Mixed Alcohol Dehydration over Bronsted and Lewis Acidic Catalysts [electronic resource]

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Ngôn ngữ: eng

Ký hiệu phân loại: 664.8 Fruits and vegetables

Thông tin xuất bản: Washington, D.C. : Oak Ridge, Tenn. : United States. Dept. of Energy. Office of Energy Efficiency and Renewable Energy ; Distributed by the Office of Scientific and Technical Information, U.S. Dept. of Energy, 2015

Mô tả vật lý: Size: p. 110-124 : , digital, PDF file.

Bộ sưu tập: Metadata

ID: 263569

 Mixed alcohols are attractive oxygenated products of biomass-derived syngas because they may be catalytically converted to a range of hydrocarbon products, including liquid hydrocarbon fuels. Catalytic dehydration to form olefins is a potential first step in the conversion of C<
 sub>
 2<
 /sub>
 ?C<
 sub>
 4<
 /sub>
  alcohols into longer-chain hydrocarbons. Here, we describe the physical and chemical characterization along with catalytic activity and selectivity of 4 Br�nsted and Lewis acidic catalysts for the dehydration of two mixed alcohol feed streams that are representative of products from syngas conversion over K-CoMoS type catalysts (i.e., ethanol, 1-propanol, 1-butanol and 2-methyl-1-propanol). Specifically, a Lewis acidic Zr-incorporated mesoporous silicate (Zr-KIT-6), a commercial Al-containing mesoporous silicate (Al-MCM-41), a commercial microporous aluminosilicate (HZSM-5), and a commercial microporous silicoaluminophosphate (SAPO-34) were tested for mixed alcohol dehydration at 250, 300 and 350 �C. The zeolite materials exhibited high activity (>
 98% ethanol conversion) at all temperatures while the mesoporous materials only displayed significant activity (>
 10% ethanol conversion) at or above 300 �C. The turnover frequencies for ethanol dehydration at 300 �C decreased in the following order: HZSM-5 >
  SAPO-34 >
  Al-MCM-41 >
  Zr-KIT-6, suggesting that Br�nsted acidic sites are more active than Lewis acidic sites for alcohol dehydration. At 300 �C, SAPO-34 produced the highest yield of olefin products from both a water-free ethanol rich feed stream and a C<
 sub>
 3+<
 /sub>
 -alcohol rich feed stream containing water. Post-reaction characterization indicated changes in the Br�nsted-to-Lewis acidic site ratios for Zr-KIT-6, Al-MCM-41 and HZSM-5. Ammonia temperature programmed desorption indicated that the acid sites of post-reaction samples could be regenerated following treatment in air. The post-reaction SAPO-34 catalyst contained more aromatic, methylated aromatic and polyaromatic compounds than its zeolite counterpart HZSM-5, while no aromatic compounds were observed on post-reaction Al-MCM-41 or Zr-KIT-6 catalysts. Olefin yield at 300 �C over SAPO-34 (>
 95%) was comparable to published values for the methanol-to-olefins process, indicating the potential industrial application of mixed alcohol dehydration. Furthermore, the olefin product distribution over SAPO-34 was tunable by the composition of the alcohol feed mixture.
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