The production of butene from the ring-opening and decarboxylation of γ-valerolactone over solid acid materials: the characterization, design, and kinetics of stable catalysts

Date of Award


Degree Type


Degree Name

Master of Science (MS)


Biomedical and Chemical Engineering


Jesse Q. Bond


Chemical engineering

Subject Categories

Chemical Engineering


The lignocellulosic based molecule, γ-Valerolactone (GVL), has been identified as a promising platform chemical because, in addition to serving directly as a fuel additive or green solvent, it has a number of derivatives with applications towards fuel additives, high value chemicals, polymer precursors, or directly as biofuels. A strategy of producing renewable transportation fuels has been proposed by Bond et al. where alkenes produced from the decarboxylation of γ-valerolactone (GVL) are oligomerized into higher molecular weight alkenes (Bond et al., 2010a). However, the decarboxylation of GVL over a solid acid catalyst, such as amorphous silica-alumina (ASA) leads to significant catalyst deactivation during the reaction. The solid acids H-ZSM5, ASA, niobia, niobium phosphate, and sulfated zirconia, were all tested for GVL decarboxylation. The aluminosilicate materials exhibited the highest initial activity; but varying degrees of catalyst deactivation lowered the overall performance of the materials. To better understand the properties that influence catalyst activity and stability, series of ASA and sodium exchanged H-ZSM5 samples were also investigated. The initial rate of GVL decarboxylation was found to generally increase with Brønsted acid site density across the materials; but a more meaningful correlation was obtained when materials of equivalent acid strength were compared. Additionally, it was realized that catalyst deactivation in the GVL reaction system is solely a physical phenomenon and can therefore be influenced by tailoring certain physical properties. Ultimately it was determined that an ideal catalyst for GVL decarboxylation should have an aluminosilicate framework, a high density of Brønsted acid sites, strong acid strength, and mesoporous sized pores. From these criteria, it is suggested that a tailored ASA, aluminum-containing MCM-41, or Amberlyst-70 would be well suited for GVL decarboxylation.


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