Quantum chemical hydrogenolysis strategy for elimination of heteroatoms in biomass homologous organic compounds based on oxolane and thiolane

Simplice Koudjina; Wilfried G Kanhounnon; Gaston A Kpotin; Affi Sopi Thomas; René Sawadogo; Abderrahmane Semmeq; Naveen Kosar; Michael Badawi; Tariq Mahmood; Guy Y S Atohoun

doi:10.1016/j.jmgm.2022.108268

Quantum chemical hydrogenolysis strategy for elimination of heteroatoms in biomass homologous organic compounds based on oxolane and thiolane

J Mol Graph Model. 2022 Nov:116:108268. doi: 10.1016/j.jmgm.2022.108268. Epub 2022 Jul 14.

Authors

Affiliations

¹ Laboratory of Theoretical Chemistry and Molecular Spectroscopy (LACTHESMO), University of Abomey-Calavi (UAC), 03 BP 3409, Cotonou, Benin; National School of Applied Biosciences and Biotechnologies (ENSBBA) National University of Sciences, Technologies, Engineering and Mathematics (UNSTIM), BP 2282, Goho Abomey, Benin. Electronic address: simplice.koudjina@unstim.bj.
² Laboratory of Theoretical Chemistry and Molecular Spectroscopy (LACTHESMO), University of Abomey-Calavi (UAC), 03 BP 3409, Cotonou, Benin; Laboratory of Physics and Theoretical Chemistry, UMR 7019, CNRS University of Lorraine, Nancy, France.
³ Laboratory of Theoretical Chemistry and Molecular Spectroscopy (LACTHESMO), University of Abomey-Calavi (UAC), 03 BP 3409, Cotonou, Benin.
⁴ Laboratory of Thermodynamics and Physico-Chemistry of Medium (LTPCM), UFR-SFA, University of Nangui Abrogoua, 02 B.P. 801, Abidjan, Republic of Côte d'Ivoire.
⁵ Laboratory of Molecular Chemistry and Materials University of Ouagadougou, UFR/SEA, 03 BP 7021, Burkina Faso.
⁶ Laboratory of Physics and Theoretical Chemistry, UMR 7019, CNRS University of Lorraine, Nancy, France.
⁷ Department of Chemistry, University of Management and Technology (UMT), C11, Johar Town, Lahore, Pakistan.
⁸ Department of Chemistry, COMSATS University Islamabad, Abbottabad Campus Abbottabad, 22060, Pakistan; Department of Chemistry, College of Science, University of Bahrain, P.O. Box 32038, Bahrain. Electronic address: mahmood@cuiatd.edu.pk.

PMID: 35872464
DOI: 10.1016/j.jmgm.2022.108268

Abstract

Bio-oils obtained from biomass contain heteroatoms compounds, like oxolane and thiolane. It is quite difficult for industrialist to purify such refractory bio-oils. One of the efficient strategies for the elimination of heteroatoms is hydrogenolysis process, which results in the formation of H₂O and H₂S residues as by-products. In this work, quantum chemical studies have been used to analyse the reaction mechanism for the removal of hetero atoms (S and O) as H₂O and H₂S. We selected B3LYP functional of DFT with Pople's basis set 6-311G(d,p) for computing the hydrogenolysis steps without catalyst. LANL2DZ basis set, is used for studying hydrogenolysis steps involving AlCl₃ and WS₃H₃⁺ as catalysts. All the reactions are analysed at the temperature of 600 K and pressure of 40 bars. Structural, thermodynamic, kinetic properties have been employed to study this process. The analysis of variations parameters during the hydrogenolysis process reveals that these two organic biomass compounds undergo sequential ring opening at C-X (X = O, S) bonds. Butanol and Butanethiol are obtained as a result of first hydrogenolysis process, and these compounds are converted to butane during second catalytic process while eliminating heteroatoms.

Keywords: DFT; Hydrogenolysis; Intrinsic reaction coordinates; Oxolane; Thiolane; Transition State.

MeSH terms

Biomass
Catalysis
Kinetics
Oils*
Temperature

Substances

Oils