Upconversion of Cellulosic Waste Into a Potential “Drop in Fuel” via Novel Catalyst Generated Using Desulfovibrio desulfuricans and a Consortium of Acidophilic Sulfidogens
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5-hydroxymethylfurfural upgrade5-HMF upgradePdRu catalystDesulfovibrio desulfuricansWaste sulfidogenic bacteria
Mikheenko IP, Gomez-Bolivar J, Merroun ML, Macaskie LE, Sharma S, Walker M, Hand RA, Grail BM, Johnson DB and Orozco RL (2019) Upconversion of Cellulosic Waste Into a Potential “Drop in Fuel” via Novel Catalyst Generated Using Desulfovibrio desulfuricans and a Consortium of Acidophilic Sulfidogens. Front. Microbiol. 10:970. [doi: 10.3389/fmicb.2019.00970]
SponsorshipThis project was funded by NERC grant NE/L014076/1 to LM (Program: “Resource Recovery from Wastes”). The Science City Photoemission Facility used in this research was funded through the Science Cities Advanced Materials Project 1: “Creating and Characterizing Next Generation of Advanced Materials” with support from AWM and ERDF funds. The microscopy work was conducted at “Centro de Instrumentación Cientifica” at the University of Granada, Spain. This work was partially supported by the Spanish Government Sistema Nacional de Grantia Juvenil grant PEJ-2014-P-00391 (Promocion de Empleo Joven e Implantacion de la Garantia Juvenil 2014, MINECO) with a scholarship to JGB.
Biogas-energy is marginally profitable against the “parasitic” energy demands of processing biomass. Biogas involves microbial fermentation of feedstock hydrolyzate generated enzymatically or thermochemically. The latter also produces 5-hydroxymethyl furfural (5-HMF) which can be catalytically upgraded to 2, 5-dimethyl furan (DMF), a “drop in fuel.” An integrated process is proposed with side-stream upgrading into DMF to mitigate the “parasitic” energy demand. 5-HMF was upgraded using bacterially-supported Pd/Ru catalysts. Purpose-growth of bacteria adds additional process costs; Pd/Ru catalysts biofabricated using the sulfate-reducing bacterium (SRB) Desulfovibrio desulfuricans were compared to those generated from a waste consortium of acidophilic sulfidogens (CAS). Methyl tetrahydrofuran (MTHF) was used as the extraction-reaction solvent to compare the use of bio-metallic Pd/Ru catalysts to upgrade 5-HMF to DMF from starch and cellulose hydrolyzates. MTHF extracted up to 65% of the 5-HMF, delivering solutions, respectively, containing 8.8 and 2.2 g 5-HMF/L MTHF. Commercial 5% (wt/wt) Ru-carbon catalyst upgraded 5-HMF from pure solution but it was ineffective against the hydrolyzates. Both types of bacterial catalyst (5wt%Pd/3-5wt% Ru) achieved this, bio-Pd/Ru on the CAS delivering the highest conversion yields. The yield of 5-HMF from starch-cellulose thermal treatment to 2,5 DMF was 224 and 127 g DMF/kg extracted 5-HMF, respectively, for CAS and D. desulfuricans catalysts, which would provide additional energy of 2.1 and 1.2 kWh/kg extracted 5-HMF. The CAS comprised a mixed population with three patterns of metallic nanoparticle (NP) deposition. Types I and II showed cell surface-localization of the Pd/Ru while type III localized NPs throughout the cell surface and cytoplasm. No metallic patterning in the NPs was shown via elemental mapping using energy dispersive X-ray microanalysis but co-localization with sulfur was observed. Analysis of the cell surfaces of the bulk populations by X-ray photoelectron spectroscopy confirmed the higher S content of the CAS bacteria as compared to D. desulfuricans and also the presence of Pd-S as well as Ru-S compounds and hence a mixed deposit of PdS, Pd(0), and Ru in the form of various +3, +4, and +6 oxidation states. The results are discussed in the context of recently-reported controlled palladium sulfide ensembles for an improved hydrogenation catalyst.