Chemistry of Furan Conversion into Aromatics and Olefins over HZSM-5: A Model Biomass Conversion Reaction

被引:288
作者
Cheng, Yu-Ting [1 ]
Huber, George W. [1 ]
机构
[1] Univ Massachusetts, Dept Chem Engn, Goessmann Lab 159, Amherst, MA 01003 USA
来源
ACS CATALYSIS | 2011年 / 1卷 / 06期
关键词
furan; catalytic fast pyrolysis; biomass; aromatics; olefins; zeolites; HZSM-5; hydrocarbon pool; TEMPERATURE-PROGRAMMED DESORPTION; CATALYTIC FAST PYROLYSIS; FIXED-BED REACTOR; LIQUID FUEL; BIO-OIL; PRODUCT DISTRIBUTION; DESIGN PARAMETERS; ZEOLITE; HYDROCARBONS; ADSORPTION;
D O I
10.1021/cs200103j
中图分类号
O64 [物理化学(理论化学)、化学物理学];
学科分类号
070304 ; 081704 ;
摘要
The conversion of furan (a model of cellulosic biomass) over HZSM-5 was investigated in a thermogravimetric analysis-mass spectrometry system, in situ Fourier transform infrared analysis, and in a continuous-flow fixed-bed reactor. Furan adsorbed as oligomers at room temperature with a 1.73 of adsorbed furan/A1 ratio. These oligomers were polycyclic aromatic compounds that were converted to CO, CO2, aromatics, and olefins at temperatures from 400 to 600 degrees C. Aromatics (e:g:, benzene, toluene, and naphthalene), oligomer isomers (e.g., benzofuran, 2,2-methylenebisfuran, and benzodioxane), and heavy oxygenates (C12+ oligomers) were identified as intermediates formed inside HZSM-5 at different reaction temperatures. During furan conversion, graphite-type coke formed on the catalyst surface, which caused the aromatics and olefins formation to deactivate within the first 30 mm of time on stream We have measured the effects of space velocity and temperature for furan conversion to help us understand the chemistry of biomass conversion inside zeolite catalysts. The major products for furan conversion included CO, CO2, allene, C-2-C-6 olefins, benzene, toluene, styrene, benzofuran, indene, and naphthalene. The aromatics (benzene and toluene) and olefins (ethylene and propylene) selectivity decreased with increasing space velocity. Unsaturated hydrocarbons such as allene, cyclopentadiene, and aromatics selectivity increased with increasing space velocity. The product distribution was selective to olefins and CO at high temperatures (650 degrees C) but was selective to aromatics (benzene and toluene) at intermediate temperatures (450-600 degrees C). At low temperatures (450 degrees C), benzofuran and coke contributed 60% of the carbon selectivity. Several different reactions were occurring for furan conversion over zeolites. Some important reactions that we have identified in this study include Diels-Alder condensation (e.g., two furans form benzofuran and water), decarbonylation (e.g., furan forms CO and allene), oligomerization (allene forms olefins and aromatics plus hydrogen), and alkylation (e.g., furan plus olefins). The product distribution was far from thermodynamic equilibrium.
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收藏
页码:611 / 628
页数:18
相关论文
共 77 条
[51]   The critical role of heterogeneous catalysis in lignocellulosic biomass conversion [J].
Lin, Yu-Chuan ;
Huber, George W. .
ENERGY & ENVIRONMENTAL SCIENCE, 2009, 2 (01) :68-80
[52]   Biocommodity engineering [J].
Lynd, LR ;
Wyman, CE ;
Gerngross, TU .
BIOTECHNOLOGY PROGRESS, 1999, 15 (05) :777-793
[53]   The conversion of methanol to hydrocarbons over zeolite H-beta [J].
Mikkelsen, O ;
Kolboe, S .
MICROPOROUS AND MESOPOROUS MATERIALS, 1999, 29 (1-2) :173-184
[54]   Space- and Time-Resolved In-situ Spectroscopy on the Coke Formation in Molecular Sieves: Methanol-to-Olefin Conversion over H-ZSM-5 and H-SAPO-34 [J].
Mores, Davide ;
Stavitski, Eli ;
Kox, Marianne H. F. ;
Kornatowski, Jan ;
Olsbye, Unni ;
Weckhuysen, Bert M. .
CHEMISTRY-A EUROPEAN JOURNAL, 2008, 14 (36) :11320-11327
[55]   Kinetic study of fast pyrolysis of sawdust in a conical spouted bed reactor in the range 400-500°C [J].
Olazar, M ;
Aguado, R ;
San José, MJ ;
Bilbao, J .
JOURNAL OF CHEMICAL TECHNOLOGY AND BIOTECHNOLOGY, 2001, 76 (05) :469-476
[56]   TRANSFORMATION OF LOWER ALKANES INTO AROMATIC-HYDROCARBONS OVER ZSM-5 ZEOLITES [J].
ONO, Y .
CATALYSIS REVIEWS-SCIENCE AND ENGINEERING, 1992, 34 (03) :179-226
[57]   ACETYLENE POLYMERIZATION IN A H-ZSM-5 ZEOLITE [J].
PEREIRA, C ;
KOKOTAILO, GT ;
GORTE, RJ .
JOURNAL OF PHYSICAL CHEMISTRY, 1991, 95 (02) :705-709
[58]   Modeling of gas transport in a microporous solid using a slice selection procedure: Application to the diffusion of benzene in ZSM5 [J].
Petryk, Michel ;
Leclerc, Sebastien ;
Canet, Daniel ;
Fraissard, Jacques .
CATALYSIS TODAY, 2008, 139 (03) :234-240
[59]   ADSORPTION OF AROMATIC-HYDROCARBONS IN NAX ZEOLITE .2. KINETICS [J].
RUTHVEN, DM ;
KAUL, BK .
INDUSTRIAL & ENGINEERING CHEMISTRY RESEARCH, 1993, 32 (09) :2053-2057
[60]   Methylbenzene chemistry on zeolite HBeta: Multiple insights into methanol-to-olefin catalysis [J].
Sassi, A ;
Wildman, MA ;
Ahn, HJ ;
Prasad, P ;
Nicholas, JB ;
Haw, JF .
JOURNAL OF PHYSICAL CHEMISTRY B, 2002, 106 (09) :2294-2303