C. Luke Williams

Ultra-selective cycloaddition of dimethylfuran for renewable p-xylene with H-BEA

p-Xylene, the precursor for PET bottles, was synthesized at 90% yield by [4 + 2] cycloaddition of biomass-derived ethylene and dimethylfuran followed by subsequent dehydration with Beta zeolite.

Aerosol generation by reactive boiling ejection of molten cellulose

The generation of primary aerosols from biomass hinders the production of biofuels by pyrolysis, intensifies the environmental impact of forest fires, and exacerbates the health implications associated with cigarette smoking. High speed photography is utilized to elucidate the ejection mechanism of aerosol particles from thermally decomposing cellulose at the timescale of milliseconds. Fluid modeling, based on first principles, and experimental measurement of the ejection phenomenon supports the proposed mechanism of interfacial gas bubble collapse forming a liquid jet which subsequently fragments to form ejected aerosol particles capable of transporting nonvolatile chemicals. Identification of the bubble-collapse/ejection mechanism of intermediate cellulose confirms the transportation of nonvolatile material to the gas phase and provides fundamental understanding for predicting the rate of aerosol generation.

Fast Pyrolysis of Wood for Biofuels: Spatiotemporally Resolved Diffuse Reflectance In situ Spectroscopy of Particles

Fast pyrolysis of woody biomass is a promising process capable of producing renewable transportation fuels to replace gasoline, diesel, and chemicals currently derived from nonrenewable sources. However, biomass pyrolysis is not yet economically viable and requires significant optimization before it can contribute to the existing oil-based transportation system. One method of optimization uses detailed kinetic models for predicting the products of biomass fast pyrolysis, which serve as the basis for the design of pyrolysis reactors capable of producing the highest value products. The goal of this work is to improve upon current pyrolysis models, usually derived from experiments with low heating rates and temperatures, by developing models that account for both transport and pyrolysis decomposition kinetics at high heating rates and high temperatures (>400 °C). A new experimental technique is proposed herein: spatiotemporally resolved diffuse reflectance in situ spectroscopy of particles (STR-DRiSP), which is capable of measuring biomass composition during fast pyrolysis with high spatial (10 μm) and temporal (1 ms) resolution. Compositional data were compared with a comprehensive 2D single-particle model, which incorporated a multistep, semiglobal reaction mechanism, prescribed particle shrinkage, and thermophysical properties that varied with temperature, composition, and orientation. The STR-DRiSP technique can be used to determine the transport-limited kinetic parameters of biomass decomposition for a wide variety of biomass feedstocks.

Kinetic regimes in the tandem reactions of H-BEA catalyzed formation of p-xylene from dimethylfuran

Reaction kinetics and pathways of p-xylene formation from 2,5-dimethylfuran (DMF) and ethylene via cascade reactions of Diels–Alder cycloaddition and subsequent dehydration over H-BEA zeolite (Si/Al = 12.5) were characterized. Two distinct kinetic regimes were discovered corresponding to the rate limiting reaction, namely Diels–Alder cycloaddition and cycloadduct dehydration, as the concentration of Bronsted acid sites decreases. At catalyst loadings with effective acid site concentrations exceeding a critical value (~2.0 mM), the rate of formation of Diels–Alder products becomes constant. Under these conditions, the measured activation energy of 17.7 ± 1.4 kcal mol−1 and reaction orders correspond to the [4 + 2] Diels–Alder cycloaddition reaction of DMF and ethylene. Conversely, at catalyst loadings below the critical value, the formation rate of p-xylene becomes first order in catalyst loading, and the measured activation energy of 11.3 ± 3.5 kcal mol−1 is consistent with dehydration of the Diels–Alder cycloadduct to p-xylene. Experimental comparison between H-BEA and H-Y zeolite catalysts at identical conditions indicates that the micropore structure controls side reactions such as furan dimerization and hydrolysis; the latter is supported via molecular simulation revealing a substantially higher loading of DMF within H-Y than within H-BEA zeolites at reaction conditions.

Aqueous-phase hydrodeoxygenation of highly oxygenated aromatics on platinum

Utilization of renewable sugars from biomass by a hybrid chemical process produces highly oxygenated aromatic compounds, such as phloroglucinol, which require catalytic reduction for desirable aromatic products. Aqueous phase hydrodeoxygenation of phloroglucinol on carbon-supported platinum produces resorcinol, phenol, cyclohexanol, cyclohexanone, and 1,3-cyclohexanediol by combinations of carbon–oxygen bond cleavage and carbon–carbon double bond hydrogenation. Carbon–carbon σ-bond cleavage was not observed. Hydrodeoxygenation was the primary reaction of phloroglucinol, leading to the production of resorcinol in the overall rate-limiting reaction, with an activation energy barrier of Ea = 117 kJ mol−1. Subsequent reactions of resorcinol produced 1,3-cyclohexanediol and phenol with similar energy barriers, Ea = 46 and Ea = 54 kJ mol−1, respectively. Further hydrogenation of phenol (Ea = 42 kJ mol−1) occurs through the intermediate, cyclohexanone, which is further reduced (Ea = 14 kJ mol−1) to the dominant product, cyclohexanol.

Biomass Compositional Analysis for Conversion to Renewable Fuels and Chemicals

As the world continues to deplete its nonrenewable resources, there has begun a shift toward using renewable materials for the production of fuels and chemicals. Terrestrial biomass, as well as municipal solid wastes, provides renewable feedstocks for fuel and chemical production. However, one of the major challenges to using biomass as a feedstock for fuel and chemical production is the great amount of innate variability between different biomass types and within individual biomass species. This inconsistency arises from varied growth and harvesting conditions and presents challenges for conversion processes, which frequently require physically and chemically uniform materials. This chapter will examine intrinsic biomass compositional characteristics including cellulose, hemicellulose, lignin, extractives/volatiles, and ash for a wide array of biomass types. Additionally, extrinsic properties, such as moisture content and particle grind size, will be examined for their effect on biomass conversion to fuels using four major conversion processes: direct combustion, pyrolysis, hydrothermal liquefaction, and fermentation. A brief discussion on recent research for the production of building block chemicals from biomass will also be presented.