Novel pathways for fuels and lubricants from biomass optimized using life-cycle greenhouse gas assessment.

Decarbonizing the transportation sector is critical to achieving global climate change mitigation. Although biofuels will play an important role in conventional gasoline and diesel applications, bioderived solutions are particularly important in jet fuels and lubricants, for which no other viable renewable alternatives exist. Producing compounds for jet fuel and lubricant base oil applications often requires upgrading fermentation products, such as alcohols and ketones, to reach the appropriate molecular-weight range. Ketones possess both electrophilic and nucleophilic functionality, which allows them to be used as building blocks similar to alkenes and aromatics in a petroleum refining complex. Here, we develop a method for selectively upgrading biomass-derived alkyl methyl ketones with >95% yields into trimer condensates, which can then be hydrodeoxygenated in near-quantitative yields to give a new class of cycloalkane compounds. The basic chemistry developed here can be tailored for aviation fuels as well as lubricants by changing the production strategy. We also demonstrate that a sugarcane biorefinery could use natural synergies between various routes to produce a mixture of lubricant base oils and jet fuels that achieve net life-cycle greenhouse gas savings of up to 80%.

Highly selective condensation of biomass-derived methyl ketones as a source of aviation fuel.

Aviation fuel (i.e., jet fuel) requires a mixture of C9 -C16 hydrocarbons having both a high energy density and a low freezing point. While jet fuel is currently produced from petroleum, increasing concern with the release of CO2 into the atmosphere from the combustion of petroleum-based fuels has led to policy changes mandating the inclusion of biomass-based fuels into the fuel pool. Here we report a novel way to produce a mixture of branched cyclohexane derivatives in very high yield (>94 %) that match or exceed many required properties of jet fuel. As starting materials, we use a mixture of n-alkyl methyl ketones and their derivatives obtained from biomass. These synthons are condensed into trimers via base-catalyzed aldol condensation and Michael addition. Hydrodeoxygenation of these products yields mixtures of C12 -C21 branched, cyclic alkanes. Using models for predicting the carbon number distribution obtained from a mixture of n-alkyl methyl ketones and for predicting the boiling point distribution of the final mixture of cyclic alkanes, we show that it is possible to define the mixture of synthons that will closely reproduce the distillation curve of traditional jet fuel.

Selective hydrogenation of furan-containing condensation products as a source of biomass-derived diesel additives.

In this study, we demonstrate that while the energy density and lubricity of the C15 and C16 products of furan condensation of biomass-derived aldehydes with 2-methylfuran are consistent with requirements for diesel, these products do not meet specifications for cetane number and pour point due to their aromatic furan rings. However, a novel class of products that fully meet or exceed most specifications for diesel can be produced by converting the furan rings in these compounds to cyclic ether moieties. Full hydrodeoxygenation of furan condensation products to alkanes would require 55-60% higher hydrogen demand, starting from biomass, compared to the products of furan ring saturation, providing an additional incentive to support the saturated products. We also report here on a tunable class of catalysts that contain Pd nanoparticles supported on ionic liquid-modified SiO2 that can achieve complete saturation of the furan rings in yields of 95% without opening these rings.

Syntheses of biodiesel precursors: sulfonic acid catalysts for condensation of biomass-derived platform molecules.

Synthesis of transportation fuel from lignocellulosic biomass is an attractive solution to the green alternative-energy problem. The production of biodiesel, in particular, involves the process of upgrading biomass-derived small molecules to diesel precursors containing a specific carbon range (C11 -C23). Herein, a carbon-upgrading process utilizing an acid-catalyzed condensation of furanic platform molecules from biomass is described. Various types of sulfonic acid catalysts have been evaluated for this process, including biphasic and solid supported catalysts. A silica-bound alkyl sulfonic acid catalyst has been developed for promoting carbon-carbon bond formation of biomass-derived carbonyl compounds with 2-methylfuran. This hydrophobic solid acid catalyst exhibits activity and selectivity that are comparable to those of a soluble acid catalyst. The catalyst can be readily recovered and recycled, possesses appreciable hydrolytic stability in the presence of water, and retains its acidity over multiple reaction cycles. Application of this catalyst to biomass-derived platform molecules led to the synthesis of a variety of furanic compounds, which are potential biodiesel precursors.