成果報告書詳細
管理番号20100000001266
タイトル*平成21年度中間年報 新エネルギー技術研究開発 バイオマスエネルギー等高効率転換技術開発(先導技術開発) セルロース系バイオマスエタノールからプロピレンを製造するプロセス開発 (独立行政法人産業技術総合研究所)
公開日2010/9/9
報告書年度2009 - 2009
委託先名独立行政法人産業技術総合研究所
プロジェクト番号P07015
部署名新エネルギー技術開発部
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 本研究では、2015-2020年頃の実用化をめざし、セルロース系エタノールからプロピレンを製造するための触媒開発、反応および分離精製プロセス開発を行う。本事業の目的を達成するための主な開発項目は、1)エタノールを直接プロピレンへ化学変換する高性能で長寿命の触媒を開発し、その評価を行うこと、2)原料中に存在する触媒被毒成分の分離除去、およびポリマーグレードのプロピレンを触媒反応生成物から分離精製する技術を開発すること、3)上記触媒および分離精製工程を含むコスト競争力のあるプロセスを開発し、ベンチプラントの設計を行うことである。
英文要約Title: Development of technologies to produce propylene from cellulosic ethanol (FY2008-2010) FY2009 Annual Report.
In the project, the following technologies will be developed, 1) development of high-performance and long-lifetime catalysts to convert cellulosic ethanol to propylene, 2) separation technologies to remove catalytic poison in bio-ethanol or produced olefins, 3) process design of a bench plant to produce polymer-grade propylene.1) Catalyst performances of MFI-type H-ZSM-5 zeolite with Si/Al2 ratio between 20 and 80 were examined. Addition of some transition metals was effective. Decrease in propylene selectivity was associated with carbon deposition and catalyst regeneration by air caused zeolite degradation. In high silica-type H-ZSM-5 zeolite with Si/Al2 ratio of 280, the propylene STY was lower than that of low silica-H-ZSM-5 (Si/Al2=50), but propylene selectivity and catalyst stability were a little better than low silica-type and additives such as La and W were also effective. In order to get information on ethylene/C4 recycle, isobutene/H2O was added to ethanol using H-ZSM-5 (280), and the propylene selectivity and catalyst stability were improved with C3’/C2’=0.95 and C3’+C2’=60-70%.The yield of ethylene increased with P/Al ratio, while the yields of higher hydrocarbon (>C5) and paraffins decreased, considering that the strong acidic sites were decreased by the modification of phosphorous. The addition of phosphorus to ZSM-5 improved the catalytic durability for the ethanol conversion. The dealumination from ZSM-5 structure was drastically suppressed by the modification of phosphorous.2) The sufuric impurities in six kinds of crude ethanol were examined. One from Brazil and one from China contained sulfur at 2-3 ppm by weight as dimethylsulfoxide or dimethylsulfide. Gas-phase adsorptive desulfurization of propylene was investigated by employing commercial zeolite and activated carbon with different porous characteristics. For sulfur impurities, such as hydrogen sulfide, methanethiol, and ethanethiol, the adsorption performance of zeolite was higher than that of activated carbon. By exchanging a sodium cation in the pores of zeolite with a zinc cation, the adsorption selectivity of the zeolite for methanethiol was significantly improved.We have examined the dehydration properties of olefins using two types of carbon hollow fiber membrane modules with the mean pore size of 0.3 nm and 0.4 nm. The carbon membrane having smaller pore size showed higher performance due to the inhibition of olefin adsorption into the pores. In addition, this membrane had enough pressure resistance of 4 MPa under ethylene atmosphere.3) We decided the reaction mechanism and kinetic parameter in the propylene synthesis from the ethanol over ZSM-5 catalyst. Based on these kinetic data, we designed a micro reactor with the scale of 10 kg/day. A process flow diagram was created for the plant where polymer-grade propylene was produced from bio-ethanol.
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