Scopus (CiteScore 2022 =3.0, Q3) , ISC

Document Type : Original Research Article

Authors

1 Department of Chemistry, Kulliyyah of Science, International Islamic University Malaysia (IIUM), Jalan Sultan Ahmad Shah, Bandar Indera Mahkota, 25200 Kuantan, Pahang, Malaysia

2 School of Chemistry and Environment, Faculty of Applied Sciences, UiTM, 40450 Shah Alam, Selangor, Malaysia

3 School of Chemical Sciences, Universiti Sains Malaysia, 11800 Gelugor, Pulau Pinang, Malaysia

10.48309/ecc.2024.426542.1740

Abstract

Photocatalytic conversion of crude glycerol into high-value products offers economic and environmental benefits. However, impurities such as organic and inorganic salts, heavy metals, soap, and matter organic non-glycerol (MONG) can hinder direct conversion. This study investigates the transformation of non-purified crude glycerol into value-added products such as ethyl acetate using a newly developed fluorine-doped tin oxide (FTO) photocatalyst immobilized on polyurethane foam (PU). FTO-PU was synthesized by a simple mixture method, and the FTO cluster was evenly distributed on the PU foam, obstructing intrinsic PU pores and leading to a smaller surface area for FTO-PU than FTO catalysts. Despite the smaller surface area, the FTO-PU catalyst demonstrated exceptional performance, achieving 94% conversion of crude glycerol with 86% selectivity to ethyl acetate, resulting in an 81% yield. The stability and reusability of the FTO-PU catalyst were confirmed over six cycles, demonstrating its potential for efficient crude glycerol conversion and laying the foundation for advanced materials in photocatalytic systems. Critical parameters, including light power, reaction time, crude glycerol concentration, and FTO loading within the PU structure, were optimized, with 2% FTO loading on PU, 70 W light intensity, 60 min reaction time, and 10 wt% crude glycerol concentration identified as optimal conditions. Importantly, this study aligns with Sustainable Development Goal 12, emphasizing sustainable consumption and production patterns. By addressing impurities in crude glycerol and converting it into high-value products, this research contributes to efficient resource management and supports the responsible disposal of waste, aligning with global efforts for a sustainable future.

Graphical Abstract

High-performance of fluorine-doped tin oxide immobilized on polyurethane foam composite for crude glycerol to ethyl acetate photoconversion

Keywords

Main Subjects

[1] B. Dudley, BP statistical review of world energy, Energy economic, Centre for energy economics research and policy. British Petroleum, Available via https://www. bp. com/en/global/corporate/energy-economics/statistical-review-of-world-energy/electricity. html5, 2018. [Google Scholar], [Publisher]
[2] J.L. Holechek, H.M.E. Geli, M.N. Sawalhah, R. Valdez, A Global Assessment: Can Renewable Energy Replace Fossil Fuels by 2050? Sustainability (Switzerland), 2022, 14, 4792 [Crossref], [Google Scholar], [Publisher]
[3] P.A. Owusu, S. Asumadu-Sarkodie, A review of renewable energy sources, sustainability issues and climate change mitigation, Cogent Engineering, 2016, 3, 1167990. [Crossref], [Google Scholar], [Publisher]
[4] C.R. Chilakamarry, A.M. Sakinah, A.W. Zularisam and A. Pandey, Glycerol waste to value added products and its potential applications, Systems Microbiology and Biomanufacturing2021, 1, 378–396. [Crossref], [Google Scholar], [Publisher]
[5] C.C. Chong, A. Aqsha, M. Ayoub, M. Sajid, A. Z. Abdullah, S. Yusup, B.  Abdullah, A review over the role of catalysts for selective short-chain polyglycerol production from biodiesel derived waste glycerol, Environmental Technology & Innovation2020, 19, 100859. [Crossref], [Google Scholar], [Publisher]
[6] S. Konstantinovic, B. Danilovic, J. Ciric, S. Ilic, D. Savic, V. Veljkovic, Valorization of crude glycerol from biodiesel production, Chemical Industry and Chemical Engineering Quarterly 2016, 22 461–489. [Crossref], [Google Scholar], [Publisher]
[7] S. Nomanbhay, R. Hussein, M.Y. Ong, Sustainability of biodiesel production in Malaysia by production of bio-oil from crude glycerol using microwave pyrolysis: a review, Green Chemistry Letters and Reviews, 2018, 11, 135–157. [Crossref], [Google Scholar], [Publisher]
[8] U.I. Nda-Umar, I. Ramli, Y.H. Taufiq-Yap, E.N. Muhamad, An overview of recent research in the conversion of glycerol into biofuels, fuel additives and other bio-based chemicals,  Catalysts, 2019, 9, 15 [Crossref], [Google Scholar], [Publisher]
[9] M.N. Gatti, J.L. Cerioni, F. Pompeo, G.F. Santori, N.N. Nichio, High yield to 1-propanol from crude glycerol using two reaction steps with ni catalysts, Catalysts, 2020, 10, 615. [Crossref], [Google Scholar], [Publisher]
[10] P.S. Kong, M.K. Aroua, W.M. Daud, Conversion of crude and pure glycerol into derivatives: A feasibility evaluation, Renewable and Sustainable Energy Reviews, 2016, 63, 533–555. [Crossref], [Google Scholar], [Publisher]
 [11] J. Kaur, A.K. Sarma, M.K. Jha, P. Gera, Valorisation of crude glycerol to value-added products: Perspectives of process technology, economics and environmental issues, Biotechnology Reports, 2020, 27. [Crossref], [Google Scholar], [Publisher]
[12] I.C. Freitas, R.L. Manfro, M.M.V.M. Souz, Hydrogenolysis of glycerol to propylene glycol in continuous system without hydrogen addition over Cu-Ni catalysts, Applied Catalysis B: Environmental, 2018, 220, 31–41. [Crossref], [Google Scholar], [Publisher]
[13] V. K. Garlapati, U. Shankar, A. Budhiraja, Bioconversion technologies of crude glycerol to value added industrial products, Biotechnology Reports, 2016, 9, 9–14.  Crossref], [Google Scholar], [Publisher]
[14] O. Monfort, Y. Wu, Photocatalytic Processes for Environmental Applications, Processes, 2021, 9, 2080. [Crossref], [Google Scholar], [Publisher]
[15] L.I. Granone, F. Sieland, N. Zheng, R. Dillert, D.W. Bahnemann, Photocatalytic conversion of biomass into valuable products: a meaningful approach?, Green chemistry, 2018, 20,  1169-1192. [Crossref], [Google Scholar], [Publisher]
[16] R. Chong, J. Li, X. Zhou, Y. Ma, J. Yang, L. Huang, H. Han, F. Zhang, C. Li, Selective photocatalytic conversion of glycerol to hydroxyacetaldehyde in aqueous solution on facet tuned TiO 2-based catalysts, Chemical communications, 2014, 50, 165–167. [Crossref], [Google Scholar], [Publisher]
[17] J. Yu, F. Dappozze, J. Martín-Gomez, J. Hidalgo-Carrillo, A. Marinas, P. Vernoux, A. Caravaca, C. Guillard, Glyceraldehyde production by photocatalytic oxidation of glycerol on WO3-based materials, Applied Catalysis B: Environmental, 2021, 299, 120616. [Crossref], [Google Scholar], [Publisher]
[18] T. Yamamoto, H. Mine, S. Katada, T. Tone, Direct ethyl acetate synthesis from ethanol over amorphous-, monoclinic-, tetragonal ZrO2 supported copper catalysts prepared from the same zirconium source, Applied Catalysis B: Environmental2023, 327, 122433. [Crossref], [Google Scholar], [Publisher]
[19] Y. Chen, Q. Zhang, K. Liu, S. Zhang, X. Zhang, H. Liu, Simulation, optimization and intensification of the process for co-production of ethyl acetate and amyl acetate by reactive distillation, Process Safety and Environmental Protection, 2023, 171, 607-618. [Crossref], [Google Scholar], [Publisher]
[20] W. Piotrowski, R. Kubica, Integration of the process for production of ethyl acetate by an enhanced extraction process, Processes, 2021, 9, 1425. [Crossref], [Google Scholar], [Publisher]
[21] W.Z. Samad, W.N. Roslam, W. Isahak, N. Nordin, M.A. Yarmo, M.R. Yusop, Gylcerol conversion over novel fluorine-doped tin oxide supported catalyst: effect of metal loadings and glycerol concentration, Malaysian Journal of Analytical Sciences, 2015, 19, 55-64. [Google Scholar], [Publisher]
[22] W.Z. Samad, M. Goto, H. Kanda, Wahyudiono, N. Nordin, K.H. Liew, M.A. Yarmo, M.R. Yusop, Fluorine-doped tin oxide catalyst for glycerol conversion to methanol in sub-critical water, J, Supercrit. Fluids, 2017, 120, 366–378. [Crossref], [Google Scholar], [Publisher]
[23] F.V. Amorim, R.J.R. Padilha, G.M. Vinhas, M.R. Luiz, N.C. de Souza and Y.M.B. de Almeida, Development of hydrophobic polyurethane/castor oil biocomposites with agroindustrial residues for sorption of oils and organic solvents, J, Colloid Interface Sci, 2021, 581, 442–454. [Crossref], [Google Scholar], [Publisher]
[24] M. Anju, N.K. Renuka, Magnetically actuated graphene coated polyurethane foam as potential sorbent for oils and organics, Arabian Journal of Chemistry, 2020, 13, 1752–1762. [Crossref], [Google Scholar], [Publisher]
[25] D.S. Pattanayak, J. Mishra, J. Nanda, P.K. Sahoo, R. Kumar, N.K. Sahoo, Photocatalytic degradation of cyanide using polyurethane foam immobilized Fe-TCPP-S-TiO2-rGO nano-composite, Journal of Environmental Management, 2021, 297, 113312. [Crossref], [Google Scholar], [Publisher]
[26] H. Peng, T. Romero, P. Bertani, V. Ritleng, Polydopamine-Coated Polyurethane Foam as a Structured Support for the Development of an Easily Reusable Heterogeneous Photocatalyst Based on Eosin Y. Catalysts, 2023, 13, 589. [Crossref], [Google Scholar], [Publisher]
[27] L. Xiao, R. Liao, S. Yang, Y. Qiu, M. Wang, Z. Zhang, J. Du, Z. Xie, Facile Fabrication of F-Doped SnO2 Nanomaterials for Improved Photocatalytic Activity. Coatings, 2022, 12, 795. [Crossref], [Google Scholar], [Publisher]
[28] O.F. Olorundare, T.A.M. Msagati, R.W.M. Krause, J.O. Okonkwo, B.B. Mamba, Polyurethane composite adsorbent using solid phase extraction method for preconcentration of metal ion from aqueous solution, International Journal of Environmental Science and Technology, 2015, 12, 2389–2400. [Crossref], [Google Scholar], [Publisher]
[29] M.R. Lubis, R.  Saputra, M.D.  Alfarabi, S. Sarah, May. Characterization of modified polyurethane foam adsorbents for mercury adsorption applications, In IOP Conference Series: Materials Science and Engineering, 2022, 845, 12002. [Crossref], [Google Scholar], [Publisher]
[30] G. Sung, J.S. Kim, J.H. Kim, Sound absorption behavior of flexible polyurethane foams including high molecular‐weight copolymer polyol, Polymers for Advanced Technologies, 2017, 29, 852–859. [Crossref], [Google Scholar], [Publisher]
[31] A.D.  Macalino, V.A. Salen, L.Q. Reyes, September. Castor oil based polyurethanes: synthesis and characterization. In IOP Conference Series: Materials Science and Engineering, IOP Publishing, 2017, 229, 12016. [Crossref], [Google Scholar], [Publisher]
[32] H. Yang, C. Li, A. Tang, Synthesis and Characterization of Fluorine-Doped Tin Dioxide Nanocomposites,  In Proceedings of the 8 th Pacific Rim International Congress on Advanced Materials and Processing, 2013, 1507–1514. [Crossref], [Google Scholar], [Publisher]
[33] M. Kardeş, H.C. Yatmaz, K. Öztürk, ZnO Nanorods Grown on Flexible Polyurethane Foam Surfaces for Photocatalytic Azo Dye Treatment, ACS Applied Nano Materials, 2023 6, 6605–6613. [Crossref], [Google Scholar], [Publisher]
[34] S.Y. Mak, K.H. Liew, C.C. Chua, M.A. Yarmo, B.H. Yahaya, W.Z. Samad, M.S.M. Jamil, R.M. Yusop, Palladium nanoparticles supported on fluorine-doped tin oxide as an efficient heterogeneous catalyst for Suzuki coupling and 4-nitrophenol reduction, Journal of Chemical Sciences, 2019, 131, 1-12. [Crossref], [Google Scholar], [Publisher]
[35] G. Trovati, E.A. Sanches, S.C. Neto, Y.P. Mascarenhas, G.O. Chierice, Characterization of polyurethane resins by FTIR, TGA, and XRD, Journal of Applied Polymer Science, 2010, 115, 263–268. [Crossref], [Google Scholar], [Publisher]
[36] M.S.J. Khan, T. Kamal, F. Ali, A.M. Asiri, S.B. Khan, Chitosan-coated polyurethane sponge supported metal nanoparticles for catalytic reduction of organic pollutants, International journal of biological macromolecules, 2019, 132, 772–783. [Crossref], [Google Scholar], [Publisher]
[37] M.M. Ghobashy, Z.I. Abdeen, Radiation crosslinking of polyurethanes: characterization by FTIR, TGA, SEM, XRD, and raman spectroscopy, Journal of Polymers, 2016, 1–9. [Crossref], [Google Scholar], [Publisher]
[38] L. Motevalizadeh, M. Tahani, A Phenomenological Study of Chromium Impurity Effects on Lattice Microstrains of SnO2 Nanoparticles Prepared Using Sol–Gel Technique, Crystals2023, 13, 919. [Crossref], [Google Scholar], [Publisher]
[39] M.E. Bourain, A. Abdelghany, Sorption Features of Polyurethane Foam Functionalized with Salicylate for Chlorpyrifos: Equilibrium, Kinetic Models and Thermodynamic Studies, Polymers, 2020, 12, 2036. [Crossref], [Google Scholar], [Publisher]
[40] L. Stroea, A.L. Chibac-Scutaru, V. Melinte, Aliphatic polyurethane elastomers quaternized with silane-functionalized TiO2 nanoparticles with UV-shielding features, Polymers, 2021, 13, 1318. [Crossref], [Google Scholar], [Publisher]
[41] A. Ahmad, S.A.M. Jamil, T. Shean, Y. Choong, A.H. Abdullah, M.S. Mastuli, N. Othman, N. Jiman, Green flexible polyurethane foam as a potent support for Fe-Si adsorbent, Polymers, 2019, 11, 2011. [Crossref], [Google Scholar], [Publisher]
[42] M.A. Islam, Competitive sorption of metal ions and humic acid onto manganese oxides and boehmite, La Trobe University, Australia, 2018. [Google Scholar], [Publisher]
[43] K.M. Reza, A. Kurny, F. Parameters affecting the photocatalytic degradation of dyes using TiO 2: a review, Applied Water Science, 2017, 7, 1569–1578. [Crossref], [Google Scholar], [Publisher]
[44] L. Zhu, M. Zhang, J. Xu, C. Li, J. Yan, G. Zhou, W. Zhong, T. Hao, J. Song, X. Xue, Z. Zhou, R. Zeng, H. Zhu, C.C. Chen, R.C.I. Chen, Y. Zou, J. Nelson, Y. Zhang, Y. Sun, F. Liu, Single-junction organic solar cells with over 19% efficiency enabled by a refined double-fibril network morphology, Nature Materials, 2022, 21, 656–663. [Crossref], [Google Scholar], [Publisher]
[45] M.R. Karimi Estahbanati, M. Feilizadeh, F. Attar, M.C. Iliuta, Current developments and future trends in photocatalytic glycerol valorization: process analysis, Reaction Chemistry & Engineering, 2021, 6, 197–219. [Crossref], [Google Scholar], [Publisher]
[46] R. Gusain, N. Kumar, S.S. Ray, Factors influencing the photocatalytic activity of photocatalysts in wastewater treatment. Photocatalysts in Advanced Oxidation Processes for Wastewater Treatment, 2020, 229-270. [Crossref], [Google Scholar], [Publisher]
 [47] S. Zhang, P. Gu, R. Ma, C. Luo, T. Wen, G. Zhao, W. Cheng, X. Wang, Recent developments in fabrication and structure regulation of visible-light-driven g-C3N4-based photocatalysts towards water purification: a critical review, Catalysis Today, 2019, 335, 65–77. [Crossref], [Google Scholar], [Publisher]
[48] M.D. Argyle, C.H. Bartholomew, Heterogeneous catalyst deactivation and regeneration: a review, Catalysts2015, 5, 145-269. [Crossref], [Google Scholar], [Publisher]
[49] M.D. Nasrallah, Sintering process and catalysis, Int J Nanomater Nanotechnol Nanomed, 2018, 4, 1–3. [Crossref], [Google Scholar], [Publisher]
[50] H. Yang, T. Han, W. Yang, L. Sandström, P. G. Jönsson, Influence of the porosity and acidic properties of aluminosilicate catalysts on coke formation during the catalytic pyrolysis of lignin, Journal of Analytical and Applied Pyrolysis, 2022, 165, 105536. [Crossref], [Google Scholar], [Publisher]