担持量が１質量％未満では、触媒性能が発揮されず、また担持量が４９質量％を越える場合は、分散性が低下するだけでなく、経済的な面からも好ましくない。触媒に対する酸化ニッケルと酸化亜鉛の担持量の和は５〜５０質量％であり、８〜４７質量％が好ましく、特に１０〜４５質量％が好ましい。担持量の和が５質量％未満では、触媒性能が発揮されず、また担持量の和が５０質量％を超える場合は、酸化ニッケルおよび酸化亜鉛の分散性が低下するだけでなく、経済的な面からも好ましくない。
【００２２】
上記の方法で調製された触媒を使用する場合、そのまま反応に供することもできるが、前処理として水素等による還元処理を行ってもよい。その条件として温度は１５０〜５００℃、好ましくは２５０〜４００℃が望ましく、時間は０．１〜１０時間、好ましくは０．５〜５時間が望ましい。
【００２３】
触媒の形状については特に限定するものではないが、例えば、打錠成形し粉砕後適当な範囲に整粒した触媒、押し出し成形した触媒、適当なバインダーを加え押し出し成形した触媒、粉末状とした触媒などを用いることができる。もしくは、打錠成形し粉砕後適当な範囲に整粒した担体、押し出し成形した担体、粉末あるいは球形、リング状、タブレット状、円筒状、フレーク状など適当な形に成形した担体、粉末炭、破砕炭、顆粒炭、円柱状炭、球状炭などの活性炭そのものを用いた担体に酸化ニッケルおよび酸化亜鉛を担持した触媒などを用いることができる。
本発明の触媒は、硫黄を吸着することにより脱硫することが主要な特徴である。
【００２４】
また本発明は、前記した炭化水素用脱硫触媒を用いて、硫黄を含有する炭化水素原料を常圧〜１ＭＰａの圧力下、室温〜４５０℃の反応温度にて脱硫処理することにより、該炭化水素原料の硫黄濃度を０．１質量ｐｐｍ以下に脱硫する方法に関する。硫黄濃度は、紫外蛍光法により測定される。
本発明で用いられる硫黄を含有する炭化水素原料としては、特に限定されるものではないが、メタン、エタン、プロパン、ブタン、天然ガス、ＬＰＧ、ナフサ、ガソリン、灯油およびこれらの混合物等が挙げられる。なお、原料中には水素が含まれていてもよい。
本発明で用いられるこれらの炭化水素原料中には、通常、１００質量ｐｐｍ以下の硫黄が含有されている。
【００２５】
脱硫反応における圧力は、燃料電池システムの経済性、安全性等も考慮し、常圧〜１ＭＰａの範囲の低圧が好ましく、特に常圧〜０．２ＭＰａが好ましい。反応温度としては、硫黄濃度を低下させる温度であれば、特に限定はないが、機器スタート時も考慮して、室温から有効に作用することが必要であり、また定常時も考慮して、室温〜４５０℃が好ましい。より好ましくは室温〜３５０℃、特に好ましくは室温〜３００℃が採用される。ＳＶは過剰に高すぎると脱硫反応が進行しにくくなり、一方低すぎると装置が大きくなるため適した範囲が存在する。液体原料を用いる場合は、０．０１〜１５ｈ-1の範囲が好ましく、０．０５〜５ｈ-1の範囲がさらに好ましく、０．１〜３ｈ-1の範囲が特に好ましい。ガス燃料を用いる場合は、１００〜１００００ｈ-1の範囲が好ましく、２００〜５０００ｈ-1の範囲がさらに好ましく、３００〜２０００ｈ-1の範囲が特に好ましい。本発明では、水素なしで用いることができることが特徴であるが、水素を追加してもよい。そのときの水素の流量は、例えば、炭化水素原料１ｇあたり０．０５〜１．０ＮＬである。
【００２６】
本発明の脱硫触媒を充填した脱硫装置の形態は特に限定するものではないが、例えば流通式固定床方式を用いることができる。脱硫装置の形状としては、円筒状、平板状などそれぞれのプロセスの目的に応じた公知のいかなる形状を取ることができる。
【００２７】
本発明の脱硫触媒を用いることにより、前記した硫黄を含有する炭化水素原料から硫黄濃度０．１質量ｐｐｍ以下とすることができる。
硫黄濃度０．１質量ｐｐｍ以下に脱硫された炭化水素原料は、次いで、改質工程、シフト工程、一酸化炭素選択酸化工程等を経ることにより、生成した水素リッチガスを燃料電池用燃料として使うことができる。
改質工程としては、特に限定するものではないが、原料を水蒸気とともに触媒上で高温処理して改質する水蒸気改質や、酸素含有気体との部分酸化、また水蒸気と酸素含有気体が共存する系において自己熱回収型の改質反応を行うオートサーマルリフォーミングなどを用いることができる。
【００２８】
なお改質の反応条件は限定されるものではないが、反応温度は２００〜１０００℃が好ましく、特に５００〜８５０℃が好ましい。反応圧力は常圧〜１ＭＰａが好ましく、特に常圧〜０．２ＭＰａが好ましい。ＬＨＳＶは０．０１〜４０ｈ-1が好ましく、特に０．１〜１０ｈ-1が好ましい。
このとき得られる一酸化炭素と水素を含む混合ガスは、固体酸化物形燃料電池のような場合であればそのまま燃料電池用の燃料として用いることができる。また、リン酸形燃料電池や固体高分子形燃料電池のように一酸化炭素の除去が必要な燃料電池に対しては、該燃料電池用水素の原料として好適に用いることができる。
【００２９】
燃料電池用水素の製造は、公知の方法を採用することができ、例えばシフト工程と一酸化炭素選択酸化工程で処理することにより実施できる。
シフト工程とは一酸化炭素と水とを反応させ水素と二酸化炭素に転換する工程であり、例えば、Ｆｅ−Ｃｒの混合酸化物、Ｚｎ−Ｃｕの混合酸化物、白金、ルテニウム、イリジウムなどを含有する触媒を用い、一酸化炭素含有量を２ｖｏｌ％以下、好ましくは１ｖｏｌ％以下、さらに好ましくは０．５ｖｏｌ％以下に低減させる。
シフト反応は原料となる改質ガス組成等によって、必ずしも反応条件は限定されるものではないが、反応温度は１２０〜５００℃が好ましく、特に１５０〜４５０℃が好ましい。圧力は常圧〜１ＭＰａが好ましく、特に常圧〜０．２ＭＰａが好ましい。ＧＨＳＶは１００〜５００００ｈ-1が好ましく、特に３００〜１００００ｈ-1が好ましい。通常、リン酸形燃料電池ではこの状態の混合ガスを燃料として用いることができる。
【００３０】
一方、固体高分子形燃料電池では、一酸化炭素濃度をさらに低減させることが必要であるので一酸化炭素を除去する工程を設けることが望ましい。この工程としては、特に限定するものではなく、吸着分離法、水素分離膜法、一酸化炭素選択酸化工程などの各種の方法を用いることができるが、装置のコンパクト化、経済性の面から、一酸化炭素選択酸化工程を用いるのが特に好ましい。この工程では、鉄、コバルト、ニッケル、ルテニウム、ロジウム、パラジウム、オスミウム、イリジウム、白金、銅、銀、金などを含有する触媒を用い、残存する一酸化炭素モル数に対し０．５〜１０倍モル、好ましくは０．７〜５倍モル、さらに好ましくは１〜３倍モルの酸素を添加し一酸化炭素を選択的に二酸化炭素に転換することにより一酸化炭素濃度を低減させる。この方法の反応条件は限定されるものではないが、反応温度は８０〜３５０℃が好ましく、特に１００〜３００℃が好ましい。圧力は常圧〜１ＭＰａが好ましく、特に常圧〜０．２ＭＰａが好ましい。ＧＨＳＶは１０００〜５００００ｈ-1が好ましく、特に３０００〜３００００ｈ-1が好ましい。この場合、一酸化炭素の酸化と同時に共存する水素と反応させメタンを生成させることで一酸化炭素濃度の低減を図ることもできる。
【００３１】
また本発明は、前記した炭化水素用脱硫触媒が充填された、硫黄を含有する炭化水素原料を脱硫する脱硫装置と、該脱硫装置により脱硫された炭化水素原料を、水素を主成分とする燃料ガスに改質する改質装置を少なくとも有する燃料電池システムに関する。
【００３２】
以下、この燃料電池システムの一例を図１をもって説明する。
燃料タンク３内の原燃料は燃料ポンプ４を経て脱硫器５に流入する。この時、必要であれば選択酸化反応器１１からの水素含有ガスを添加できる。脱硫器５には、本発明の炭化水素用脱硫触媒が充填されている。脱硫器５で脱硫された燃料は水タンク１から水ポンプ２を経た水と混合した後、気化器６に導入され、改質器７に送り込まれる。
【００３３】
改質器７は加温用バーナー１８で加温される。加温用バーナー１８の燃料には主に燃料電池１７のアノードオフガスを用いるが必要に応じて燃料ポンプ４から吐出される燃料を補充することもできる。改質器７に充填する触媒としてはニッケル系、ルテニウム系、ロジウム系などの触媒を用いることができる。
この様にして製造された水素と一酸化炭素を含有するガスは高温シフト反応器９、低温シフト反応器１０、選択酸化反応器１１を順次通過させることで一酸化炭素濃度は燃料電池の特性に影響を及ぼさない程度まで低減される。これらの反応器に用いる触媒の例としては高温シフト反応器９には鉄−クロム系触媒、低温シフト反応器１０には銅−亜鉛系触媒、選択酸化反応器１１にはルテニウム系触媒等をあげることができる。
【００３４】
固体高分子形燃料電池１７はアノード１２、カソード１３、固体高分子電解質１４からなり、アノード側には上記の方法で得られた高純度の水素を含有する燃料ガスが、カソード側には空気ブロアー８から送られる空気が、それぞれ必要であれば適当な加湿処理を行なったあと（加湿装置は図示していない）導入される。この時、アノードでは水素ガスがプロトンとなり電子を放出する反応が進行し、カソードでは酸素ガスが電子とプロトンを得て水となる反応が進行する。これらの反応を促進するため、それぞれ、アノードには白金黒、活性炭担持のＰｔ触媒あるいはＰｔ−Ｒｕ合金触媒などが、カソードには白金黒、活性炭担持のＰｔ触媒などが用いられる。通常アノード、カソードの両触媒とも、必要に応じてポリテトラフロロエチレン、低分子の高分子電解質膜素材、活性炭などと共に多孔質触媒層に成形される。
【００３５】
次いでＮａｆｉｏｎ（デュポン社製）、Ｇｏｒｅ（ゴア社製）、Ｆｌｅｍｉｏｎ（旭硝子社製）、Ａｃｉｐｌｅｘ（旭化成社製）等の商品名で知られる高分子電解質膜の両側に該多孔質触媒層を積層しＭＥＡ（Ｍｅｍｂｒａｎｅ Ｅｌｅｃｔｒｏｄｅ Ａｓｓｅｍｂｌｙ）が形成される。さらにＭＥＡを金属材料、グラファイト、カーボンコンポジットなどからなるガス供給機能、集電機能、特にカソードにおいては重要な排水機能等を持つセパレータで挟み込むことで燃料電池が組み立てられる。電気負荷１５はアノード、カソードと電気的に連結される。アノードオフガスは加温用バーナー１８において消費される。カソードオフガスは排気口１６から排出される。
【００３６】
【発明の効果】
本発明の触媒は、硫黄を含有する炭化水素原料を脱硫して、硫黄濃度を０．１質量ｐｐｍ以下に低減することができ、得られる燃料ガスは、特に固体高分子形燃料電池を用いた燃料電池システムに好適に採用できる。
【００３７】
【実施例】
以下、本発明について実施例をあげて説明するが、本発明はこれらに限定されるものではない。
【００３８】
（実施例１）
武田薬品（株）社製活性炭（炭素含有量９５質量％、表面積１２００ｍ2／ｇ）２０ｇに対し、１８．３ｇの硝酸亜鉛を２０ｇの水に溶解し、含浸担持した。この硝酸亜鉛を担持した活性炭を１２０℃にて一晩乾燥後、窒素雰囲気、３５０℃の条件下で３時間焼成し酸化亜鉛を担持した活性炭とした。次いで８．７ｇの硝酸ニッケルを２０ｇの水に溶解し、酸化亜鉛を担持した活性炭に含浸担持し、１２０℃にて一晩乾燥後、窒素雰囲気、３５０℃の条件下で３時間焼成し、酸化亜鉛と酸化ニッケルを担持した触媒（１）とした。担持された酸化亜鉛量および酸化ニッケル量は触媒に対してそれぞれ１８質量％および１０質量％であった。
【００３９】
（実施例２）
武田薬品（株）社製活性炭（炭素含有量９８質量％、表面積９００ｍ2／ｇ）２０ｇに対し、４．９ｇの硝酸亜鉛と２０．８ｇの硝酸ニッケルを２０ｇの水に溶解し、含浸担持した。担持後の活性炭を１２０℃にて一晩乾燥後、窒素雰囲気、３５０℃の条件下で３時間焼成し、酸化亜鉛と酸化ニッケルを担持した触媒（２）とした。担持された酸化亜鉛量および酸化ニッケル量は触媒に対してそれぞれ５質量％および２０質量％であった。
【００４０】
（実施例３）
武田薬品（株）社製活性炭（炭素含有量９８質量％、表面積１６００ｍ2／ｇ）１８ｇに対し、２ｇのアルミナゾルを添加し、混練し、押出し成型した。この成型体を１２０℃で一晩乾燥後、窒素雰囲気、４００℃にて焼成を行った。得られたアルミナ含有活性炭に対し、４．９ｇの硝酸亜鉛と２０．８ｇの硝酸ニッケルを２０ｇの水に溶解し、含浸担持した。担持後の活性炭を１２０℃にて一晩乾燥後、窒素雰囲気、３５０℃の条件下で３時間焼成し、酸化亜鉛と酸化ニッケルを担持した触媒（３）とした。担持された酸化亜鉛量および酸化ニッケル量は触媒に対してそれぞれ５質量％および２０質量％であった。
【００４１】
（比較例１）
武田薬品（株）社製活性炭（炭素含有量９０質量％、表面積５００ｍ2／ｇ）２０ｇに対し、１８．３ｇの硝酸亜鉛を２０ｇの水に溶解し、含浸担持した。この硝酸亜鉛を担持した活性炭を１２０℃にて一晩乾燥後、窒素雰囲気、３５０℃の条件下で３時間焼成し酸化亜鉛を担持した活性炭とした。次いで８．７ｇの硝酸ニッケルを２０ｇの水に溶解し、酸化亜鉛を担持した活性炭に含浸担持し、１２０℃にて一晩乾燥後、窒素雰囲気、３５０℃の条件下で３時間焼成し、酸化亜鉛と酸化ニッケルを担持した触媒（４）とした。担持された酸化亜鉛量および酸化ニッケル量は触媒に対してそれぞれ１８質量％および１０質量％であった。
【００４２】
（比較例２）
武田薬品（株）社製活性炭（炭素含有量９８質量％、表面積９００ｍ2／ｇ）２０ｇに対し、３１．３ｇの硝酸亜鉛を２０ｇの水に溶解し、含浸担持した。この硝酸亜鉛を担持した活性炭を１２０℃にて一晩乾燥後、窒素雰囲気、３５０℃の条件下で３時間焼成し、酸化亜鉛を担持した触媒（５）とした。担持された酸化亜鉛量は触媒に対して３０質量％であった。
【００４３】
これらの触媒（１）から（５）をそれぞれ１０ｃｍ3ずつ反応管に充填し、水素気流中、３００℃にて２時間還元した後、１号灯油（硫黄濃度１５質量ｐｐｍ）の脱硫反応評価を行った。反応評価は、温度２８０℃、常圧、ＬＨＳＶ１．０ｈ-1の条件で行い、灯油１Ｌに対し、２５０ＮＬの水素を流通させた。５００時間後の生成灯油中の硫黄濃度を表１に示した。
【００４４】
【表１】
また、これらの触媒（１）から（５）をそれぞれ１０ｃｍ3ずつ反応管に充填し、水素気流中、３００℃にて２時間還元した後、１号灯油（硫黄濃度１５質量ｐｐｍ）の脱硫反応評価を行った。反応評価は、温度１８０℃、常圧、ＬＨＳＶ１．０ｈ-1、水素を流通させない条件で行った。２００時間後の生成灯油中の硫黄濃度を表２に示した。
【００４６】
【表２】
また、これらの触媒（１）から（５）をそれぞれ１０ｃｍ3ずつ反応管に充填し、水素気流中、３００℃にて２時間還元した後、１号灯油（硫黄濃度１５質量ｐｐｍ）の脱硫反応評価を行った。反応評価は、室温、常圧、ＬＨＳＶ０．５ｈ-1、水素を流通させない条件で行った。２００時間後の生成灯油中の硫黄濃度を表３に示した。
【００４８】
【表３】
（実施例４）
図１の燃料電池システムにおいて、実施例１で得られた触媒（１）を脱硫器５に充填して、１号灯油（硫黄濃度１５質量ｐｐｍ）を燃料とし、発電試験を行なった。２００時間の運転中、脱硫器は正常に作動し、触媒の活性低下は認められなかった。脱硫条件は、温度１８０℃、常圧、水素流通なし、ＬＨＳＶ＝０．５ｈ-1であった。
このとき水蒸気改質にはＲｕ系触媒を用い、Ｓ／Ｃ＝３、温度７００℃、ＬＨＳＶ＝５ｈ-1の条件で、シフト工程（反応器１０）ではＣｕ−Ｚｎ系触媒を用い、２００℃、ＧＨＳＶ＝２０００ｈ-1の条件で、一酸化炭素選択酸化工程（反応器１１）ではＲｕ系触媒を用い、Ｏ2／ＣＯ＝３、温度１５０℃、ＧＨＳＶ＝５０００ｈ-1の条件で運転を行った。燃料電池も正常に作動し電気負荷１５も順調に運転された。
【図面の簡単な説明】
【図１】本発明の燃料電池システムの一例を示す概略図である。
【符号の説明】
１ 水タンク
２ 水ポンプ
３ 燃料タンク
４ 燃料ポンプ
５ 脱硫器
６ 気化器
７ 改質器
８ 空気ブロアー
９ 高温シフト反応器
１０ 低温シフト反応器
１１ 選択酸化反応器
１２ アノード
１３ カソード
１４ 固体高分子電解質
１５ 電気負荷
１６ 排気口
１７ 固体高分子形燃料電池
１８ 加温用バーナー[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a hydrocarbon desulfurization catalyst. The present invention also relates to a desulfurization method using this catalyst, and further to a fuel cell system provided with a desulfurization apparatus filled with this catalyst.
[0002]
[Prior art]
A fuel cell has a feature that high efficiency can be obtained because a free energy change caused by a combustion reaction of fuel can be directly taken out as electric energy. In addition to the fact that it does not emit harmful substances, it is being developed for various uses. In particular, solid polymer fuel cells are characterized by high power density, compactness, and operation at low temperatures.
[0003]
As a fuel gas for a fuel cell, a gas containing hydrogen as a main component is generally used, and the raw materials thereof include natural gas, hydrocarbons such as LPG, naphtha and kerosene, alcohol such as methanol, ethanol, and dimethyl ether. Ether or the like is used. These carbon and hydrogen raw materials are reformed by treating them with steam at a high temperature on a catalyst, or they are partially oxidized with an oxygen-containing gas, or a self-heat recovery type reforming reaction in a system in which steam and an oxygen-containing gas coexist. The hydrogen obtained by performing is basically used as fuel hydrogen for fuel cells.
[0004]
However, since elements other than hydrogen exist in these raw materials, it is inevitable that impurities derived from carbon are mixed in the fuel gas to the fuel cell. Among these, carbon monoxide poisons platinum-based noble metals used as electrode catalysts for fuel cells. Therefore, if carbon monoxide is present in the fuel gas, sufficient power generation characteristics cannot be obtained. In particular, carbon monoxide adsorption is stronger and more susceptible to poisoning in a fuel cell operated at a low temperature. Therefore, in a system using a polymer electrolyte fuel cell, it is indispensable that the concentration of carbon monoxide in the fuel gas is reduced.
[0005]
Therefore, a method is adopted in which carbon monoxide in the reformed gas obtained by reforming the raw material is reacted with water vapor to convert it into hydrogen and carbon dioxide, or a small amount of remaining carbon monoxide is removed by selective oxidation. .
Finally, the fuel hydrogen removed until the carbon monoxide concentration is sufficiently low is introduced into the cathode of the fuel cell where it is converted into protons and electrons on the electrocatalyst. The produced protons move to the anode side in the electrolyte, react with oxygen together with the electrons that have passed through the external circuit, and produce water. Electrons generate electricity by passing through an external circuit.
[0006]
The catalyst used for the reforming of raw materials until the production of fuel hydrogen for fuel cells, the removal of carbon monoxide, and the cathode electrode is often used in a reduced state such as noble metal or copper. When a large amount of sulfur coexists, it becomes a catalyst poison, which reduces the catalytic activity of the hydrogen production process or the battery itself, and decreases the efficiency.
Therefore, it is considered that it is indispensable to sufficiently remove the sulfur content contained in the fuel in order to use the catalyst used in the hydrogen production process and further the electrode catalyst in its original performance.
The so-called desulfurization process, which basically removes sulfur, takes place at the very beginning of the hydrogen production process. Although it is necessary to reduce the sulfur concentration to a level at which the catalyst used in the reforming process immediately after that functions sufficiently, it is usually 0.1 ppm by mass or less.
[0007]
Until now, the sulfur content of fuel cell raw materials has been removed by hydrodesulfurizing difficult-to-desulfurize organic sulfur compounds with a desulfurization catalyst, once converted to hydrogen sulfide that can be easily adsorbed and removed, and treated with an appropriate adsorbent. It seemed that the method to do was suitable. However, a general hydrodesulfurization catalyst is used at a high hydrogen pressure. However, when it is used in a fuel cell system, since the technological development is limited to atmospheric pressure or at most 1 MPa, an ordinary desulfurization catalyst is used. The current situation is that the system cannot handle it.
[0008]
Therefore, an invention related to an adsorbent that sufficiently exhibits a desulfurization function even in a low-pressure system has been proposed, and various catalyst systems have been introduced so far. For example, JP-A-1-188404 and JP-A-1-188405 report a method for producing hydrogen by steam reforming kerosene desulfurized with a nickel-based desulfurizing agent. However, in this case, the temperature range in which desulfurization is possible under good conditions is 150 to 300 ° C., and there is a restriction on the process. The inlet temperature of the steam reformer in the subsequent stage of desulfurization is 400 to 500 ° C., and the desulfurization temperature is preferably close to this temperature in terms of the process. JP-A-2-302302 and JP-A-2-302303 disclose copper-zinc-based desulfurization agents. However, even if this catalyst is used at a relatively high temperature, carbon deposition is small. However, since the desulfurization activity is lower than that of nickel, light hydrocarbons such as natural gas, LPG and naphtha can be desulfurized. Is insufficient.
Japanese Patent Application Laid-Open No. 1-143155 discloses a method using activated carbon or a chemical solution for desulfurization. However, this catalyst has been shown to be effective for desulfurization at room temperature at start-up, but the raw material is limited to a gas body at room temperature and has no effect on naphtha and kerosene.
[0009]
[Problems to be solved by the invention]
As described above, noble metal or copper is often used in a reduced state as the catalyst used for the reforming of raw materials until the production of fuel hydrogen for fuel cells, the removal of carbon monoxide, and the cathode electrode. In such a state, when sulfur coexists, it becomes a catalyst poison, which reduces the catalytic activity of the hydrogen production process or the battery itself, and reduces the efficiency. Therefore, it is indispensable to sufficiently remove the sulfur contained in the fuel in order to use the catalyst used in the hydrogen production process and further the electrode catalyst in its original performance. In addition, it is necessary to effectively desulfurize hardly desulfurization substances under low pressure conditions.
The present invention provides a catalyst that satisfies such difficult conditions and a fuel cell system based on the catalyst.
[0010]
[Means for Solving the Problems]
The present inventor has found a catalyst for efficiently desulfurizing a sulfur compound contained in a raw material through intensive research, and has completed the present invention.
That is, the present invention is a catalyst in which nickel oxide and zinc oxide are supported on a support containing at least 50% by mass of activated carbon having a surface area of 600 m 2 / g or more, and the amount of nickel oxide and zinc oxide supported on the catalyst is The present invention relates to a hydrocarbon desulfurization catalyst, which is 1 to 49% by mass, and the sum of supported amounts of nickel oxide and zinc oxide is 5 to 50% by mass.
[0011]
Further, the present invention provides a hydrocarbon raw material containing sulfur by desulfurizing a hydrocarbon raw material containing sulfur at a reaction temperature of room temperature to 450 ° C. under a pressure of normal pressure to 1 MPa. The present invention relates to a method of desulfurizing a raw material sulfur concentration to 0.1 mass ppm or less.
Furthermore, the present invention provides a desulfurization apparatus for desulfurizing a hydrocarbon raw material containing sulfur, which is filled with the above-mentioned hydrocarbon desulfurization catalyst, and a fuel containing hydrogen as a main component of the hydrocarbon raw material desulfurized by the desulfurization apparatus. The present invention relates to a fuel cell system having at least a reformer for reforming into gas.
[0012]
DETAILED DESCRIPTION OF THE INVENTION
The present invention is described in detail below.
The present invention is a catalyst in which nickel oxide and zinc oxide are supported on a support containing at least 50% by mass or more of activated carbon having a surface area of 600 m 2 / g or more, and the amount of nickel oxide and zinc oxide supported on the catalyst is 1 respectively. The present invention relates to a hydrocarbon desulfurization catalyst characterized in that it is ˜49 mass% and the sum of the supported amounts of nickel oxide and zinc oxide is 5 to 50 mass%.
[0013]
The kind of activated carbon is not particularly limited, and for example, coal-based activated carbon, coconut shell-based activated carbon, wood-based activated carbon, and the like can be used. The shape of the activated carbon is not particularly limited, and for example, powdered coal, crushed coal, granulated coal, columnar coal, spherical coal, and the like can be used. The particle size of the activated carbon is not particularly limited, and those having a particle size of 1 μm to 10 mm can be usually used. The bulk density of the activated carbon is not particularly limited, and those of 0.1 to 0.8 g / cm 3 can be usually used.
[0014]
The surface area of the activated carbon is preferably 600 m 2 / g or more, and more preferably 800 m 2 / g or more. When the surface area of the activated carbon is less than 600 m 2 / g, the dispersibility of the metal is lowered and the desulfurization activity is deteriorated. The upper limit is not particularly limited, it is preferably usually 3500 m 2 / g or less, and more preferably less 3000 m 2 / g. Here, the surface area refers to the BET surface area measured by the nitrogen adsorption method.
[0015]
The amount of activated carbon in the carrier is preferably 50% by mass or more, particularly preferably 70% by mass or more. If it is less than 50% by mass, the surface area of the carrier is lowered, and the desulfurization activity is lowered. The upper limit is 100% by mass. The carrier can contain a binder and the like in addition to the activated carbon.
[0016]
The shape, size, and molding method of the carrier are not particularly limited. Further, at the time of molding, an appropriate binder may be added to improve moldability. The binder is not particularly limited, and alumina, silica, titania, zirconia, or a composite oxide thereof can be used. The amount of binder added to the carrier is preferably 50% by mass or less, and more preferably 30% by mass or less. The lower limit is not particularly limited as long as the function as a binder is exhibited, and is usually 1% by mass or more, preferably 5% by mass or more.
[0017]
The method for supporting nickel oxide and zinc oxide on a carrier is not particularly limited, and a known method such as a normal impregnation method or an ion exchange method can be used. For example, in the impregnation method, a metal salt or metal complex of nickel and zinc is dissolved in water, a solvent such as ethanol or acetone, particularly preferably water, and impregnated on a support. Thereafter, a catalyst carrying nickel oxide and zinc oxide can be obtained by forming nickel oxide and zinc oxide by performing treatments such as drying and firing.
[0018]
The metal salt or metal complex of nickel and zinc is not particularly limited as long as it is soluble in a solvent, and examples thereof include various chlorides, nitrates, sulfates, and organic acid salts. Nickel, zinc nitrate, zinc acetate and the like can be used.
[0019]
The drying method is not particularly limited, and for example, drying in air, deaeration drying under reduced pressure, or the like can be used. The drying temperature is usually from room temperature to 150 ° C, preferably from 50 to 140 ° C, particularly preferably from 80 to 120 ° C.
Also, the firing method is not particularly limited, and it is usually desirable to perform in a nitrogen atmosphere. As a calcination temperature, 250-450 degreeC is preferable and 300-400 degreeC is more preferable. The firing time is preferably 0.1 to 10 hours, and more preferably 0.5 to 5 hours.
[0020]
The order of supporting nickel oxide and zinc oxide is not particularly limited, and may be supported simultaneously, or after supporting zinc oxide, nickel oxide may be supported, or after supporting nickel oxide, zinc oxide. However, it is preferable to support nickel oxide and zinc oxide simultaneously, or to support nickel oxide after supporting zinc oxide.
[0021]
The supported amounts of nickel oxide and zinc oxide with respect to the catalyst are each 1 to 49% by mass, preferably 5 to 45% by mass, and particularly preferably 10 to 40% by mass. When the supported amount is less than 1% by mass, the catalyst performance is not exhibited, and when the supported amount exceeds 49% by mass, not only the dispersibility is lowered, but also from the economical viewpoint. The sum of the amount of nickel oxide and zinc oxide supported on the catalyst is 5 to 50% by mass, preferably 8 to 47% by mass, and particularly preferably 10 to 45% by mass. When the sum of the supported amounts is less than 5% by mass, the catalyst performance is not exhibited, and when the sum of the supported amounts exceeds 50% by mass, not only the dispersibility of nickel oxide and zinc oxide is lowered but also economical. It is not preferable also from a surface.
[0022]
When the catalyst prepared by the above method is used, it can be subjected to the reaction as it is, but a reduction treatment with hydrogen or the like may be performed as a pretreatment. As the conditions, the temperature is 150 to 500 ° C., preferably 250 to 400 ° C., and the time is 0.1 to 10 hours, preferably 0.5 to 5 hours.
[0023]
The shape of the catalyst is not particularly limited. For example, a catalyst formed by tableting and pulverized to an appropriate range, an extruded catalyst, an extruded catalyst added with an appropriate binder, and a powdered catalyst Etc. can be used. Or, a carrier formed by tableting and pulverized to an appropriate range, an extruded carrier, a powder or a carrier formed into an appropriate shape such as a sphere, ring, tablet, cylinder, flake, powdered charcoal, crushed A catalyst in which nickel oxide and zinc oxide are supported on a carrier using activated carbon itself such as charcoal, granular charcoal, columnar charcoal, and spherical charcoal can be used.
The main feature of the catalyst of the present invention is that it is desulfurized by adsorbing sulfur.
[0024]
The present invention also provides a hydrocarbon desulfurization catalyst by desulfurizing a hydrocarbon raw material containing sulfur at a reaction temperature of room temperature to 450 ° C. under a pressure of normal pressure to 1 MPa. The present invention relates to a method of desulfurizing a raw material sulfur concentration to 0.1 mass ppm or less. The sulfur concentration is measured by an ultraviolet fluorescence method.
The hydrocarbon raw material containing sulfur used in the present invention is not particularly limited, and examples thereof include methane, ethane, propane, butane, natural gas, LPG, naphtha, gasoline, kerosene, and mixtures thereof. . In addition, hydrogen may be contained in the raw material.
These hydrocarbon raw materials used in the present invention usually contain 100 ppm by mass or less of sulfur.
[0025]
The pressure in the desulfurization reaction is preferably a low pressure in the range of normal pressure to 1 MPa, and more preferably normal pressure to 0.2 MPa in consideration of the economics and safety of the fuel cell system. The reaction temperature is not particularly limited as long as it is a temperature that lowers the sulfur concentration. However, it is necessary to act effectively from room temperature in consideration of the start of the equipment, and it is necessary to consider room temperature in consideration of the steady state. ˜450 ° C. is preferred. More preferably, room temperature to 350 ° C., particularly preferably room temperature to 300 ° C. is employed. If the SV is too high, the desulfurization reaction does not proceed easily. On the other hand, if the SV is too low, the apparatus becomes large. When using a liquid material is preferably in the range of 0.01～15H -1, more preferably in the range of 0.05～5H -1, range 0.1～3H -1 are particularly preferred. In the case of using a gas fuel, preferably in the range of 100～10000H -1, more preferably in the range of 200～5000H -1, range 300～2000H -1 are particularly preferred. The present invention is characterized in that it can be used without hydrogen, but hydrogen may be added. The flow rate of hydrogen at that time is, for example, 0.05 to 1.0 NL per 1 g of hydrocarbon raw material.
[0026]
Although the form of the desulfurization apparatus filled with the desulfurization catalyst of the present invention is not particularly limited, for example, a flow-type fixed bed system can be used. The shape of the desulfurization device can be any known shape depending on the purpose of each process, such as a cylindrical shape or a flat plate shape.
[0027]
By using the desulfurization catalyst of the present invention, the sulfur concentration can be reduced to 0.1 mass ppm or less from the hydrocarbon raw material containing sulfur.
The hydrocarbon raw material desulfurized to a sulfur concentration of 0.1 mass ppm or less is then used as a fuel for fuel cells through the reforming step, shift step, carbon monoxide selective oxidation step, etc. Can do.
Although it does not specifically limit as a reforming process, steam reforming which reforms raw materials with steam at a high temperature treatment on a catalyst, partial oxidation with oxygen-containing gas, and steam and oxygen-containing gas coexist For example, autothermal reforming that performs a self-heat recovery type reforming reaction in the system can be used.
[0028]
The reaction conditions for the reforming are not limited, but the reaction temperature is preferably 200 to 1000 ° C, particularly preferably 500 to 850 ° C. The reaction pressure is preferably normal pressure to 1 MPa, and particularly preferably normal pressure to 0.2 MPa. LHSV is preferably 0.01 to 40 h −1 , particularly preferably 0.1 to 10 h −1 .
The mixed gas containing carbon monoxide and hydrogen obtained at this time can be used as a fuel for a fuel cell as it is in the case of a solid oxide fuel cell. In addition, it can be suitably used as a raw material for hydrogen for a fuel cell, such as a phosphoric acid fuel cell or a polymer electrolyte fuel cell, in which carbon monoxide needs to be removed.
[0029]
The production of hydrogen for a fuel cell can employ a known method, and can be carried out, for example, by treating in a shift step and a carbon monoxide selective oxidation step.
The shift process is a process in which carbon monoxide and water are reacted to convert them into hydrogen and carbon dioxide. For example, a mixed oxide of Fe—Cr, a mixed oxide of Zn—Cu, platinum, ruthenium, iridium and the like are contained. The carbon monoxide content is reduced to 2 vol% or less, preferably 1 vol% or less, and more preferably 0.5 vol% or less.
Although the reaction conditions for the shift reaction are not necessarily limited by the reformed gas composition or the like as a raw material, the reaction temperature is preferably 120 to 500 ° C, and particularly preferably 150 to 450 ° C. The pressure is preferably normal pressure to 1 MPa, particularly preferably normal pressure to 0.2 MPa. GHSV is preferably 100~50000h -1, especially 300～10000H -1 are preferred. Usually, in the phosphoric acid fuel cell, the mixed gas in this state can be used as fuel.
[0030]
On the other hand, in the polymer electrolyte fuel cell, since it is necessary to further reduce the carbon monoxide concentration, it is desirable to provide a step of removing carbon monoxide. This step is not particularly limited, and various methods such as an adsorption separation method, a hydrogen separation membrane method, and a carbon monoxide selective oxidation step can be used. It is particularly preferred to use a carbon monoxide selective oxidation step. In this step, using a catalyst containing iron, cobalt, nickel, ruthenium, rhodium, palladium, osmium, iridium, platinum, copper, silver, gold, etc., 0.5 to 10 times the remaining number of moles of carbon monoxide Mole, preferably 0.7 to 5 times mole, more preferably 1 to 3 times mole oxygen is added to selectively convert carbon monoxide to carbon dioxide, thereby reducing the carbon monoxide concentration. Although the reaction conditions of this method are not limited, the reaction temperature is preferably 80 to 350 ° C, particularly preferably 100 to 300 ° C. The pressure is preferably normal pressure to 1 MPa, particularly preferably normal pressure to 0.2 MPa. GHSV is preferably 1000~50000h -1, especially 3000～30000H -1 are preferred. In this case, the carbon monoxide concentration can be reduced by reacting with the coexisting hydrogen simultaneously with the oxidation of carbon monoxide to generate methane.
[0031]
The present invention also relates to a desulfurization apparatus for desulfurizing a hydrocarbon raw material containing sulfur, which is filled with the above-mentioned hydrocarbon desulfurization catalyst, and a fuel containing hydrogen as a main component of the hydrocarbon raw material desulfurized by the desulfurization apparatus. The present invention relates to a fuel cell system having at least a reformer for reforming into gas.
[0032]
An example of this fuel cell system will be described below with reference to FIG.
The raw fuel in the
[0033]
The reformer 7 is heated by a
The gas containing hydrogen and carbon monoxide produced in this way is passed through the high temperature shift reactor 9, the low
[0034]
The polymer
[0035]
Next, the porous catalyst layer is laminated on both sides of a polymer electrolyte membrane known by a trade name such as Nafion (manufactured by DuPont), Gore (manufactured by Gore), Flemion (manufactured by Asahi Glass), Aciplex (manufactured by Asahi Kasei). An MEA (Membrane Electrode Assembly) is formed. Further, the fuel cell is assembled by sandwiching the MEA with a separator having a gas supply function, a current collecting function, particularly an important drainage function in the cathode, and the like made of a metal material, graphite, carbon composite and the like. The
[0036]
【The invention's effect】
The catalyst of the present invention can desulfurize a hydrocarbon raw material containing sulfur to reduce the sulfur concentration to 0.1 mass ppm or less, and the obtained fuel gas is a solid polymer fuel cell in particular. It can be suitably used for a fuel cell system.
[0037]
【Example】
EXAMPLES Hereinafter, although an Example is given and this invention is demonstrated, this invention is not limited to these.
[0038]
Example 1
18.3 g of zinc nitrate was dissolved in 20 g of water against 20 g of activated carbon (carbon content 95 mass%, surface area 1200 m 2 / g) manufactured by Takeda Pharmaceutical Co., Ltd., and impregnated. The activated carbon carrying zinc nitrate was dried at 120 ° C. overnight and then calcined for 3 hours in a nitrogen atmosphere at 350 ° C. to obtain activated carbon carrying zinc oxide. Next, 8.7 g of nickel nitrate is dissolved in 20 g of water, impregnated and supported on activated carbon supporting zinc oxide, dried at 120 ° C. overnight, and then calcined for 3 hours under conditions of 350 ° C. in a nitrogen atmosphere. A catalyst (1) supporting zinc and nickel oxide was obtained. The amounts of zinc oxide and nickel oxide supported were 18% by mass and 10% by mass, respectively, with respect to the catalyst.
[0039]
(Example 2)
4.9 g of zinc nitrate and 20.8 g of nickel nitrate were dissolved in 20 g of water and impregnated on 20 g of activated carbon (carbon content 98 mass%, surface area 900 m 2 / g) manufactured by Takeda Pharmaceutical Co., Ltd. . The supported activated carbon was dried at 120 ° C. overnight and then calcined under a nitrogen atmosphere and 350 ° C. for 3 hours to obtain a catalyst (2) supporting zinc oxide and nickel oxide. The amounts of zinc oxide and nickel oxide supported were 5% by mass and 20% by mass, respectively, with respect to the catalyst.
[0040]
(Example 3)
2 g of alumina sol was added to 18 g of activated carbon (carbon content 98 mass%, surface area 1600 m 2 / g) manufactured by Takeda Pharmaceutical Co., Ltd., kneaded, and extruded. The molded body was dried at 120 ° C. overnight and then fired at 400 ° C. in a nitrogen atmosphere. To the obtained activated carbon containing alumina, 4.9 g of zinc nitrate and 20.8 g of nickel nitrate were dissolved in 20 g of water and impregnated. The supported activated carbon was dried at 120 ° C. overnight and then calcined under a nitrogen atmosphere and at 350 ° C. for 3 hours to obtain a catalyst (3) supporting zinc oxide and nickel oxide. The amounts of zinc oxide and nickel oxide supported were 5% by mass and 20% by mass, respectively, with respect to the catalyst.
[0041]
(Comparative Example 1)
18.3 g of zinc nitrate was dissolved in 20 g of water against 20 g of activated carbon (carbon content 90 mass%, surface area 500 m 2 / g) manufactured by Takeda Pharmaceutical Co., Ltd., and impregnated and supported. The activated carbon carrying zinc nitrate was dried at 120 ° C. overnight and then calcined for 3 hours in a nitrogen atmosphere at 350 ° C. to obtain activated carbon carrying zinc oxide. Next, 8.7 g of nickel nitrate is dissolved in 20 g of water, impregnated and supported on activated carbon supporting zinc oxide, dried at 120 ° C. overnight, and then calcined for 3 hours under conditions of 350 ° C. in a nitrogen atmosphere. A catalyst (4) supporting zinc and nickel oxide was obtained. The amounts of zinc oxide and nickel oxide supported were 18% by mass and 10% by mass, respectively, with respect to the catalyst.
[0042]
(Comparative Example 2)
31.3 g of zinc nitrate was dissolved in 20 g of water and impregnated on 20 g of activated carbon (carbon content 98 mass%, surface area 900 m 2 / g) manufactured by Takeda Pharmaceutical Co., Ltd. The activated carbon supporting zinc nitrate was dried at 120 ° C. overnight and then calcined under a nitrogen atmosphere and at 350 ° C. for 3 hours to obtain a catalyst (5) supporting zinc oxide. The amount of zinc oxide supported was 30% by mass with respect to the catalyst.
[0043]
Each of these catalysts (1) to (5) was filled into a reaction tube at a rate of 10 cm 3 and reduced at 300 ° C. for 2 hours in a hydrogen stream, and then the desulfurization reaction evaluation of No. 1 kerosene (
[0044]
[Table 1]
In addition, 10 cm 3 of each of these catalysts (1) to (5) was filled in a reaction tube and reduced at 300 ° C. for 2 hours in a hydrogen stream, and then desulfurization reaction of No. 1 kerosene (
[0046]
[Table 2]
In addition, 10 cm 3 of each of these catalysts (1) to (5) was filled in a reaction tube and reduced at 300 ° C. for 2 hours in a hydrogen stream, and then desulfurization reaction of No. 1 kerosene (
[0048]
[Table 3]
Example 4
In the fuel cell system of FIG. 1, the catalyst (1) obtained in Example 1 was filled in the
At this time, a Ru-based catalyst is used for steam reforming, and a Cu-Zn-based catalyst is used in the shift step (reactor 10) at 200 ° C. under the conditions of S / C = 3, temperature 700 ° C., LHSV = 5h −1. The carbon monoxide selective oxidation step (reactor 11) uses a Ru-based catalyst under the conditions of GHSV = 2000h −1 , and is operated under the conditions of O 2 / CO = 3, temperature 150 ° C., and GHSV = 5000h −1. It was. The fuel cell also operated normally and the
[Brief description of the drawings]
FIG. 1 is a schematic view showing an example of a fuel cell system of the present invention.
[Explanation of symbols]
DESCRIPTION OF
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| US9352297B2 (en) | 2013-11-27 | 2016-05-31 | King Fahd University Of Petroleum And Minerals | Methods for preparing composites of activated carbon/zinc oxide and activated carbon/zinc oxide/nickel oxide for desulfurization of fuels |
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| JP4521172B2 (en) * | 2003-09-26 | 2010-08-11 | 出光興産株式会社 | Desulfurization agent and desulfurization method using the same |
| JP2006117921A (en) * | 2004-09-22 | 2006-05-11 | Idemitsu Kosan Co Ltd | Method for removing sulfur from liquid fuel and method for producing hydrogen and fuel battery system |
| JP4922783B2 (en) * | 2006-02-24 | 2012-04-25 | コスモ石油株式会社 | Hydrocarbon desulfurization agent |
| JP4897434B2 (en) * | 2006-11-07 | 2012-03-14 | Ｊｘ日鉱日石エネルギー株式会社 | Kerosene desulfurization agent, desulfurization method, and fuel cell system using the same |
| JP5372338B2 (en) * | 2007-03-30 | 2013-12-18 | Ｊｘ日鉱日石エネルギー株式会社 | Porous desulfurization agent and hydrocarbon oil desulfurization method using the same |
| JP5275114B2 (en) * | 2009-03-31 | 2013-08-28 | Ｊｘ日鉱日石エネルギー株式会社 | Hydrocarbon desulfurization agent and production method thereof, hydrocarbon desulfurization method, and fuel cell system |
| CN102365348A (en) * | 2009-03-31 | 2012-02-29 | 吉坤日矿日石能源株式会社 | Desulfurizing agent precursor for hydrocarbons and method for producing same, fired desulfurizing agent precursor for hydrocarbons and method for producing same, desulfurizing agent for hydrocarbons and method for producing same, method for desulfuri |
| JP5275113B2 (en) * | 2009-03-31 | 2013-08-28 | Ｊｘ日鉱日石エネルギー株式会社 | Hydrocarbon desulfurizing agent precursor and production method thereof, hydrocarbon desulfurization agent firing precursor and production method thereof, hydrocarbon desulfurization agent and production method thereof, hydrocarbon desulfurization method, and fuel cell system |
| JP2010001480A (en) * | 2009-07-17 | 2010-01-07 | Idemitsu Kosan Co Ltd | Desulfurizing agent and desulfurization method using the same |
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| US9352297B2 (en) | 2013-11-27 | 2016-05-31 | King Fahd University Of Petroleum And Minerals | Methods for preparing composites of activated carbon/zinc oxide and activated carbon/zinc oxide/nickel oxide for desulfurization of fuels |
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