Science Talks 8 (2023) 100264

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Science Talks
journal homepage: www.elsevier.es/sctalk

Biomass derived heterogenous catalyst for synthesis of solketal

from biodiesel byproduct glycerol
Supongsenla Ao, Samuel Lalthazuala Rokhum
⁎
Department of Chemistry, National Institute of Technology Silchar, Silchar 788010, Assam, India

A R T I C L E I N F O A B S T R A C T

Glycerol valorisation is crucial for long-term economic viability due to the rise in biodiesel synthesis on a global scale.
Keywords: Therefore, it is highly desirable to convert bioglycerol into platform chemicals like solketal, a fuel additive which will
Biodiesel help sustain the biodiesel industry. Herein, glycerol is transformed into solketal utilising a heterogeneous catalyst de-
Bioglycerol
rived from SO3H-functionalized derived aromatic carbonaceous material with auxiliary hydrophilic groups and micro-
Solketal
Acetalization
wave irradiation. An ideal glycerol to acetone molar ratio of 1:5 was found for the acetalization process that produces
Sustainability solketal. A conversion of glycerol 98.1.4% with 100% selectivity to solketal was obtained using an 8 wt% catalyst dose
at 70 °C for just 10 min using the method of microwave heating (50 W, 100 pressure). The acetalization reaction's ac-
tivation energy was found to be 35.8 kJ mol−1. The reusability of the catalyst was studied exhaustively over the course
of six cycles, and EDX results revealed that there was only a minor loss of activity in the 6th reaction cycle due to mod-
erate leaching of active sites.

Video to this article can be found online at https://doi.org/10.1016/

j.sctalk.2023.100264.

Figures and tables

Fig. 1. Biodiesel production via transesterification reaction [1,2].

Abbreviations: BET, Brunauer-Emmett-Teller; FTIR, Fourier Transform Infra-Red; GC–MS, Gas Chromatography-Mass Spectrometry; MTOR, Methanol-to-oil-ratio; SEM-EDX, Scanning Electron
Microscopy- Energy - dispersive X-ray spectroscopy; TEM, Transmission Electron Microscopy; TGA, Thermogravimetric Analysis; NMR, Nuclear Magnetic Resonance; XPS, X-ray Photoelectron
Spectroscopy; XRD, X-Ray Diffraction.
⁎ Corresponding author.
E-mail address: rokhum@che.nits.ac.in (S.L. Rokhum).

http://dx.doi.org/10.1016/j.sctalk.2023.100264
Received 17 May 2023; Accepted 18 July 2023
Available online xxxx
2772-5693/© 2023 The Authors. Published by Elsevier Ltd. This is an open access article under the CC BY license (http://creativecommons.org/licenses/by/4.0/).
S. Ao, S.L. Rokhum Science Talks 8 (2023) 100264

Fig. 2. Biodiesel production synthesis and acetalization of glycerol to form solketal [3].

Fig. 3. Synthesis of solketal via acetalization reaction using as-prepared SAFACAM catalyst ( SO3H) [1,2].

Fig. 4. Proposed mechanism of glycerol acetalization using SAFACAM catalyst [1,4].

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S. Ao, S.L. Rokhum Science Talks 8 (2023) 100264

Fig. 5. Scanning Electron Microscopy of as prepared SAFACAM (a-c). Scale bars: 500 μm (a), 100 μm (b), 20 μm (c)) and elemental mapping of an individual as prepared solid
catalyst particle displaying the presence of carbon (d), oxygen (e) and sulfur (f) (scale bars: 100 μm) along with the EDS data shown in ‘g’ indicated by the white box in (b)
[1,2].

Fig. 6. N2 adsorption-desorption isotherms and BJH pore size distribution curve (inset) for the current SAFACAM [1,2].

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S. Ao, S.L. Rokhum Science Talks 8 (2023) 100264

Fig. 7. XRD pattern (a), FT-IR spectrum (b), and TGA/DTG data (black and red lines, respectively; c) of the current, SAFACAM solid catalyst [1,2]. (For interpretation of the
references to colour in this figure legend, the reader is referred to the web version of this article.)

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S. Ao, S.L. Rokhum Science Talks 8 (2023) 100264

Fig. 8. XPS analysis of as prepared SAFACAM catalyst (a), showing deconvoluted signals (in blue and green) along with raw (black) and smoothed (red) data for C1s (b), O1s
(c), and S2p (d) regions [1,2]. (For interpretation of the references to colour in this figure legend, the reader is referred to the web version of this article.)

Fig. 9. (a) –ln(1–X) vs. time (X = glycerol conversion) at subsequent heating temperatures for the acetalization, and (b) Arrhenius plot of ln k vs 1/T [1].

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Fig. 10. a) 1H NMR and b) 13C NMR spectra at 28 °C in methanol‑d4 of the product of glycerol acetalization using the SAFACAM catalyst [1].

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Fig. 11. GC–MS analysis of product solketal [1,5].

Fig. 12. Reusability test of SAFACAM solid catalyst in the acetalization (conversion) of glycerol over 6 cycles [1].

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Fig. 13. 13C ssNMR data for fresh (shown in red) and spent (after 6 reaction cycles; shown in blue) SAFACAM solid catalyst [1,2]. (For interpretation of the references to
colour in this figure legend, the reader is referred to the web version of this article.)

Fig. 14. 1H ssNMR of fresh (shown in red) and spent (after 6 reaction cycles) SAFACAM solid catalyst (shown in blue) [1,2]. (For interpretation of the references to colour in
this figure legend, the reader is referred to the web version of this article.)

CRediT authorship contribution statement Conflicts of Interest

Supongsenla Ao: Methodology, Software, Data curation, Writing – The authors confirm no conflicts of interest.
original draft, Visualization, Investigation. Samuel Lalthazuala Rokhum:
Conceptualization, Visualization, Writing – review & editing, Supervision.
References
Data availability
[1] S. Ao, L.A. Alghamdi, T. Kress, M. Selvaraj, G. Halder, A.E.H. Wheatley, S. Lalthazuala
Rokhum, Microwave-assisted valorization of glycerol to solketal using biomass-derived
The datasets used and/or analyzed during the current study are available heterogeneous catalyst, Fuel. 345 (2023), 128190, https://doi.org/10.1016/J.FUEL.
from the corresponding author on reasonable request. 2023.128190.

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S. Ao, S.L. Rokhum Science Talks 8 (2023) 100264

[2] S.L. Rokhum, B. Changmai, T. Kress, A.E.H. Wheatley, A one-pot route to tunable sugar-
derived sulfonated carbon catalysts for sustainable production of biodiesel by fatty acid
esterification, Renew. Energy 184 (2022), https://doi.org/10.1016/j.renene.2021.12.001.
[3] M. Van Lal, A. Chumpi, K. Belur, S. Ao, J. Vl, S. Lalthazuala, Bioresource technology
reports valorisation of food waste to sustainable energy and other value-added products:
a review, Bioresour. Technol. Rep. 17 (2022), 100945, https://doi.org/10.1016/j.biteb.
2022.100945.
[4] K. Rajkumari, B. Changmai, A.K. Meher, C. Vanlalveni, P. Sudarsanam, A.E.H. Wheatley,
S.L. Rokhum, A reusable magnetic nanocatalyst for bio-fuel additives: the ultrasound-
assisted synthesis of solketal, Sustain. Energy Fuel 5 (2021) 2362–2372, https://doi.
org/10.1039/d0se01900c.
[5] S. Ao, S.L. Rokhum, Recent Advances in the Valorization of Biodiesel By-Product Glycerol
to Solketal, 2022, 2022, https://doi.org/10.1155/2022/4938672.
Samuel Lalthazuala Rokhum is an Assistant Professor at
National Institute of Technology Silchar. He has worked as a
postdoctoral fellow in the Department of Chemistry, Cambridge
University, UK (2019–21). His research interests include
organic chemistry, renewable energy, biofuels, heterogeneous
catalysis. He has published more than 70 research papers and
21 book chapters. He has served as an Academic Editor of Inter-
national Journal of Energy Research (Hindawi | Wiley) and
Journal of Chemistry (Hindawi).

Supongsenla Ao is a doctoral student at National Institute of

Technology Silchar at the Department of Chemistry (2021-).
She completed her M.Sc. in Chemistry from Kumaun University
Nainital in the year 2020. Her research interests are synthesis of
biomass derived heterogenous catalyst for the synthesis of bio-
diesel and various value additives products in the field of biofuel
industry.