Ivan Kumaniaev
Stockholm University
Ivan Kumaniaev acquired his MSc degree from University of Chemical Technology of Russia, Moscow, in 2016. In the same year he started his PhD studies in the group of prof. Joseph Samec in Stockholm University, Sweden. His research is focused on biomass processing and valorization, and also green organic chemistry.
A reductive process for valorization of Quercus suber bark towards hydrocarbons of gasoline and deiesel ranges and optionally 4-ethylguaiacol has been developed1. The procedure involves three steps: 1) tandem hydrogen-free Pd/C-catalyzed transfer hydrogenolysis of lignin under slightly alkaline conditions to facilitate depolymerization of suberin; 2) distillation to separate monomeric lignin derivative 4-ethylguaiacol; 3) hydrodeoxygenation of the residue in a hydrogen atmosphere in the presence of Pt-MoO3/TiO2 catalyst2, yielding a range of hydrocarbons.
Yield of hydrocarbon bio-oil is 42% of dry bark weight (77% the sum of lignin and suberin contents). Carbon yield of the obtained bio-oil is 64% from total initial bark carbon. Gas chromatography showed that the obtained oil consists of C6–C27 hydrocarbons (composition given in the table) and has average molecular formula C14.9H28.4O0.00–0.06. H:C ratio changes throughout the process, taking a value of 1.47 for dry bark and 1.90 for the hydrocarbon oil. O:C ratio changes even more substantially: from 0.46 for bark to 0.004 for the hydrocarbonic bio-oil. Results of simulated distillation were in accordance with gas chromatography data and showed that the obtained bio-oil includes components with boiling point ranges typical for different types of hydrocarbonic fuels, such as gasoline (<200°C, 20 wt.%), diesel (200–300°C, 45 wt.%), and heavy gas oil (300–420°C, 33 wt.%). The higher heating value of such a fuel estimated for this compostion using several common linear formulas (Dulong, Boie, Mott-Spooner) is 46–49 MJ∙kg–1.
Lignin domain of bark was converted into 4-ethylguaiacol with high selectivity (90%) in relation to other monomeric phenols and 12% yield from lignin mass content. Due to high degree of functionalization, this product can serve as a synthetic precursor of valuable compounds3.
1) Ivan Kumaniaev, Joseph Samec. Valorization of Quercus suber bark toward hydrocarbon bio-oil and 4-ethylguaiacol. ACS Sustainable Chem. Eng., Article ASAP, DOI: 10.1021/acssuschemeng.8b00537
2) K. Shimizu et al. Hydrodeoxygenation of Fatty Acids, Triglycerides, and Ketones to Liquid Alkanes by a Pt–MoOx/TiO2 Catalyst. ChemCatChem 2017, 9, 2822–2827.
3) B.F.Sels et al. Sustainable bisphenols from renewable softwood lignin feedstock for polycarbonates and cyanate ester resins. Green Chem. 2017, 19, 2561–2570.
Bioenergy and biofuels , Biomass conversion technologies
