ab initio mechanistic and thermochemical study of...
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Ab initio mechanistic and thermochemical study ofthe adsorption of phenanthrene over a
hydrocracking catalyst
1
C.M. Celis-Cornejo1, M.M. Garnica-Mantilla1,2, P. Balbuena2, V.G. Baldovino-Medrano1, , G.E.
Ramírez-Caballero1*
1Centro de Investigaciones en Catálisis (@CICAT), Universidad Industrialde Santander, Parque Tecnológico Guatiguará (PTG), km. 2 vía El Refugio,Piedecuesta (Santander), 681011, Colombia, V.G.B.M. orcid.org/0000‐0003‐3227‐0251 Twitter: @vigabalme2Department of Chemical Engineering, Texas A&M University, CollegeStation, Texas 77843, United States*Contact information. E‐mail: vicbaldo@uis.edu.co Twitter: @vigabalme
Email: carlos.celis@outlook.es Twitter: @CelisCornejoC
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Molecule ∆ (kJ·mol-1)Carbazole -116.581,2,3,4-Tetrahydrocarbazole -99.4Quinoline -150.771,2,3,4-Tetrahydronaphthalene -71.431,2,3,4-Tetrahydrophenanthrene -78.571,2,3,4-Tetrahydrocrysene -78.38
ObjectiveTo study the kinetics and thermodynamics for the catalyticcracking reaction of the phenanthrene, for betterunderstanding the way this nitrogenated molecules inhibitthe hydrocracking.
HDT
VGO
HDT-VGO
Gases (NH3, H2S)
HYDROCRACKING Nitrogen content:< 20 ppm of total N2
N
H
Non-basic nitrogenmolecules
N
Basic nitrogenmolecules
3 3
(a) (b)
∆
MethodologyAdsorption study
Software VASP + Bader
Method PBE
Energy cut off 600 eV
VdW Forces Yes
Kpoints Gamma
Mechanistic study
Software Gaussian
Method b3lyp/6-311G(d,p)
Fragment UnconstrainedMordenite Zeolite: Bulk, Cluster.
1
2
34
4a
Position Distance (Å) ∆HADS (kJ·mol-1)C(3)-H+ 2.28 -61.87104C(4)-H+ 2.38 -78.82464C(4a)-H+ 2.24 -82.51104H-H+ 2.42* -67.35264
Adosrption energies of phenanthrene over mordenite:
Feasible protonation of phenanthrene at the aromatic ring
Phenanthrene
Results
H
H
O
O
H
O
H
O
Al
O
AlO
Si
O
O
H
Si
O
H
OSi Si
H
O
H
O
O
Si
O
H
O
H
O
O
H
O O
H
H
O O
O
H
OAl
O
H
O
SiO
OO O O
AlSi4O16H13+AlSi47O116H33
+
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