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Title: Active Phase of a Nickel Phosphide (Ni2P) Catalyst Supported on KUSY Zeolite for the Hydrodesulfurization of 4,6-DMDBT

Abstract

Ni{sub 2}P catalysts supported on potassium ion-exchanged ultrastable Y zeolites (KUSY) were prepared by temperature-programmed reduction (TPR), and the effect of Ni{sub 2}P loading and initial Ni/P ratios on the hydroprocessing performance was studied. X-ray diffraction (XRD), and extended X-ray absorption fine structure (EXAFS) were used to obtain structural parameters. Transmission electron microscopy (TEM) analysis showed that the KUSY-supported Ni{sub 2}P samples consisted of nanoparticles, which were likely situated in the mesoporous cavities or the external surfaces of the zeolite crystals. The catalytic activity was measured at 613 K and 3.1 MPa in a three-phase fixed bed reactor for hydrodesulfurization (HDS) and hydrodenitrogenation (HDN) using a model liquid feed containing 500 ppm S as 4,6-dimethyldibenzothiophene (4,6-DMDBT), 500 ppm N as quinoline, and 3000-6000 ppm S as dimethyldisulfide (DMDS). Partial exchange with K enhanced the catalytic activity for the HDS of 4,6-DMDBT and resistance to N-compound inhibition. The Ni{sub 2}P/KUSY had high activity with an HDS conversion of 99%, and an HDN conversion of 100%, which were much higher than those of a commercial Ni-Mo-S/Al{sub 2}O{sub 3} catalyst with an HDS conversion of 80% and HDN conversion of 100%, based on equal sites (240 {mu}mol) loaded in the reactor. The sitesmore » were counted by CO chemisorption for the phosphide and by low-temperature O{sub 2} chemisorption for the sulfide. Deficiency of P in the Ni{sub 2}P resulted in deactivation, probably due to susceptibility to sulfidation. EXAFS analysis of the catalysts showed that the addition of extra P led to an increase in Ni-P coordination with lengthening of Ni-Ni bond distances, resulting in a high and stable catalytic activity.« less

Authors:
; ;
Publication Date:
Research Org.:
Brookhaven National Laboratory (BNL) National Synchrotron Light Source
Sponsoring Org.:
Doe - Office Of Science
OSTI Identifier:
930386
Report Number(s):
BNL-81108-2008-JA
Journal ID: ISSN 0926-860X; ACAGE4; TRN: US200904%%533
DOE Contract Number:  
DE-AC02-98CH10886
Resource Type:
Journal Article
Resource Relation:
Journal Name: Applied Catalysis A: General; Journal Volume: 322
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; NICKEL PHOSPHIDES; CATALYTIC EFFECTS; HYDROGENATION; DESULFURIZATION; POLYCYCLIC SULFUR HETEROCYCLES; ZEOLITES; CATALYST SUPPORTS; national synchrotron light source

Citation Formats

Lee,Y., Shu, Y., and Oyama, S.. Active Phase of a Nickel Phosphide (Ni2P) Catalyst Supported on KUSY Zeolite for the Hydrodesulfurization of 4,6-DMDBT. United States: N. p., 2007. Web. doi:10.1016/j.apcata.2007.01.007.
Lee,Y., Shu, Y., & Oyama, S.. Active Phase of a Nickel Phosphide (Ni2P) Catalyst Supported on KUSY Zeolite for the Hydrodesulfurization of 4,6-DMDBT. United States. doi:10.1016/j.apcata.2007.01.007.
Lee,Y., Shu, Y., and Oyama, S.. Mon . "Active Phase of a Nickel Phosphide (Ni2P) Catalyst Supported on KUSY Zeolite for the Hydrodesulfurization of 4,6-DMDBT". United States. doi:10.1016/j.apcata.2007.01.007.
@article{osti_930386,
title = {Active Phase of a Nickel Phosphide (Ni2P) Catalyst Supported on KUSY Zeolite for the Hydrodesulfurization of 4,6-DMDBT},
author = {Lee,Y. and Shu, Y. and Oyama, S.},
abstractNote = {Ni{sub 2}P catalysts supported on potassium ion-exchanged ultrastable Y zeolites (KUSY) were prepared by temperature-programmed reduction (TPR), and the effect of Ni{sub 2}P loading and initial Ni/P ratios on the hydroprocessing performance was studied. X-ray diffraction (XRD), and extended X-ray absorption fine structure (EXAFS) were used to obtain structural parameters. Transmission electron microscopy (TEM) analysis showed that the KUSY-supported Ni{sub 2}P samples consisted of nanoparticles, which were likely situated in the mesoporous cavities or the external surfaces of the zeolite crystals. The catalytic activity was measured at 613 K and 3.1 MPa in a three-phase fixed bed reactor for hydrodesulfurization (HDS) and hydrodenitrogenation (HDN) using a model liquid feed containing 500 ppm S as 4,6-dimethyldibenzothiophene (4,6-DMDBT), 500 ppm N as quinoline, and 3000-6000 ppm S as dimethyldisulfide (DMDS). Partial exchange with K enhanced the catalytic activity for the HDS of 4,6-DMDBT and resistance to N-compound inhibition. The Ni{sub 2}P/KUSY had high activity with an HDS conversion of 99%, and an HDN conversion of 100%, which were much higher than those of a commercial Ni-Mo-S/Al{sub 2}O{sub 3} catalyst with an HDS conversion of 80% and HDN conversion of 100%, based on equal sites (240 {mu}mol) loaded in the reactor. The sites were counted by CO chemisorption for the phosphide and by low-temperature O{sub 2} chemisorption for the sulfide. Deficiency of P in the Ni{sub 2}P resulted in deactivation, probably due to susceptibility to sulfidation. EXAFS analysis of the catalysts showed that the addition of extra P led to an increase in Ni-P coordination with lengthening of Ni-Ni bond distances, resulting in a high and stable catalytic activity.},
doi = {10.1016/j.apcata.2007.01.007},
journal = {Applied Catalysis A: General},
number = ,
volume = 322,
place = {United States},
year = {Mon Jan 01 00:00:00 EST 2007},
month = {Mon Jan 01 00:00:00 EST 2007}
}