Innovations
Vol. 13 (2025), Issue 2, pg(s) 61-64

INNOVATIVE SOLUTIONS

Optimization of long-chain alkene synthesis from lignocellulosic wastes using photocatalysis

  • 1 Food Colloids and Rheology Lab., Department of Food Science and Technology, Faculty of Agriculture, Tarbiat Modares University, Tehran, Iran

Abstract

Tall oil fatty acid (TOFA) is a valuable byproduct derived from the processing of lignocellulosic biomass, particularly in the pulp and paper industry. In the present study, TOFA, under optimized alkaline conditions, was firstly converted to soap, then TOFA-based soap was utilized to produce long-chain alkenes using photocatalysis (photoreactor equipped with a UVA-LED lamp). In addition, the performance of TiO2, as photocatalyst, was enhanced by introducing NH4 + onto its surface. Using response surface methodology (RSM), the effect of reaction time (135, 180, and 225 min), catalyst (80, 110, and 140 mg), and TOFA-based soap quantity (50, 100, and 150 mg) were
evaluated. The highest yield (77.7 mg) of Cn-1 long-chain alkenes was attained when ~1:1 ratio of TOFA-based soap:NH4-TiO2 was photocatalyzed at 365 nm for 180 min. The findings demonstrated that ~55% of TOFA-based soap can be converted to long chain alkenes by using photocatalysis under optimized conditions. Then, by using sulfuric acid, the alkenes were hydrated into corresponding long-chain alcohols that can serve as precursor for fabrication of bio-based extended surfactants. These findings highlighted the potential of the byproducts of lignocellulosic wastes (i.e., TOFA) as a sustainable feedstock for producing high-value chemicals

Keywords

References

  1. Altıparmak, D., Keskin, A., Koca, A., & Gürü, M. (2007). Alternative fuel properties of tall oil fatty acid methyl ester–diesel fuel blends. Bioresource Technology, 98(2), 241–246. (https://doi.org/10.1016/j.biortech.2006.01.020).
  2. Murillo, E. A., Vallejo, P. P., & López, B. L. (2011). Effect of tall oil fatty acids content on the properties of novel hyperbranched alkyd resins. Journal of Applied Polymer Science, 120(6), 3151– 3158. (https://doi.org/10.1002/app.33502)
  3. White, K., Lorenz, N., Potts, T., Roy Penney, W., Babcock, R., Hardison, A., Canuel, E. A., & Hestekin, J. A. (2011). Production of biodiesel fuel from tall oil fatty acids via high temperature methanol reaction. Fuel, 90(11), 3193–3199 (https://doi.org/10.1016/j.fuel.2011.06.017)
  4. Cnudde, P., De Wispelaere, K., Vanduyfhuys, L., Demuynck, R., Van der Mynsbrugge, J., Waroquier, M., & Van Speybroeck, V. (2018). How Chain Length and Branching Influence the Alkene Cracking Reactivity on H-ZSM-5. ACS Catalysis, 8(10), 9579– 9595. (https://doi.org/10.1021/acscatal.8b01779)
  5. Stanton, M. P., & Hoover, J. M. (2023). Copper-Catalyzed Decarboxylative Elimination of Carboxylic Acids to Alkenes. The Journal of Organic Chemistry88, 3, 1713–1719 (https://doi.org/10.1021/acs.joc.2c02705)
  6. Yongdong, Z., Yaling, S., Zhengwen, L., Xiangchao, C., Jinlei, Y., Xiaodan, D., & Miao, J. (2015). Long-chain n-alkenes in recent sediment of Lake Lugu (SW China) and their ecological implications. Limnologica, 52, 30–40. (https://doi.org/10.1016/j.limno.2015.02.004)
  7. Alfano, O. M., & Cassano, A. E. (2008). Photoreactor Modeling: Applications to Advanced Oxidation Processes. International Journal of Chemical Reactor Engineering, 6(1). (https://doi.org/10.2202/1542-6580.1617)
  8. Howe, R. F. (1998). Recent developments in photocatalysis. Developments in Chemical Engineering and Mineral Processing. 6, 1,2 (https://doi.org/10.1002/apj.5500060105).
  9. Alfano, O. M., & Cassano, A. E. (2009). Scaling-Up of Photoreactors, 229–287. (https://doi.org/10.1016/S0065- 2377(09)00407-4)
  10. Chen, X., Shen, S., Guo, L., & Mao, S. S. (2010). Semiconductor-based photocatalytic hydrogen generation. Chemical Reviews. 110, 11, 6503–6570. (https://doi.org/10.1021/cr1001645).
  11. Hashimoto, K., Irie, H., & Fujishima, A. (2005). TiO2 Photocatalysis: A Historical Overview and Future Prospects. Japanese Journal of Applied Physics, 44(12R), 8269. https://doi.org/10.1143/JJAP.44.8269
  12. Pelizzetti, E., & Minero, C. (1994). Metal Oxides as Photocatalysts for Environmental Detoxification. Comments on Inorganic Chemistry. A Journal of Critical Discussion of the Current Literature 15, 5,6
  13. Chen, Z., Zhou, H., Kong, F., Dou, Z., & Wang, M. (2024). Photocatalytic Conversion of Lipid to Diesel and Syngas via engineering the Surface Proton Transfer. ACS Catalysis, 14, 3, 1699–1705 ( https://doi.org/10.1021/acscatal.3c04818)
  14. Li, X., Peng, Y., Huang, Z., Feng, G., Kong, L., Jiang, H., & Yang, W. (2024). Combined hydrogen and alkane production by photocatalytic decarboxylative C-C homocoupling of fatty acid by constructing a hydrogen-deficient catalytic interface. ACS Catalysis 14, 5, 3675–3686. (https://doi.org/10.1021/acscatal.3c06070)
  15. Tang, X., Gan, L., Zhang, X., & Huang, Z. (2020). n-Alkanes to n-alcohols: Formal primary C─H bond hydroxymethylation via quadruple relay catalysis. In Sci. 6. (https://doi.org/10.1021/acs.joc.2c02705)
  16. Chng, L. L., Erathodiyil, N., & Ying, J. Y. (2013). Nanostructured catalysts for organic transformations. Accounts of Chemical Research. 46, 8, 1825–1837. (https://doi.org/10.1021/ar300197s)
  17. Hashimoto, K., Irie, H., & Fujishima, A. (2005). TiO2 Photocatalysis: A Historical Overview and Future Prospects. Japanese Journal of Applied Physics, 44(12R), 8269. https://doi.org/10.1143/JJAP.44.8269
  18. Huang, Z., Zhao, Z., Zhang, C., Lu, J., Liu, H., Luo, N., Zhang, J., & Wang, F. (2020). Enhanced photocatalytic alkane production from fatty acid decarboxylation via inhibition of radical oligomerization. Nature Catalysis, 3(2), 170–178. (https://doi.org/10.1038/s41929-020-0423-3)
  19. Mills, A., & Hunte, S. Le. (2000). An overview of semiconductor photocatalysis. Photochemistry and Photobiology.
  20. Zhou, C., & Zhang, T. (2020). Photocatalytic alkane production from fatty acid decarboxylation over hydrogenated catalyst. In Science Bulletin 65, 11, 870–871, (https://doi.org/10.1016/j.scib.2020.03.017)

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