The increasing demands placed on natural resources for fuel and food production require that we explore the use of efficient, sustainable feedstocks such as brown macroalgae. The full potential of brown macroalgae as feedstocks for commercial-scale fuel ethanol production, however, requires extensive re-engineering of the alginate and mannitol catabolic pathways in the standard industrial microbe Saccharomyces cerevisiae. Here we present the discovery of an alginate monomer (4-deoxy-L-erythro-5-hexoseulose uronate, or DEHU) transporter from the alginolytic eukaryote Asteromyces cruciatus. The genomic integration and overexpression of the gene encoding this transporter, together with the necessary bacterial alginate and deregulated native mannitol catabolism genes, conferred the ability of an S. cerevisiae strain to efficiently metabolize DEHU and mannitol. When this platform was further adapted to grow on mannitol and DEHU under anaerobic conditions, it was capable of ethanol fermentation from mannitol and DEHU, achieving titres of 4.6% (v/v) (36.2 g l(-1)) and yields up to 83% of the maximum theoretical yield from consumed sugars. These results show that all major sugars in brown macroalgae can be used as feedstocks for biofuels and value-added renewable chemicals in a manner that is comparable to traditional arable-land-based feedstocks.

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Electrocatalytic hydrogenation (ECH) of guaiacol for production of chemical and fuel in a divided cell using earth abundant metal electrodes. Specific energies shown below the organics are their higher heating values (HHV).

Catalytic conversion of lactic acid to 2,3-pentanedione over sodium salts and base on low surface area silica support has been studied. Yield and selectivity toward 2,3-pentanedione are optimal at around 300 °C, 3−4 s residence time, and 0.5 MPa total pressure. Anions of initial salt catalysts used do not participate in lactic acid condensation to 2,3-pentanedione once steady-state conditions have been achieved; instead, sodium lactate has been identified by postreaction FTIR spectroscopy as the primary, stable species on the support during reaction. Sodium lactate is believed to be an intermediate in 2,3-pentanedione formation. Conversion of a sodium salt to sodium lactate is greatest when the salt used has a low melting point and a volatile conjugate acid; the extent of conversion depends weakly on reaction time and temperature within experimental conditions. At high temperature (∼350 °C), sodium lactate decomposes to sodium propanoate and sodium acetate, which may explain reduced 2,3-pentanedione yields at higher temperatures.

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Reaction kinetics are presented for the reversible esterification reaction of citric acid with ethanol to form tri-ethyl citrate via mono-ethyl and di-ethyl citrates. The reaction was studied in batch isothermal experiments, self-catalyzed homogeneously by citric acid and the formed mono-and di-ethyl citrates, and heterogeneously catalyzed by macroporous Amberlyst-15 ion-exchange resin catalyst. Experimental data were obtained between 78 and 120 °C at different mole ratios of ethanol to citric acid and catalyst concentrations up to 5 wt % ion-exchange resin. The kinetics of ethanol etherification to form di-ethyl ether were included in the investigation. Kinetic modeling was performed using a pseudo-homogeneous UNIQUAC-based activity model, taking into consideration the rate of self-catalyzed esterification and the side reaction to form diethyl ether. The activity coefficients for the tri-ethyl citrate-ethanol and tri-ethyl citrate-water binary pairs were obtained from experimental vapor-liquid equilibrium data. Kinetics of the di-ethyl citrate to tri-ethyl citrate reaction limit the overall tri-ethyl citrate formation rate, as citric acid and mono-ethyl citrate are esterified rapidly to their equilibrium compositions. Higher temperatures lead to faster reaction kinetics but significantly increase the production of the undesired byproduct di-ethyl ether. The kinetic model developed is useful for the design and simulation of processes such as reactive distillation for tri-ethyl citrate formation.

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