Affordable and Clean Energy (SDG 7), Responsible Consumption and Production (SDG 12)
Green approaches to the upgrading of levulinic acid to gamma valerolactone
Freida Kauffmann* The University of the West Indies, Trinidad and Tobago
Greenhouse gas emissions stemming from the processing and combustion of fossil fuels and their derivatives have plunged the planet into disastrous climate change patterns which are feared to be irreversible. Mitigation strategies are focused on utilizing renewable energy sources and chemicals produced from biomass. A major challenge of utilizing biomass for chemical production is the reliance on fossil fuel derived heat or chemical inputs. These issues are related to the UN sustainable development goals (SDGs): 7 (affordable and clean energy), 12 (responsible consumption and production) and 13 (climate action) with other goals also being indirectly impacted. Levulinic acid (LA) is a versatile platform molecule derived from living biomass (i.e. lignocellulose) with the potential to replace several fossil-fuel derived chemicals and fuels in a carbon neutral manner. Typically, LA can be transformed into drop-in chemicals in food, drug and the agricultural sectors, fuel blenders and fuel precursors, 1-3 fulfilling SDG goals 7 and 12, allowing for a sustainable and green pathway to the production of chemicals and fuels. Once such derivative is the fuel blender gamma valerolactone (GVL) whose commercial value is up to five times more than its feedstock precursor LA. GVL is produced by the catalyst enabled LA hydrogenation reaction which is reported to be most effective at relatively high temperatures, high overpressures of (fossil fuel derived) hydrogen and using catalysts with high metal loading. 5-7 This work examined the thermocatalytic LA to GVL transformation where it was found that low loaded noble metal catalysts of <1% metal content, prepared via chemical vapour impregnation, afforded high yields of GVL at very moderate temperatures. Thus, the work demonstrates more sustainable chemical production. In order to increase the overall sustainability and use of renewable materials, in-situ green hydrogen sources were also evaluated as hydrogen sources in the target reaction. Ethanol, which is currently well utilized in the literature, and glycerol, a by-product of the biodiesel industry which has not been previously applied as a donor in LA hydrogenation have been specifically investigated. Glycerol, a renewable raw material, was found to be an effective hydrogen source under mild reaction conditions, and comparable to established donors such as 2-propanol. These findings are directly related to SDG 13 because fossil fuel derived hydrogen is directly addressed. The reduction of waste streams increases the sustainability index of biodiesel production as well as the LA upgrade reaction in this novel coupled approach. These tie into SDG goals 7 and 12 as well. Recent advances also employ photocatalytic approaches with high powered UV light sources in just four articles. 8-11 Proof of principle experiments on photocatalytic levulinic acid hydrogenation to GVL showed that LA can be upgraded using visible light (and external hydrogen). These findings have implications to further improve the energy economics of this reaction, since there is potential for sunlight to be utilized in the transformation, tackling all the SDGs mentioned before (goals 7,12 and 13). References 1. Zhang, J.; Wu, S.; Li, B.; Zhang, H., Advances in the Catalytic Production of Valuable Levulinic Acid Derivatives. ChemCatChem 2012, 4 (9), 1230-1237. 2. Yan, K.; Jarvis, C.; Gu, J.; Yan, Y., Production and catalytic transformation of levulinic acid: A platform for speciality chemicals and fuels. Renewable and Sustainable Energy Reviews 2015, 51, 986-997. 3. Girisuta, B.; Heeres, H. J., Levulinic Acid from Biomass: Synthesis and Applications. In Production of Platform Chemicals from Sustainable Resources, Fang, Z.; Smith, J. R. L.; Qi, X., Eds. Springer Singapore: Singapore, 2017; pp 143-169. 4. Alonso, D. M.; Wettstein, S. G.; Dumesic, J. A., Gamma-valerolactone, a sustainable platform molecule derived from lignocellulosic biomass. Green Chemistry 2013, 15 (3), 584-595. 5. Yan, Z.-p.; Lin, L.; Liu, S., Synthesis of γ-Valerolactone by Hydrogenation of Biomass-derived Levulinic Acid over Ru/C Catalyst. Energy & Fuels 2009, 23 (8), 3853-3858. 6. Luo, W.; Sankar, M.; Beale, A. M.; He, Q.; Kiely, C. J.; Bruijnincx, P. C. A.; Weckhuysen, B. M., High performing and stable supported nano-alloys for the catalytic hydrogenation of levulinic acid to γ-valerolactone. 2015, 6, 6540. 7. Testa, M. L.; Corbel-Demailly, L.; La Parola, V.; Venezia, A. M.; Pinel, C., Effect of Au on Pd supported over HMS and Ti doped HMS as catalysts for the hydrogenation of levulinic acid to γ-valerolactone. Catalysis Today 2015, 257, 291-296. 8. Zhang, H.; Zhao, M.; Zhao, T.; Li, L.; Zhu, Z., Hydrogenative cyclization of levulinic acid into γ-valerolactone by photocatalytic intermolecular hydrogen transfer. Green Chemistry 2016, 18 (8), 2296-2301. 9. Filho, J. B. G.; Rios, R. D. F.; Bruziquesi, C. G. O.; Ferreira, D. C.; Victória, H. F. V.; Krambrock, K.; Pereira, M. C.; Oliveira, L. C. A., A promising approach to transform levulinic acid into γ-valerolactone using niobic acid photocatalyst and the accumulated electron transfer technique. Applied Catalysis B: Environmental 2021, 285, 119814. 10. Bunrit, A.; Butburee, T.; Liu, M.; Huang, Z.; Meeporn, K.; Phawa, C.; Zhang, J.; Kuboon, S.; Liu, H.; Faungnawakij, K.; Wang, F., Photo–Thermo-Dual Catalysis of Levulinic Acid and Levulinate Ester to γ-Valerolactone. ACS Catalysis 2022, 12 (3), 1677- 1685. 11. Filho, J. B. G.; Gomes, G. H. M.; Silva, I. F.; Rios, R. D. F.; Victória, H. F. V.; Krambrock, K.; Pereira, M. C.; Oliveira, L. C. A., Photocatalytic reduction of levulinic acid using thermally modified niobic acid. Chemical Engineering Journal 2022, 450, 137935.
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