成果報告書詳細
管理番号20110000000666
タイトル*平成22年度中間年報 バイオマスエネルギー技術研究開発 戦略的次世代バイオマスエネルギー利用技術開発事業(次世代技術開発) 新規カプセル触媒によるバイオプレミアガソリンの一段合成の研究開発
公開日2011/6/7
報告書年度2010 - 2010
委託先名国立大学法人富山大学 株式会社東産商
プロジェクト番号P10010
部署名新エネルギー部
和文要約和文要約等以下本編抜粋:1.研究開発の内容及び成果等 目的 バイオマス資源から高品位な軽油代替燃料が製造できる技術であるFT合成によるBTL製造技術により、研究開発責任者が保有する「カプセル触媒」の技術を用い、FT合成によって、付加価値が高いプレミアガソリン基材として用いうるイソパラフィンを選択的に高収率で、単段のプロセス(単一の反応器とそこで用いる触媒(カプセル触媒))によって得る技術を開発する。カプセル触媒とはFT合成触媒を覆うゼオライト膜を持つ触媒であり、一段階のFT合成でガソリンに相当するイソパラフィンを合成することができる。
英文要約Research and Development on Biomass Energy Technology
Research and Development on Next-Generation Strategic Biomass Energy Utilization Technology (Next-Generation Technology)
Research and Development on One-Step Synthesis of Bio Premier Gasoline with Novel Capsule Catalyst
Noritatsu Tsubaki, Graduate School of Engineering, University of Toyama
Yoshihito Umemura, Azuma Sansho Co. Ltd
Background and outline
To produce alternative fuels instead of petroleum, this project aims to convert biomass via synthesis gas (CO+H2) to premier gasoline (isoparaffin) with the newly developed multi-functional capsule catalyst, coupled with novel carbonization-gasification technology to obtain tar-free synthesis gas from any kind of raw biomass.
On the first engineering unit, as illustrated above, all kinds of biomass are carbonized to pure carbon by pyrolysis and then soon gasified in situ by the steam, producing very pure synthesis gas. Until now, all reported gasifier to convert biomass to synthesis gas can not solve the formation of tar which is a severe poison to catalysts used at the down-stream synthesis conversion engineering, because raw biomass contacting steam will inevitably produce tar automatically. With our present new method, the tar formation problem can be overcome completely.
After obtaining pure synthesis gas without tar, it is generally converted to diesel without sulfur and aromatics, by Fischer-Tropsch synthesis (FTS) using Co, Ru, or Fe-based catalyst. Different from all previous FTS process, our project here suggests a new process to directly synthesize gasoline (isoparaffin) from synthesis gas using our newly-developed capsule catalyst.
The capsule catalyst consists of FTS catalyst core and acidic zeolite shell where synthesis gas diffuses into core through zeolite shell nanopores smoothly due to its small molecule size, and forms normal paraffin (diesel) with linear shape there. Linear normal paraffin then enters into zeolite channel and is catalyzed by acidic catalytic sites therein to form isoparaffin by hydrocracking and isomerization reaction mechanism, aided by hydrogen in synthesis gas.
During the hydrocracking, some olefin will be produced from normal paraffin decomposition. Accumulation of olefin will deactivate zeolite catalyst and lower quality of final isoparaffin as gasoline. To eliminate olefin, Pd is introduced by several methods to the capsule catalyst, such as loading into core part as Co/Pd/SiO2, to hydrogenate olefin to paraffin with hydrogen in reactant gas in situ.
As compared below, for classic FTS catalyst, Pd addition lowers olefinic hydrocarbon from 20% to 11.8% selectivity. More significantly, for HZSM-5 zeolite encapsulated catalyst, co-existing Pd effectively reduces olefinic hydrocarbon further from 16.5% to 9.9% selectivity, demonstrating the expected role of the loaded Pd.
Pd addition effect on FT hydrocarbon products
catalyst CO
conv. (%) Hydrocarbon sel. (%)
isoparaffin olefin
Co/SiO2 93.5 0 20.0
Co/Pd/SiO2 99.0 0.5 11.8
capsule
HZSM-5/Co/SiO2 93.8 20.8 16.5
capsule
HZSM-5/Co/Pd/SiO2 84.2 22.3 9.9
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