Cobalt-Molybdenum Single-Layered Nanocatalysts Decorated on Carbon Nanotubes and the Influence of Preparation Conditions on Their Hydrodesulfurization Catalytic Activity

Whelan, Jamie; Katsiotis, Marios S.; Stephen, Samuel; Luckachan, Gisha E.; Tharalekshmy, Anjana; Banu, Nicoleta Doriana; Idrobo, Juan-Carlos; Pantelides, Sokrates T.; Vladea, Radu V.; Banu, Ionut; Alhassan, Saeed M.

doi:10.1021/acs.energyfuels.8b01571

Cobalt-Molybdenum Single-Layered Nanocatalysts Decorated on Carbon Nanotubes and the Influence of Preparation Conditions on Their Hydrodesulfurization Catalytic Activity

Journal Article · Tue Jun 19 04:00:00 EDT 2018 · Energy and Fuels

DOI:https://doi.org/10.1021/acs.energyfuels.8b01571· OSTI ID:1597897

^[1]; ^[2]; Stephen, Samuel ^[3]; Luckachan, Gisha E. ^[3]; Tharalekshmy, Anjana ^[3]; Banu, Nicoleta Doriana ^[4]; Idrobo, Juan-Carlos ^[5]; Pantelides, Sokrates T. ^[6]; Vladea, Radu V. ^[3]; Banu, Ionut ^[7]; ^[3]

Khalifa Univ. of Science and Technology, Abu Dhabi (United Arab Emirates); New York Univ., Abu Dhabi (United Arab Emirates); Vanderbilt University
Khalifa Univ. of Science and Technology, Abu Dhabi (United Arab Emirates); TITAN Cement Company, Athens (Greece)
Khalifa Univ. of Science and Technology, Abu Dhabi (United Arab Emirates)
Khalifa Univ. of Science and Technology, Abu Dhabi (United Arab Emirates); Romanian Academy, Bucharest (Romania)
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
Vanderbilt Univ., Nashville, TN (United States)
Khalifa Univ. of Science and Technology, Abu Dhabi (United Arab Emirates); Univ. Politehnica of Bucharest, Bucharest (Romania)

Hydrodesulfurization (HDS) of crude oil plays a vital role in the refining of petroleum products. With ever-increasing regulations restricting the allowable concentrations of sulfur in fuel, further research is required to produce more efficient and effective catalysts. Herein, we have synthesized carbon nanotube (CNT)-supported cobalt-molybdenum (CoMo) catalysts for HDS of dibenzothiophene (DBT) via Co-first and Mo-first sequential impregnation as well as co-impregnation. Spectroscopic analysis shows the formation of a CoMo catalyst with no free sulfided Co phase present. Additionally, CoMo catalysts are found to be predominantly single-layered nanocatalysts layered on the CNT support. Temperature-programmed reduction (TPR) measurements show differences in reducing temperature of the sulfided CoMo catalysts prepared by the different methods, but catalyst activities for HDS of DBT did not fully align with the TPR-predicted order. Thus, provided the reaction temperature is high enough, reducibility may not always be an adequate gauge of catalytic activity. Conversion of DBT was highest in Mo-first sequential impregnation (81.5%), followed by co-impregnation (64%) and Co-first sequential impregnation (60%) on a CNT support. Finally, while these results contrast with some others regarding the order of impregnation, we propose that the preferred impregnation order is actually support-dependent, rather than an absolute quality.

View Accepted Manuscript (DOE)

Research Organization:: Vanderbilt Univ., Nashville, TN (United States)

Sponsoring Organization:: USDOE Office of Science (SC)

Grant/Contract Number:: FG02-09ER46554

OSTI ID:: 1597897

Journal Information:: Energy and Fuels, Journal Name: Energy and Fuels Journal Issue: 7 Vol. 32; ISSN 0887-0624

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

References (33)

A new reaction model for aquathermolysis of Athabasca bitumen Kapadia, Punitkumar R.; Kallos, Michael S.; Gates, Ian D. The Canadian Journal of Chemical Engineering, Vol. 91, Issue 3 https://doi.org/10.1002/cjce.21662	journal	February 2012
Effect of tungsten loading on the physiochemical properties of nanocatalysts of Ni–Mo–W/carbon nanotubes for the hydrodesulfurization of thiophene Nejad, Dariush Moghadam; Rahemi, Nader; Allahyari, Somaiyeh Reaction Kinetics, Mechanisms and Catalysis, Vol. 120, Issue 1 https://doi.org/10.1007/s11144-016-1093-7	journal	October 2016
Synthesis of Nanocatalyst for Hydrodesulfurization of Gasoil Using Laboratory Hydrothermal Rig Mohammed, Mohammed I.; Abdul Razak, Adnan A.; Shehab, Mohammed A. Arabian Journal for Science and Engineering, Vol. 42, Issue 4 https://doi.org/10.1007/s13369-016-2249-5	journal	June 2016
A comparative study on the basis of adsorption capacity between CNTs and activated carbon as adsorbents for removal of noxious synthetic dyes: a review Zare, Karim; Gupta, Vinod Kumar; Moradi, Omid Journal of Nanostructure in Chemistry, Vol. 5, Issue 2 https://doi.org/10.1007/s40097-015-0158-x	journal	April 2015
Influence of the impregnation order of molybdenum and cobalt in carbon-supported catalysts for hydrodeoxygenation reactions Ferrari, Maria; Delmon, Bernard; Grange, Paul Carbon, Vol. 40, Issue 4 https://doi.org/10.1016/S0008-6223(01)00128-2	journal	April 2002
Mesoscopic thermal and thermoelectric measurements of individual carbon nanotubes Small, Joshua P.; Shi, Li; Kim, Philip Solid State Communications, Vol. 127, Issue 2 https://doi.org/10.1016/S0038-1098(03)00341-7	journal	July 2003
Support effects on the chemical property and catalytic activity of Co-Mo HDS catalyst in sulfur recovery Pour, Ali Nakhaei; Rashidi, Ali Morad; Jozani, Kherolah Jafari Journal of Natural Gas Chemistry, Vol. 19, Issue 1 https://doi.org/10.1016/S1003-9953(09)60032-3	journal	January 2010
Influence of the preparation method on the activity of phosphate-containing CoMo/HMS catalysts in deep hydrodesulphurization Nava, R.; Morales, J.; Alonso, G. Applied Catalysis A: General, Vol. 321, Issue 1 https://doi.org/10.1016/j.apcata.2007.01.038	journal	March 2007
Synthesis of CoMo-based carbon hydrodesulfurization catalysts: Influence of the order of metal impregnations on the activity Farag, Hamdy Applied Catalysis B: Environmental, Vol. 84, Issue 1-2 https://doi.org/10.1016/j.apcatb.2008.02.026	journal	October 2008
Accelerated deactivation studies of the natural-gas oxidation catalyst—Verifying the role of sulfur and elevated temperature in catalyst aging Honkanen, Mari; Kärkkäinen, Marja; Kolli, Tanja Applied Catalysis B: Environmental, Vol. 182 https://doi.org/10.1016/j.apcatb.2015.09.054	journal	March 2016
Nanoparticle technology for heavy oil in-situ upgrading and recovery enhancement: Opportunities and challenges Hashemi, Rohallah; Nassar, Nashaat N.; Pereira Almao, Pedro Applied Energy, Vol. 133 https://doi.org/10.1016/j.apenergy.2014.07.069	journal	November 2014
Probing the interaction of single walled carbon nanotubes within cell culture medium as a precursor to toxicity testing Casey, A.; Davoren, M.; Herzog, E. Carbon, Vol. 45, Issue 1 https://doi.org/10.1016/j.carbon.2006.08.009	journal	January 2007
Spectroscopic analysis confirms the interactions between single walled carbon nanotubes and various dyes commonly used to assess cytotoxicity Casey, A.; Herzog, E.; Davoren, M. Carbon, Vol. 45, Issue 7 https://doi.org/10.1016/j.carbon.2007.03.033	journal	June 2007
Highly dispersed CoMoS phase on titania nanotubes as efficient HDS catalysts Cortés-Jácome, M. A.; Escobar, J.; Angeles Chávez, C. Catalysis Today, Vol. 130, Issue 1 https://doi.org/10.1016/j.cattod.2007.07.012	journal	January 2008
Recent studies on the preparation, activation and design of active phases and supports of hydrotreating catalysts Breysse, Michèle; Geantet, Christophe; Afanasiev, Pavel Catalysis Today, Vol. 130, Issue 1 https://doi.org/10.1016/j.cattod.2007.08.018	journal	January 2008
Unsupported transition metal sulfide catalysts: 100 years of science and application Chianelli, Russell R.; Berhault, Gilles; Torres, Brenda Catalysis Today, Vol. 147, Issue 3-4 https://doi.org/10.1016/j.cattod.2008.09.041	journal	October 2009
Anthropogenic Carbon Nanotubes Found in the Airways of Parisian Children Kolosnjaj-Tabi, Jelena; Just, Jocelyne; Hartman, Keith B. EBioMedicine, Vol. 2, Issue 11 https://doi.org/10.1016/j.ebiom.2015.10.012	journal	November 2015
Aquathermolysis of heavy oil: A review and perspective on catalyst development Muraza, Oki; Galadima, Ahmad Fuel, Vol. 157 https://doi.org/10.1016/j.fuel.2015.04.065	journal	October 2015
Single-walled carbon nanotubes supported Ni–Y as catalyst for ultra-deep hydrodesulfurization of gasoline and diesel Xu, Kai; Li, Yongfeng; Xu, Xiuwen Fuel, Vol. 160 https://doi.org/10.1016/j.fuel.2015.07.105	journal	November 2015
Support effects in CoMo hydrodesulfurization catalysts prepared with EDTA as a chelating agent Rana, M.; Ramirez, J.; Gutierrezalejandre, A. Journal of Catalysis, Vol. 246, Issue 1 https://doi.org/10.1016/j.jcat.2006.11.025	journal	February 2007
Preparation of Co–Mo supported multi-wall carbon nanotube for hydrocracking of extra heavy oil Rad, Mohsen Rahimi; Rashidi, Alimorad; Vafajoo, Leila Journal of Industrial and Engineering Chemistry, Vol. 20, Issue 6 https://doi.org/10.1016/j.jiec.2014.01.036	journal	November 2014
Co–Mo catalysts for ultra-deep HDS of diesel fuels prepared via synthesis of bimetallic surface compounds Klimov, Oleg V.; Pashigreva, Anastasiya V.; Fedotov, Martin A. Journal of Molecular Catalysis A: Chemical, Vol. 322, Issue 1-2 https://doi.org/10.1016/j.molcata.2010.02.020	journal	May 2010
An electron microscope for the aberration-corrected era Krivanek, O. L.; Corbin, G. J.; Dellby, N. Ultramicroscopy, Vol. 108, Issue 3 https://doi.org/10.1016/j.ultramic.2007.07.010	journal	February 2008
Diesel Ultradeep Hydrodesulfurization over Trimetallic WMoNi Catalysts by a Liquid-Phase Preparation Method in a Slurry Bed Reactor Liu, Yong-Jun; Song, Shu-Zheng; Deng, Xuan Energy & Fuels, Vol. 31, Issue 7 https://doi.org/10.1021/acs.energyfuels.7b00122	journal	June 2017
Fuel Sulfur and Iron Additives Contribute to the Formation of Carbon Nanotube-like Structures in an Internal Combustion Engine Swanson, Jacob J.; Febo, Ryder; Boies, Adam M. Environmental Science & Technology Letters, Vol. 3, Issue 10 https://doi.org/10.1021/acs.estlett.6b00313	journal	September 2016
Hydrodesulfurization Activity of CoMo Catalysts Supported on Stabilized TiO ₂ Schacht, P.; Hernández, G.; Cedeño, L. Energy & Fuels, Vol. 17, Issue 1 https://doi.org/10.1021/ef020144u	journal	January 2003
Enhanced Heavy Oil Recovery by in Situ Prepared Ultradispersed Multimetallic Nanoparticles: A Study of Hot Fluid Flooding for Athabasca Bitumen Recovery Hashemi, Rohallah; Nassar, Nashaat N.; Pereira Almao, Pedro Energy & Fuels, Vol. 27, Issue 4 https://doi.org/10.1021/ef3020537	journal	March 2013
Macroscopic Wall Number Analysis of Single-Walled, Double-Walled, and Few-Walled Carbon Nanotubes by X-ray Diffraction Futaba, Don N.; Yamada, Takeo; Kobashi, Kazufumi Journal of the American Chemical Society, Vol. 133, Issue 15 https://doi.org/10.1021/ja2005994	journal	April 2011
Thermogravimetric Analysis of the Oxidation of Multiwalled Carbon Nanotubes: Evidence for the Role of Defect Sites in Carbon Nanotube Chemistry Bom, David; Andrews, Rodney; Jacques, David Nano Letters, Vol. 2, Issue 6 https://doi.org/10.1021/nl020297u	journal	June 2002
Characterization of the Interaction of Gamma Cyclodextrin with Single-Walled Carbon Nanotubes Chambers, Gordon; Carroll, Clodagh; Farrell, Garrett F. Nano Letters, Vol. 3, Issue 6 https://doi.org/10.1021/nl034181p	journal	June 2003
The future of airborne sulfur-containing particles in the absence of fossil fuel sulfur dioxide emissions Perraud, Véronique; Horne, Jeremy R.; Martinez, Andrew S. Proceedings of the National Academy of Sciences, Vol. 112, Issue 44 https://doi.org/10.1073/pnas.1510743112	journal	October 2015
Catalytic Properties of Single Layers of Transition Metal Sulfide Catalytic Materials Chianelli, Russell R.; Siadati, Mohammad H.; De la Rosa, Myriam Perez Catalysis Reviews, Vol. 48, Issue 1, p. 1-41 https://doi.org/10.1080/01614940500439776	journal	January 2006
Hydrodesulphurisation activity of CoMo catalyst supported on multi wall carbon nanotube: sulphur species study Khorami, Payman; Kalbasi, Mansour Journal of Experimental Nanoscience, Vol. 6, Issue 4 https://doi.org/10.1080/17458080.2010.497948	journal	August 2011

Cited By (1)

Sacrificial carbonaceous coating over alumina supported Ni–MoS ₂ catalyst for hydrodesulfurization Xu, Yingrui; Li, Pengyun; Yuan, Shenghua RSC Advances, Vol. 9, Issue 21 https://doi.org/10.1039/c9ra00884e	journal	January 2019

Similar Records

Hydrodesulfurization of sulfur heterocyclic compounds: kinetics of dibenzothiophene. [Hydrodesulfurization of dibenzothiophene]

Journal Article · Sat Jan 31 23:00:00 EST 1981 · J. Catal.; (United States) · OSTI ID:6395247

Kinetics of dibenzothiophene hydrodesulfurization

Journal Article · Sun Mar 31 23:00:00 EST 1991 · Journal of Catalysis; (USA) · OSTI ID:5721215

Sulfided Co-Mo/. gamma. -Al/sub 2/O/sub 3/ catalyst: evidence of structural changes during hydrodesulfurization of dibenzothiphene. [Dibenzothiophene]

Journal Article · Sat Dec 31 23:00:00 EST 1977 · J. Catal.; (United States) · OSTI ID:6464926

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
77 NANOSCIENCE AND NANOTECHNOLOGY
carbon nanotubes
catalysts
materials
order
thiophenes

Cobalt-Molybdenum Single-Layered Nanocatalysts Decorated on Carbon Nanotubes and the Influence of Preparation Conditions on Their Hydrodesulfurization Catalytic Activity

Citation Formats

References (33)

Cited By (1)

Similar Records

Related Subjects