SummaryHerein, a lignin-centered convergent approach to produce either aliphatic or aromatic bio-hydrocarbons is introduced. First, poplar or spruce wood was deconstructed by a lignin-first biorefining process, a technique based on the early-stage catalytic conversion of lignin, yielding lignin oils along with cellulosic pulps. Next, the lignin oils were catalytically upgraded in the presence of a phosphidated Ni/SiO2 catalyst under H2 pressure. Notably, selectivity toward aliphatics or aromatics can simply be adjusted by changes in H2 pressure and temperature. The process renders two distinct main cuts of branched hydrocarbons (gasoline: C6-C10, and kerosene/diesel: C14-C20). As the approach is H2-intensive, we examined the utilization of pulp as an H2 source via gasification. For several biomass sources, the H2 obtainable by gasification stoichiometrically meets the H2 demand of the deep converting lignin-first biorefinery, making this concept plausible for the production of high-energy-density drop-in biofuels.

A simple and efficient hydrodeoxygenation strategy is described to selectively generate and separate high-value alkylphenols from pyrolysis bio-oil, produced directly from lignocellulosic biomass. The overall process is efficient and only requires low pressures of hydrogen gas (5 bar). Initially, an investigation using model compounds indicates that MoC /C is a promising catalyst for targeted hydrodeoxygenation, enabling selective retention of the desired Ar-OH substituents. By applying this procedure to pyrolysis bio-oil, the primary products (phenol/4-alkylphenols and hydrocarbons) are easily separable from each other by short-path column chromatography, serving as potential valuable feedstocks for industry. The strategy requires no prior fractionation of the lignocellulosic biomass, no further synthetic steps, and no input of additional (e.g., petrochemical) platform molecules.

Hydrodeoxygenation (HDO) of lignocellulose‐derived pyrolysis oils offers an option to produce fuel substitutes. However, catalyst deactivation and stability constitute a significant issue. Herein, the dependence of stability and activity of Ni2P/SiO2 HDO catalysts on the support surface polarity is addressed in detail. The support surface polarity was adjusted by copolymerizing tetraethyl orthosilicate (TEOS) with different types and amounts of organosilanes by a sol–gel process in the presence of nickel nitrate and citric acid. After thermal treatment under an inert atmosphere, Ni/SiO2 precursors were formed. They were converted into Ni2P/SiO2 catalysts by using NaH2PO2 as a PH3 source. The catalyst surface polarity was characterized by inverse gas chromatography measurements of the free energy of methanol adsorption, and specific and dispersive surface energies derived from polar and nonpolar probe molecule adsorption. The correlation between catalyst performance and support surface polarity indicates that, to prevent deactivation of the catalyst by water under reaction conditions, the affinity of the support towards polar substances must be decreased below a threshold value.

Asimple and efficient hydrodeoxygenation strategy is described to selectively generate and separate high-value alkylphenols from pyrolysis bio-oil, produced directly from lignocellulosic biomass.T he overall process is efficient and only requires low pressures of hydrogen gas (5 bar). Initially, an investigation using model compounds indicates that MoC x / Ci sapromising catalyst for targeted hydrodeoxygenation, enabling selective retention of the desired ArÀOH substituents. By applying this procedure to pyrolysis bio-oil, the primary products (phenol/4-alkylphenols and hydrocarbons) are easily separable from each other by short-path column chromatography,s erving as potential valuable feedstocks for industry. The strategy requires no prior fractionation of the lignocellulosic biomass,n of urther synthetic steps,a nd no input of additional (e.g., petrochemical) platform molecules.Supportinginformation and the ORCID identification number(s) for the author(s) of this article can be found under: http://dx.

The present study describes an interesting and practical catalytic system that allows flexible conversion of lignin into aromatic or aliphatic hydrocarbons, depending on the hydrogen partial pressure. A combination of experiment and theory shows that the product distribution between aromatics and aliphatics can be simply tuned by controlling the availability of hydrogen on the catalyst surface. Noticeably, these pathways lead to almost complete oxygen removal from lignin biomass, yielding high-quality hydrocarbons. Thus, hydrogen-lignin corefining by using this catalytic system provides high flexibility in hydrogen storage/consumption towards meeting different regional and temporal demands.