Increasing energy demand, especially in the transportation sector, and soaring CO2 emissions necessitate the exploitation of renewable sources of energy. Despite the large variety of new energy carriers, liquid hydrocarbon still appears to be the most attractive and feasible form of transportation fuel taking into account the energy density, stability and existing infrastructure. Biomass is an abundant, renewable source of energy; however, utilizing it in a cost-effective way is still a substantial challenge. Lignocellulose is composed of three major biopolymers, namely cellulose, hemicellulose and lignin. Fast pyrolysis of biomass is recognized as an efficient and feasible process to selectively convert lignocellulose into a liquid fuel-bio-oil. However bio-oil from fast pyrolysis contains a large amount of oxygen, distributed in hundreds of oxygenates. These oxygenates are the cause of many negative properties, such as low heating value, high corrosiveness, high viscosity, and instability; they also greatly limit the application of bio-oil particularly as transportation fuel. Hydrocarbons derived from biomass are most attractive because of their high energy density and compatibility with the existing infrastructure. Thus, converting lignocellulose into transportation fuels via catalytic fast pyrolysis has attracted much attention. Many studies related to catalytic fast pyrolysis of biomass have been published. The main challenge of this process is the development of active and stable catalysts that can deal with a large variety of decomposition intermediates from lignocellulose. This review starts with the current understanding of the chemistry in fast pyrolysis of lignocellulose and focuses on the development of catalysts in catalytic fast pyrolysis. Recent progress in the experimental studies on catalytic fast pyrolysis of biomass is also summarized with the emphasis on bio-oil yields and quality.
With increased availability and decreased cost, ethanol is potentially a promising platform molecule for the production of a variety of value-added chemicals. In this review, we provide a detailed summary of recent advances in catalytic conversion of ethanol to a wide range of chemicals and fuels. We particularly focus on catalyst advances and fundamental understanding of reaction mechanisms involved in ethanol steam reforming (ESR) to produce hydrogen, ethanol conversion to hydrocarbons ranging from light olefins to longer chain alkenes/alkanes and aromatics, and ethanol conversion to other oxygenates including 1-butanol, acetaldehyde, acetone, diethyl ether, and ethyl acetate.
We report the design and synthesis of nanosized Zn(x)Zr(y)O(z) mixed oxides for direct and high-yield conversion of bio-ethanol to isobutene (~83%). ZnO is addded to ZrO(2) to selectively passivate zirconia's strong Lewis acidic sites and weaken Brönsted acidic sites, while simultaneously introducing basicity. As a result, the undesired reactions of bio-ethanol dehydration and acetone polymerization/coking are suppressed. Instead, a surface basic site-catalyzed ethanol dehydrogenation to acetaldehyde, acetaldehyde to acetone conversion via a complex pathway including aldol-condensation/dehydrogenation, and a Brönsted acidic site-catalyzed acetone-to-isobutene reaction pathway dominates on the nanosized Zn(x)Zr(y)O(z) mixed oxide catalyst, leading to a highly selective process for direct conversion of bio-ethanol to isobutene.
A novel in situ autoreduction route has been developed, by which monodispersed silver nanoparticles with tunable sizes could be easily fabricated on silica-based materials, especially inside the channels of mesoporous silica (MPS). 13C CP/MAS NMR spectroscopy was employed to monitor the whole assembly process. It was demonstrated that the amino groups of APTS (aminopropyltriethoxyl silane)-modified MPS can be used to anchor formaldehyde to form novel reducing species (NHCH2OH), on which Ag(NH3)2NO3 could be in situ reduced. Monodispersed silver nanoparticles were thus obtained. In situ XRD and in situ TEM experiments were used to investigate and compare the thermal stabilities of silver nanoparticles on the external surface of silica gels (unconfined) and those located inside the channels of SBA-15 (confined). It was observed that unconfined silver nanoparticles tended to agglomerate at low temperatures (i.e., lower than 773 K). The aggregation of silver nanoparticles became more serious at 773 K. However, for those confined silver nanoparticles, no coarsening process was observed at 773 K, much higher than its Tammann temperature (i.e., 617 K). Only when the treating temperature was higher than 873 K could the agglomeration of those confined silver nanoparticles happen with time-varying via the Ostwald ripening process. The confinement of mesopores played a key role in improving the thermal stabilities of silver nanoparticles (stable up to 773 K without any observable coarsening), which is essential to the further investigations on their chemical (e.g., catalytic) properties.
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