Tuning the selectivity of natural oils and fatty acids/esters deoxygenation to biofuels and fatty alcohols: A review

The chemical transformation of natural oils provides alternatives to limited fossil fuels and produces compounds with added value for the chemical industries. The selective deoxygenation of natural oils to diesel-ranged hydrocarbons, bio-jet fuels, or fatty alcohols with controllable selectivity is especially attractive in natural oil feedstock biorefineries. This review presents recent progress in catalytic deoxygenation of natural oils or related model compounds (e.g., fatty acids) to renewable liquid fuels (green diesel and bio-jet fuels) and valuable fatty alcohols (unsaturated and saturated fatty alcohols). Besides, it discusses and compares the existing and potential strategies to control the product selectivity over heterogeneous catalysts. Most research conducted and reviewed has only addressed the production of one category; therefore, a new integrative vision exploring how to direct the process toward fuel and/or chemicals is urgently needed. Thus, work conducted to date addressing the development of new catalysts and studying the influence of the reaction parameters (e.g., temperature, time and hydrogen pressure) is summarized and critically discussed from a green and sustainable perspective using efficiency indicators (e.g., yields, selectivity, turnover frequencies and catalysts lifetime). Special attention has been given to the chemical transformations occurring to identify key descriptors to tune the selectivity toward target products by manipulating the reaction conditions and the structures of the catalysts. Finally, the challenges and future research goals to develop novel and holistic natural oil biorefineries are proposed. As a result, this critical review provides the readership with appropriate information to selectively control the transformation of natural oils into either biofuels and/or value-added chemicals. This new flexible vision can help pave the wave to suit the present and future market needs.