Spectroscopic and Kinetic Studies of Hydrodenitrogenation and Hydrodesulfurization over Supported Nickel Phosphide (Ni₂P)

This dissertation describes preparation and characterization of Ni₂P catalysts and their application in hydrodesulfurization (HDS) and hydrodenitrogenation (HDN). The work carried out includes synthesis of Ni₂P on different siliceous supports, SiO2 and MCM-41. It also includes characterization of these catalytic materials using X-ray diffraction (XRD), temperature-programmed reduction (TPR), Fourier transform infrared (FTIR) spectroscopy and X-ray absorbance fine structure (XAFS) spectroscopy. In situ FTIR was employed to study the acidity of Ni₂P/SiO₂ and probe the catalytic sites involved in the HDN of pyridine. Transient and steady-state kinetics of a surface intermediate that is formed upon pyridine adsorption and reaction was studied to elucidate the mechanism of HDN over Ni₂P/SiO₂. Additionally, in situ FTIR and X-ray absorption near edge structure (XANES) spectroscopy was utilized to probe the bonding, mechanism and kinetics of thiophene HDS over a novel MCM-41-supported Ni₂P catalyst. The use of these techniques allowed for better understanding of the surface intermediates, mechanisms and the nature of the active sites involved in HDN and HDS.

Name thesis:degree_name

Ph. D.

Level thesis:degree_level

doctoral

Discipline thesis:degree_discipline

Chemical Engineering

Department dc:contributor.department

Chemical Engineering

Grantor dc:publisher

Virginia Tech

Year dc:date.issued

2008

Author dc:creator

• Gott, Travis Matthew

Chair dc:contributor.committeechair

• Oyama, Shigeo Ted

Committee members dc:contributor.committeemember

• Achenie, Luke E. K.
• Cox, David F.
• Hanson, Brian E.

• Nickel phosphide
• HDN
• HDS
• pyridine
• thiophene
• FTIR
• XAFS

Statement dc:rights

• In Copyright

Licence dc:rights.uri

• http://rightsstatements.org/vocab/InC/1.0/

Dc Identifier Other

etd-11112008-142534

OAI identifier oai:identifier

oai:vtechworks.lib.vt.edu:10919/29536