TY - JOUR
T1 - Catalytic methyl mercaptan coupling to ethylene in chabazite
T2 - DFT study of the first CC bond formation
AU - Baltrusaitis, J.
AU - Bučko, T.
AU - Michaels, W.
AU - Makkee, M.
AU - Mul, G.
N1 - Funding Information:
Partial financial support from Lehigh University is gratefully acknowledged. We thank SURFsara ( www.surfsara.nl ) for the support in using the Cartesius Compute Cluster (the Netherlands). Part of the calculations was performed using computational resources of supercomputing infrastructure of Computing Center of the Slovak Academy of Sciences acquired in projects ITMS 26230120002 and 26210120002 supported by the Research and Development Operational Program funded by the ERDF. T. B. acknowledges support from the project VEGA-1/0338/13. Dr. Steeve Chrétien is gratefully acknowledged for useful discussions.
Publisher Copyright:
© 2016 Elsevier B.V.
PY - 2016/6/15
Y1 - 2016/6/15
N2 - Methyl mercaptan, CH3SH, is an industrial waste as well as the reactive product of several H2 and H2S induced catalytic hydrogenation processes of COS and CS2. Its coupling into value added products is of great importance in monetizing sour natural gas. In the present work, the full theoretical cycle of catalytic CH3SH coupling to form ethene was investigated by means of density functional theory (DFT) using chabazite as a model catalyst with emphasis on the first CC bond formation. Calculated thermodynamics were compared with those of analogous and well established CH3OH processes to identify the similarities and differences in the reactive pathways. With few exceptions, CH3SH catalytic transformations are of higher free energy when compared to those of CH3OH. The trimethylsulfonium ion, TMS, isostructural with that of the trimethyloxonium ion, TMO, is shown to be a key reactive intermediate and a thermodynamically stable species leading to ethene formation.
AB - Methyl mercaptan, CH3SH, is an industrial waste as well as the reactive product of several H2 and H2S induced catalytic hydrogenation processes of COS and CS2. Its coupling into value added products is of great importance in monetizing sour natural gas. In the present work, the full theoretical cycle of catalytic CH3SH coupling to form ethene was investigated by means of density functional theory (DFT) using chabazite as a model catalyst with emphasis on the first CC bond formation. Calculated thermodynamics were compared with those of analogous and well established CH3OH processes to identify the similarities and differences in the reactive pathways. With few exceptions, CH3SH catalytic transformations are of higher free energy when compared to those of CH3OH. The trimethylsulfonium ion, TMS, isostructural with that of the trimethyloxonium ion, TMO, is shown to be a key reactive intermediate and a thermodynamically stable species leading to ethene formation.
KW - Chabazite
KW - DFT
KW - Ethylene
KW - Methyl mercaptan
KW - 2023 OA procedure
UR - https://www.scopus.com/pages/publications/84955291780
U2 - 10.1016/j.apcatb.2016.01.021
DO - 10.1016/j.apcatb.2016.01.021
M3 - Article
SN - 0926-3373
VL - 187
SP - 195
EP - 203
JO - Applied catalysis B: environmental
JF - Applied catalysis B: environmental
ER -