Global warming issues and the medium-term depletion of fossil fuel reserves are stimulating researchers around the world to find alternative sources of energy and organic carbon. Biomass is considered by experts the only sustainable source of energy and organic carbon for our industrial society, and it has the potential to displace petroleum in the production of chemicals and liquid transportation fuels. However, the transition from a petroleum-based economy to one based on biomass requires new strategies since the petrochemical technologies, well-developed over the last century, are not valid to process the biomass-derived compounds. Unlike petroleum feedstocks, biomass derived platform molecules possess a high oxygen content that gives them low volatility, high solubility in water, high reactivity and low thermal stability, properties that favour the processing of these resources by catalytic aqueous-phase technologies at moderate temperatures. This tutorial review is aimed at providing a general overview of processes, technologies and challenges that lie ahead for a range of different aqueous-phase transformations of some of the key biomass-derived platform molecules into liquid fuels for the transportation sector and related high added value chemicals.

It is imperative to develop more efficient processes for conversion of biomass to liquid fuels, such that the cost of these fuels would be competitive with the cost of fuels derived from petroleum. We report a catalytic approach for the conversion of carbohydrates to specific classes of hydrocarbons for use as liquid transportation fuels, based on the integration of several flow reactors operated in a cascade mode, where the effluent from the one reactor is simply fed to the next reactor. This approach can be tuned for production of branched hydrocarbons and aromatic compounds in gasoline, or longer-chain, less highly branched hydrocarbons in diesel and jet fuels. The liquid organic effluent from the first flow reactor contains monofunctional compounds, such as alcohols, ketones, carboxylic acids, and heterocycles, that can also be used to provide reactive intermediates for fine chemicals and polymers markets.

Concerns about diminishing fossil fuel reserves along with global warming effects caused by increasing levels of CO₂ in the atmosphere are driving society toward the search for new renewable sources of energy that can substitute for coal, natural gas and petroleum in the current energy system. Lignocellulosic biomass is abundant, and it has the potential to significantly displace petroleum in the production of fuels for the transportation sector. Ethanol, the main biomass-derived fuel used today, has benefited from production by a well-established technology and by partial compatibility with the current transportation infrastructure, leading to the domination of the world biofuel market. However, ethanol suffers from important limitations as a fuel (e.g., low energy density, high solubility in water) than can be overcome by designing strategies to convert non-edible lignocellulosic biomass into liquid hydrocarbon fuels (LHF) chemically similar to those currently used in internal combustion engines. The present review describes the main routes available to carry out such deep chemical transformation (e.g., gasification, pyrolysis, and aqueous-phase catalytic processing), with particular emphasis on those pathways involving aqueous-phase catalytic reactions. These latter catalytic routes achieve the required transformations in biomass-derived molecules with controlled chemistry and high yields, but require pretreatment/hydrolysis steps to overcome the recalcitrance of lignocellulose. To be economically viable, these aqueous-phase routes should be carried out with a small number of reactors and with minimum utilization of external fossil fuel-based hydrogen sources, as illustrated in the examples presented here.

Aqueous solutions of levulinic acid can be catalytically processed, through the intermediate formation of γ-valerolactone (GVL), to an organic liquid stream that spontaneously separates from water, and is enriched in pentanoic acid and 5-nonanone. This organic layer can serve as a source of chemicals or can be upgraded to hydrocarbon fuels.

Lignocellulosic biomass is renewable and cheap, and it has the potential to displace fossil fuels in the production of fuels and chemicals. Biomass-derived carboxylic acids are important compounds that can be used as platform molecules for the production of a variety of important chemicals on a large scale. Lactic acid, a prototypical biomass derivative, and levulinic acid, an important chemical feedstock produced by hydrolysis of waste cellulosic materials, can be upgraded using bifunctional catalysts (those containing metal and acid sites), which allows the integration of several transformations (e.g., oxygen removal and C–C coupling) in a single catalyst bed. This coupling between active sites is beneficial in that it reduces the complexity and cost of the biomass conversion processes. Deoxygenation of biomass derivatives is a requisite step for the production of fuels and chemicals, and strategies are proposed to minimize the consumption of hydrogen from an external source during this process.