No abstract

The conversion of biomass compounds to aromatics by thermal decomposition in the presence of catalysts was investigated using a pyroprobe analytical pyrolyzer. The first step in this process is the thermal decomposition of the biomass to smaller oxygenates that then enter the catalysts pores where they are converted to CO, CO 2 , water, coke and volatile aromatics. The desired reaction is the conversion of biomass into aromatics, CO 2 and water with the undesired products being coke and water. Both the reaction conditions and catalyst properties are critical in maximizing the desired product selectivity. High heating rates and high catalyst to feed ratio favor aromatic production over coke formation. Aromatics with carbon yields in excess of 30 molar carbon% were obtained from glucose, xylitol, cellobiose, and cellulose with ZSM-5 (Si/Al = 60) at the optimal reactor conditions. The aromatic yield for all the products was similar suggesting that all of these biomass-derived oxygenates go through a common intermediate. At lower catalyst to feed ratios volatile oxygenates are formed including furan type compounds, acetic acid and hydroxyacetaldehyde. The product selectivity is dependent on both the size of the catalyst pores and the nature of the active sites. Five catalysts were tested including ZSM-5, silicalite, beta, Y-zeolite and silica-alumina. ZSM-5 had the highest aromatic yields (30% carbon yield) and the least amount of coke.

Studies in the last decade suggest that microwave energy may have a unique ability to influence chemical processes. These include chemical and materials syntheses as well as separations. Specifically, recent studies have documented a significantly reduced time for fabricating zeolites, mixed oxide and mesoporous molecular sieves by employing microwave energy. In many cases, microwave syntheses have proven to synthesize new nanoporous structures. By reducing the times by over an order of magnitude, continuous production would be possible to replace batch synthesis. This lowering of the cost would make more nanoporous materials readily available for many chemical, environmental, and biological applications. Further, microwave syntheses have often proven to create more uniform (defect-free) products than from conventional hydrothermal synthesis. However, the mechanism and engineering for the enhanced rates of syntheses are unknown. We review the many studies that have demonstrated the enhanced syntheses of nanoporous oxides and analyze the proposals to explain differences in microwave reactions. Finally, the microwave reactor engineering is discussed, as it explains the discrepancies between many microwave studies.

In this paper we report a kinetic model for the dehydration of xylose to furfural in a biphasic batch reactor with microwave heating. There are four key steps in our kinetic model: (1) xylose dehydration to form furfural; (2) furfural reaction to form degradation products; (3) furfural reaction with xylose to form degradation products, and (4) mass transfer of furfural from the aqueous phase into the organic phase (methyl isobutyl ketone -MIBK). This kinetic model was used to fit experimental data collected in this study. The apparent activation energy for xylose dehydration is higher than the apparent activation energy for the degradation reactions. The biphasic system does not alter the fundamental kinetics in the aqueous phase. The organic layer, which serves as "storage" for the extracted furfural, is crucial to maximize product yield. Microwave heating does not change the kinetics compared to heating by conventional means. We use our model to describe the optimal reaction conditions for furfural production. These conditions occur in a biphasic regime at higher temperatures (i.e. 170• C) and short reaction times.We estimate that at these conditions furfural yields in a biphasic system can reach 85%. At these same conditions in a monophase system furfural yields are only 30%.

No abstract