James A. Dumesic | AIChE

James A. Dumesic

University of Wisconsin-Madison

James A. Dumesic earned his B.S. degree from UW-Madison and his M.S. and Ph.D. degrees from Stanford University, under the supervision of Professor Michel Boudart.  Dumesic joined the Department of Chemical Engineering in 1976, and he is currently the Steenbock Chair in the College of Engineering and the Michel Boudart Professor of Chemical and Biological Engineering.  Throughout his career, Dumesic has used spectroscopic, microcalorimetric, and reaction kinetics techniques to study the surface and dynamic properties of heterogeneous catalysts.  Dumesic pioneered the field of microkinetic analysis, in which diverse information from experimental and theoretical studies is combined to elucidate the essential surface chemistry that controls catalyst performance.  He has recently studied how aqueous-phase reforming of biomass-derived carbohydrates can be tailored to selectively produce H2 or directed to produce liquid hydrocarbons.  Most recently, he has been studying the use of furan compounds, levulinic acid, and gamma-valerolactone as biomass-derived platform chemicals for the production of fuels and chemicals.   Dumesic has received a variety of awards and honors in the field of catalysis and chemical engineering.  In 1998, he was elected to the National Academy of Engineering.  In 2006, he received the Somorjai Award for Creative Research in Catalysis from the American Chemical Society.  In 2007 he was awarded the Burwell National Lectureship by the North American Catalysis Society.  In 2008, he received the Hilldale Award for distinguished professional accomplishment at the University of Wisconsin, and he received the inaugural Heinz Heinemann Award by the International Association of Catalysis Societies.  He was elected as a Fellow of the American Academy of Arts and Sciences in 2009, and he was awarded the William H. Walker Award of the American Institute of Chemical Engineers for outstanding contributions to the chemical engineering literature.  In 2011 he received the Michel Boudart Award for advances in catalysis at the North American Catalysis Meeting and at the meeting of the European Federation of Catalysis Societies.  In 2012 he received the George A. Olah Award in Hydrocarbon or Petroleum Chemistry from the American Chemical Society.

Over the past 10 years, Dumesic and his group have elucidated the fundamental surface chemistry involved in the catalytic conversion of biomass-derived compounds to fuels and chemicals. In addition, Dumesic and his group have developed new catalytic processing strategies and novel reactor configurations to achieve the selective transformation of biomass-derived reactants to targeted platform chemical intermediates, such as furfural, hydroxymethylfurfural, levulinic acid, and gamma-valerolactone (GVL).  These platform molecules form the basis for a “bio-refinery” in which renewable biomass resources can be converted in a flexible manner to high-volume fuels and/or lower volume, higher values chemicals. During the past year, Dumesic and his group have focused attention on developing new methods to implement their bio-refinery concepts for real biomass feedstocks, including hemi-cellulose, cellulose, and lignin.  For example, they have shown that alkylphenol compounds, such as sec-butylphenol, form a class of solvents that is effective for the selective extraction of furfural, hydroxymethylfurfural, and levulinic acid from aqueous solutions of mineral acids (e.g., sulfuric acid), allowing these acid catalysts to be used for deconstruction of hemi-cellulose and cellulose, followed by extraction of the reaction products, and completed by recycle of the mineral acids for further cycles of biomass deconstruction.  In addition, Dumesic and his group have developed new bimetallic catalysts that operate effectively in the presence of alkylphenol solvents, such as for the selective conversion of levulinic acid to GVL, the latter being a valuable chemical that can be removed from the less-volatile alkylphenol solvent by distillation.  An important recent advance in this direction was the report by Dumesic and his group that alkylphenol solvents could be produced by catalytic conversion of lignin. In particular, they showed that the lignin in poplar wood could be converted to a mixture of propylguiacol and propylsyringol, and this lignin-derived solvent was as effective as petroleum-derived sec-butylphenol for use in the biphasic conversion of hemi-cellulose to furfural, and the conversion of cellulose to hydroxymethylfurfural, levulinic acid, and GVL.  An important aspect of work by the Dumesic group in the use of alkylphenol solvents in biomass processing is the catalytic conversion of glucose in high yields (62%) to hydroxymethylfurfural (HMF), a versatile platform chemical. In this work they employed a reaction system consisting of a Lewis acid metal chloride (e.g., AlCl3) and a Brønsted acid (HCl) in a biphasic reactor consisting of water and an alkylphenol compound (2-sec-butylphenol) as the organic phase. The conversion of glucose in the presence of Lewis and Brønsted acidity proceeds through a tandem pathway involving isomerization of glucose to fructose, followed by dehydration of fructose to HMF. The organic phase extracts 97% of the HMF produced, while both acid catalysts remain in the aqueous phase.  Importantly, they showed how the valuable HMF product could be removed from the alkylphenol solvent by contacting the solvent with water and hexane, whereby the addition of hexane partitions the more hydrophilic HMF product to the aqueous phase.  We note here that the conversion of renewable resources to HMF is becoming of major interest in the academic and industrial communities, because HMF can be oxidized to furandicarboxylic acid (FDCA), and the latter can be used to produce a plastic bottle that has better properties than PET (i.e., lower permeability of CO2 for the storage of carbonated beverages).

In addition to their work involving the synthesis of new solvents from lignin, Dumesic and his group have recently developed new catalytic processing strategies using GVL as a biomass-derived solvent.  For example, they employed a biphasic reaction systems consisting of GVL and a reactive aqueous solution to achieve high yields of levulinic and formic acids (e.g., 70%) from cellulose.  This approach leads to complete solubilization of cellulose, including cellulose degradation species (i.e., humins) that are problematic in conventional biomass processing methods.  The GVL solvent extracts the majority of the levulinic acid, which can subsequently be converted to GVL over a carbon-supported Ru-Sn catalyst. This approach for cellulose conversion eliminates the need to separate the final product from the solvent, because the GVL product is the solvent.  It is important to note that Dumesic’s previous work has shown that GVL have be converted with high yields by decarboxylation over an acid catalyst to produce butene, and butene can undergo dimerization to gasoline or oligomerization to jet fuel compounds.   In recent work, Dumesic and his group have continued to exploit the use of GVL as a solvent by demonstrating a new processing strategy which utilizes solid acid catalysts (i.e., H-mordenite) to produce furfural from hemi-cellulose xylose at high yields (80%) a monophasic system using GVL as a solvent with minimal water. They show that furfural degradation reactions, especially condensation reactions between furfural and sugar intermediates, are decreased significantly when the concentration of water in the GVL solvent is minimized. They also demonstrated that their strategy can be applied in a pulp and paper manufacturing facility to convert xylose and its oligomers in hemicellulose waste streams (i.e., pre-hydrolysis liquors) to furfural with high yields, while trace amounts of glucose and oligomers are converted simultaneously to valuable products such as furfural, 5-hydroxymethylfurfural and levulinic acid.