Developing the Glycerol Carbonylation Process Using Photocatalysis and 2-Cyanopyridine as a Water-Reducing Agent

Document Type : Original Research Article

Authors

1 Department of Environmental Engineering, Faculty of Natural Resources and Environment, University of Birjand, Birjand, Iran

2 Faculty of Natural Resources and Environment, Shahid Bahonar University of Kerman, Kerman 7616913439, Iran

Abstract

This study investigates the direct carbonylation of glycerol using a composite photocatalyst (TiO2 loaded with cellulose) and 2-cyanopyridine as a water-reducing agent. In this research, the performance of the photocatalytic system was evaluated under different conditions, including various concentrations of 2-cyanopyridine, glycerol, and catalyst dosage, as well as changing the molar ratios of CO2 to glycerol and reaction times. The optimal conditions for achieving high glycerol conversion and GlyCO3 performance were determined, resulting in a glycerol conversion of 92.43% and a yield of 91.12% towards glycerol carbonate under these conditions. Increasing the concentration of 2-cyanopyridine up to 30 mmol enhanced GlyCO3 production. However, excessive amounts led to decreased yields due to catalyst site blockage. The influence of the CO2 to glycerol molar ratio on GlyCO3 yield was marginal within a certain concentration range, indicating a non-limiting CO2 supply. Catalyst loading significantly affected product yield, with higher concentrations promoting greater GlyCO3 formation. However, catalyst reusability tests revealed a decline in activity after recycling, attributed to drying-induced deactivation. These findings provide valuable insights into optimizing the cellulose-TiO2 photocatalyst for efficient glycerol carbonylation, contributing to the advancement of sustainable chemical processes.

Keywords

Main Subjects


Ahmadizadegan, H., 2017. Surface modification of TiO2 nanoparticles with biodegradable nanocellolose and synthesis of novel polyimide/cellulose/TiO2 membrane. Journal of Colloid and Interface Science491, 390.
Ahmadpour, N., Nowrouzi, M., Avargani, V.M., Sayadi, M.H. & Zendehboudi, S., 2024. Design and optimization of TiO2-based photocatalysts for efficient removal of pharmaceutical pollutants in water: Recent developments and challenges. Journal of Water Process Engineering57, 104597.
Chamanehpour, E., Sayadi, M.H. & Hajiani, M., 2022. A hierarchical graphitic carbon nitride supported by metal–organic framework and copper nanocomposite as a novel bifunctional catalyst with long-term stability for enhanced carbon dioxide photoreduction under solar light irradiation. Advanced Composites and Hybrid Materials5(3), 2461-2477.
Gulbrandson, A.J., Larm, N.E., Stachurski, C.D., Trulove, P.C. & Durkin, D. P., 2023. Mesoporous Cellulose-TiO2 Nanoparticle Composite Textile for “Excellent” UV Protection. ACS Applied Engineering Materials1(11), 3053-3061.
Hamad, H., Bailon-Garcia, E., Morales-Torres, S., Carrasco-Marin, F., Perez-Cadenas, A.F. & Maldonado-Hodar, F. J., 2018. Physicochemical properties of new cellulose-TiO2 composites for the removal of water pollutants: Developing specific interactions and performances by cellulose functionalization. Journal of Environmental Chemical Engineering6(4), 5032-5041.
Hu, C., Yoshida, M., Chen, H C., Tsunekawa, S., Lin, Y. F. & Huang, J.H., 2021. Production of glycerol carbonate from carboxylation of glycerol with CO2 using ZIF-67 as a catalyst. Chemical Engineering Science235, 116451.
Kargar, F., Bemani, A., Sayadi, M. H. & Ahmadpour, N., 2021. Synthesis of modified beta bismuth oxide by titanium oxide and highly efficient solar photocatalytic properties on hydroxychloroquine degradation and pathways. Journal of photochemistry and photobiology A: Chemistry419, 113453.
 Li, H., Jiao, X., Li, L., Zhao, N., Xiao, F., Wei, W. ... & Zhang, B., 2015. Synthesis of glycerol carbonate by direct carbonylation of glycerol with CO2 over solid catalysts derived from Zn/Al/La and Zn/Al/La/M (M= Li, Mg and Zr) hydrotalcites. Catalysis Science & Technology5(2), 989-1005.
 Li, M., Qiu, J., Xu, J. & Yao, J., 2020. Cellulose/TiO2-based carbonaceous composite film and aerogel for highly efficient photocatalysis under visible light. Industrial & Engineering Chemistry Research59(31), 13997-14003.
Lima, P.J.M., da Silva, R.M., Neto, C.A.C.G., Gomes e Silva, N.C., Souza, J.E.D.S., Nunes, Y.L. & Sousa dos Santos, J. C., 2022. An overview on the conversion of glycerol to value‐added industrial products via chemical and biochemical routes. Biotechnology and Applied Biochemistry69(6), 2794-2818.
Liu, J., Li, Y., Liu, H. & He, D., 2019. Photo-thermal synergistically catalytic conversion of glycerol and carbon dioxide to glycerol carbonate over Au/ZnWO4-ZnO catalysts. Applied Catalysis B: Environmental244, 836-843.
Liu, J., Li, Y., Zhang, J. & He, D., 2016. Glycerol carbonylation with CO2 to glycerol carbonate over CeO2 catalyst and the influence of CeO2 preparation methods and reaction parameters. Applied Catalysis A: General513, 9-18.
Mao, J., Li, K. & Peng, T., 2013. Recent advances in the photocatalytic CO2 reduction over semiconductors. Catalysis Science & Technology3(10), 2481-2498.
 Ozorio, L.P., Pianzolli, R., da Cruz Machado, L., Miranda, J.L., Turci, C.C., Guerra, A.C. ... & Mota, C. J., 2015. Metal-impregnated zeolite Y as efficient catalyst for the direct carbonation of glycerol with CO2Applied Catalysis A: General504, 187-191.
Plermjai, K., Boonyarattanakalin, K., Mekprasart, W., Phoohinkong, W., Pavasupree, S. & Pecharapa, W., 2019. Optical absorption and FTIR study of cellulose/TiO2 hybrid composites. Chiang Mai Journal of Science46(3), 618-625.
Procopio, D. & Di Gioia, M.L., 2022. An overview of the latest advances in the catalytic synthesis of glycerol carbonate. Catalysts12(1), 50.
Raza, A., Ikram, M., Guo, S., Baiker, A. & Li, G., 2022. Green synthesis of dimethyl carbonate from CO2 and methanol: new strategies and industrial perspective. Advanced Sustainable Systems6(8), 2200087.
Sayadi, M.H., Homaeigohar, S., Rezaei, A. & Shekari, H., 2021. Bi/SnO2/TiO2-graphene nanocomposite photocatalyst for solar visible light–induced photodegradation of pentachlorophenol. Environmental Science and Pollution Research28, 15236-15247.
Sonnati, M.O., Amigoni, S., de Givenchy, E.P.T., Darmanin, T., Choulet, O. & Guittard, F., 2013. Glycerol carbonate as a versatile building block for tomorrow: synthesis, reactivity, properties and applications. Green Chemistry15(2), 283-306.
Sugashini, S., Gomathi, T., Devi, R.A., Sudha, P.N., Rambabu, K. & Banat, F., 2022. Nanochitosan/carboxymethyl cellulose/TiO2 biocomposite for visible-light-induced photocatalytic degradation of crystal violet dye. Environmental Research204, 112047.
Teng, W.K., Yusoff, R., Aroua, M.K. & Ngoh, G.C., 2021. Process optimization and kinetics of microwave assisted transesterification of crude glycerol for the production of glycerol carbonate. Sustainable Energy & Fuels5(1), 274-282.