Bimetallic Mo-Co/ZSM-5 and Mo-Ni/ZSM-5 catalysts for methane dehydroaromatization: A study of the effect of pretreatment and metal loadings on the catalytic behavior
Abstract
Here, methane dehydroaromatization is studied using different loadings (0.2 wt%, 0.6 and 1 wt%) of Co and Ni additives on a 6 wt% Mo/ZSM-5 catalyst to evaluate the promoting effect of Ni and Co on reactivity and stability of the catalysts. A synergy between Mo and the additives is observed when combining a reduction/carburization pretreatment with an optimum additive loading: benzene yield and catalytic stability are both improved. The fresh and spent samples were characterized by X-Ray Diffraction, 27Al Magic-Angle Spinning Solid State Nuclear Magnetic Resonance Spectroscopy, Temperature-Programmed Reduction and Thermogravimetric Analysis. The results suggest that catalytic enhancement in precarburized Mo-Co and Mo-Ni samples is due to a combination of effects: extraction of Al from the ZSM-5 framework to form inactive Al2(MoO4)3 is reduced, interaction of Mo with the additives enhances the retention of Mo species within the zeolite channels, prevents Mo aggregation in reaction and modifies the reducibility of the Mo sites.
- Publication Date:
- Research Org.:
- Texas Tech Univ., Lubbock, TX (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES)
- OSTI Identifier:
- 1803547
- Alternate Identifier(s):
- OSTI ID: 1573860
- Grant/Contract Number:
- SC0019074
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Applied Catalysis. A, General
- Additional Journal Information:
- Journal Volume: 589; Journal ID: ISSN 0926-860X
- Publisher:
- Elsevier
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; methane dehydroaromatization; benzene; 6 wt% Mo/HZSM-5; Co-modified Mo catalysts; regeneration
Citation Formats
Sridhar, Apoorva, Rahman, Mustafizur, Infantes-Molina, Antonia, Wylie, Benjamin J., Borcik, Collin G., and Khatib, Sheima J. Bimetallic Mo-Co/ZSM-5 and Mo-Ni/ZSM-5 catalysts for methane dehydroaromatization: A study of the effect of pretreatment and metal loadings on the catalytic behavior. United States: N. p., 2019.
Web. doi:10.1016/j.apcata.2019.117247.
Sridhar, Apoorva, Rahman, Mustafizur, Infantes-Molina, Antonia, Wylie, Benjamin J., Borcik, Collin G., & Khatib, Sheima J. Bimetallic Mo-Co/ZSM-5 and Mo-Ni/ZSM-5 catalysts for methane dehydroaromatization: A study of the effect of pretreatment and metal loadings on the catalytic behavior. United States. https://doi.org/10.1016/j.apcata.2019.117247
Sridhar, Apoorva, Rahman, Mustafizur, Infantes-Molina, Antonia, Wylie, Benjamin J., Borcik, Collin G., and Khatib, Sheima J. Tue .
"Bimetallic Mo-Co/ZSM-5 and Mo-Ni/ZSM-5 catalysts for methane dehydroaromatization: A study of the effect of pretreatment and metal loadings on the catalytic behavior". United States. https://doi.org/10.1016/j.apcata.2019.117247. https://www.osti.gov/servlets/purl/1803547.
@article{osti_1803547,
title = {Bimetallic Mo-Co/ZSM-5 and Mo-Ni/ZSM-5 catalysts for methane dehydroaromatization: A study of the effect of pretreatment and metal loadings on the catalytic behavior},
author = {Sridhar, Apoorva and Rahman, Mustafizur and Infantes-Molina, Antonia and Wylie, Benjamin J. and Borcik, Collin G. and Khatib, Sheima J.},
abstractNote = {Here, methane dehydroaromatization is studied using different loadings (0.2 wt%, 0.6 and 1 wt%) of Co and Ni additives on a 6 wt% Mo/ZSM-5 catalyst to evaluate the promoting effect of Ni and Co on reactivity and stability of the catalysts. A synergy between Mo and the additives is observed when combining a reduction/carburization pretreatment with an optimum additive loading: benzene yield and catalytic stability are both improved. The fresh and spent samples were characterized by X-Ray Diffraction, 27Al Magic-Angle Spinning Solid State Nuclear Magnetic Resonance Spectroscopy, Temperature-Programmed Reduction and Thermogravimetric Analysis. The results suggest that catalytic enhancement in precarburized Mo-Co and Mo-Ni samples is due to a combination of effects: extraction of Al from the ZSM-5 framework to form inactive Al2(MoO4)3 is reduced, interaction of Mo with the additives enhances the retention of Mo species within the zeolite channels, prevents Mo aggregation in reaction and modifies the reducibility of the Mo sites.},
doi = {10.1016/j.apcata.2019.117247},
journal = {Applied Catalysis. A, General},
number = ,
volume = 589,
place = {United States},
year = {Tue Oct 22 00:00:00 EDT 2019},
month = {Tue Oct 22 00:00:00 EDT 2019}
}
Free Publicly Available Full Text
Publisher's Version of Record
Other availability
Search WorldCat to find libraries that may hold this journal
Cited by: 55 works
Citation information provided by
Web of Science
Web of Science
Save to My Library
You must Sign In or Create an Account in order to save documents to your library.
Works referenced in this record:
Effect of addition of a second metal in Mo/ZSM-5 catalyst for methane aromatization reaction under elevated pressures
journal, November 2015
- Fila, Vlastimil; Bernauer, Milan; Bernauer, Bohumil
- Catalysis Today, Vol. 256
Temperature-programed reduction of molybdenum(VI) oxide and molybdenum(IV) oxide
journal, October 1985
- Arnoldy, P.; De Jonge, J. C. M.; Moulijn, J. A.
- The Journal of Physical Chemistry, Vol. 89, Issue 21
Methane dehydro-aromatization on Mo/ZSM-5: About the hidden role of Brønsted acid sites
journal, March 2008
- Tessonnier, Jean-Philippe; Louis, Benoît; Rigolet, Séverinne
- Applied Catalysis A: General, Vol. 336, Issue 1-2
Structure and acidity of Mo/ZSM-5 synthesized by solid state reaction for methane dehydrogenation and aromatization
journal, January 2006
- Li, Bin; Li, Shijie; Li, Neng
- Microporous and Mesoporous Materials, Vol. 88, Issue 1-3
Evolution of isomorphously substituted iron zeolites during activation: comparison of Fe-beta and Fe-ZSM-5
journal, June 2005
- Perezramirez, J.; Groen, J.; Bruckner, A.
- Journal of Catalysis, Vol. 232, Issue 2
A Radical Twist to the Versatile Behavior of Iron in Selective Methane Activation
journal, September 2014
- Ruitenbeek, Matthijs; Weckhuysen, Bert M.
- Angewandte Chemie International Edition, Vol. 53, Issue 42
Methanol-to-hydrocarbons conversion over MoO 3 /H-ZSM-5 catalysts prepared via lower temperature calcination: a route to tailor the distribution and evolution of promoter Mo species, and their corresponding catalytic properties
journal, January 2015
- Liu, Bonan; France, Liam; Wu, Chen
- Chemical Science, Vol. 6, Issue 9
Increasing the catalytic stability by optimizing the formation of zeolite-supported Mo carbide species ex situ for methane dehydroaromatization
journal, July 2019
- Rahman, Mustafizur; Infantes-Molina, Antonia; Boubnov, Alexey
- Journal of Catalysis, Vol. 375
Methane aromatization using Mo-based catalysts prepared by microwave heating
journal, December 2004
- Qi, Suitao; Yang, Bolun
- Catalysis Today, Vol. 98, Issue 4
H2-TPR Study on Mo/HZSM-5 Catalyst for CH4 Dehydroaromatization
journal, April 2006
- Liu, Hongmei; Xu, Yide
- Chinese Journal of Catalysis, Vol. 27, Issue 4
The effect of water on the reduction of nickel/alumina catalysts
journal, December 1992
- Zieliński, Jerzy
- Catalysis Letters, Vol. 12, Issue 4
Dehydrogenation and aromatization of methane under non-oxidizing conditions
journal, January 1993
- Wang, Linsheng; Tao, Longxiang; Xie, Maosong
- Catalysis Letters, Vol. 21, Issue 1-2
Dehydro-oligomerization of Methane to Ethylene and Aromatics over Molybdenum/HZSM-5 Catalyst
journal, November 1995
- Chen, L. Y.; Lin, L. W.; Xu, Z. S.
- Journal of Catalysis, Vol. 157, Issue 1
Impact of the presence of Mo carbide species prepared ex situ in Mo/HZSM-5 on the catalytic properties in methane aromatization
journal, May 2018
- Rahman, Mustafizur; Sridhar, Apoorva; Khatib, Sheima J.
- Applied Catalysis A: General, Vol. 558
Non-oxidative conversion of methane to aromatics over modified Mo/HZSM5 catalysts
journal, March 2001
- Tang, S.; Chen, H.; Lin, J.
- Catalysis Communications, Vol. 2, Issue 1
Structure and Density of Mo and Acid Sites in Mo-Exchanged H-ZSM5 Catalysts for Nonoxidative Methane Conversion
journal, July 1999
- Borry, Richard W.; Kim, Young Ho; Huffsmith, Anne
- The Journal of Physical Chemistry B, Vol. 103, Issue 28
Recent progress in methane dehydroaromatization: From laboratory curiosities to promising technology
journal, January 2013
- Ma, Shuqi; Guo, Xiaoguang; Zhao, Lingxiao
- Journal of Energy Chemistry, Vol. 22, Issue 1
Effect of Cr Addition on the Methane Aromatization Performance of the Mo/HZSM-5 Catalyst
journal, January 2002
- Zhang, Y.; Wang, D.; Fei, J.
- Australian Journal of Chemistry, Vol. 55, Issue 8
Improvement of catalyst stability during methane dehydroaromatization (MDA) on Mo/HZSM-5 comprising intracrystalline mesopores
journal, July 2011
- Martínez, A.; Peris, E.; Derewinski, M.
- Catalysis Today, Vol. 169, Issue 1
Confined Carbon Mediating Dehydroaromatization of Methane over Mo/ZSM-5
journal, December 2017
- Kosinov, Nikolay; Wijpkema, Alexandra S. G.; Uslamin, Evgeny
- Angewandte Chemie International Edition, Vol. 57, Issue 4
Direct conversion of methane on Mo/ZSM-5 catalysts to produce benzene and hydrogen: achievements and perspectives
journal, January 2008
- Ismagilov, Zinfer R.; Matus, Ekaterina V.; Tsikoza, Lidia T.
- Energy & Environmental Science, Vol. 1, Issue 5
XPS, XAES, and TG/DTA characterization of deposited carbon in methane dehydroaromatization over Ga–Mo/ZSM-5 catalyst
journal, March 2007
- Liu, B. S.; Jiang, L.; Sun, H.
- Applied Surface Science, Vol. 253, Issue 11
Study of the carbonaceous deposits formed on a Mo/HZSM-5 catalyst in methane dehydro-aromatization by using TG and temperature-programmed techniques
journal, May 2001
- Liu, Hongmei; Li, Tao; Tian, Binglun
- Applied Catalysis A: General, Vol. 213, Issue 1
Determination of Molybdenum Species Evolution during Non‐Oxidative Dehydroaromatization of Methane and its Implications for Catalytic Performance
journal, October 2018
- Agote‐Arán, Miren; Kroner, Anna B.; Islam, Husn U.
- ChemCatChem, Vol. 11, Issue 1
Aromatization of Methane over Supported and Unsupported Mo-Based Catalysts
journal, January 1997
- Solymosi, F.; Cserényi, J.; Szöke, A.
- Journal of Catalysis, Vol. 165, Issue 2
Methane dehydrogenation and aromatization in the absence of oxygen on MoHZSM-5: A study on the interaction between Mo species and HZSM-5 by using 27Al and 29Si MAS NMR
journal, June 1997
- Liu, W.; Xu, Y.; Wong, She-Tin
- Journal of Molecular Catalysis A: Chemical, Vol. 120, Issue 1-3
Silica-Alumina-Supported Acidic Molybdenum Catalysts - TPR and XRD Characterization
journal, June 1994
- Rajagopal, S.; Marini, H. J.; Marzari, J. A.
- Journal of Catalysis, Vol. 147, Issue 2
Characterization of a Mo/ZSM-5 Catalyst for the Conversion of Methane to Benzene
journal, July 1997
- Wang, Dingjun; Lunsford, Jack H.; Rosynek, Michael P.
- Journal of Catalysis, Vol. 169, Issue 1
Methane activation without using oxidants over Mo/HZSM-5 zeolite catalysts
journal, January 1995
- Xu, Yide; Liu, Shetian; Guo, Xiexian
- Catalysis Letters, Vol. 30, Issue 1-4
Using phosphorus doping of MoO3/ZSM-5 to modify performance in methane dehydroaromatisation
journal, February 2006
- Burns, S.; Hargreaves, J. S. J.; Pal, P.
- Journal of Molecular Catalysis A: Chemical, Vol. 245, Issue 1-2
Methane Dehydro-aromatization over Mo/HZSM-5 in the Absence of Oxygen: A Multinuclear Solid-State NMR Study of the Interaction between Supported Mo Species and HZSM-5 Zeolite with Different Crystal Sizes
journal, December 1999
- Zhang, Weiping; Ma, Ding; Han, Xiuwen
- Journal of Catalysis, Vol. 188, Issue 2
On the Mechanism Underlying the Direct Conversion of Methane to Methanol by Copper Hosted in Zeolites; Braiding Cu K-Edge XANES and Reactivity Studies
journal, July 2018
- Newton, Mark A.; Knorpp, Amy J.; Pinar, Ana B.
- Journal of the American Chemical Society, Vol. 140, Issue 32
Nonoxidative conversion of methane into aromatic hydrocarbons on Ni-Mo/ZSM-5 catalysts
journal, September 2009
- Vosmerikov, A. V.; Zaikovskii, V. I.; Korobitsyna, L. L.
- Kinetics and Catalysis, Vol. 50, Issue 5
Conversion of Methane to Benzene over Transition Metal Ion ZSM-5 Zeolites
journal, April 1998
- Weckhuysen, Bert M.; Wang, Dingjun; Rosynek, Michael P.
- Journal of Catalysis, Vol. 175, Issue 2
Methane decomposition into hydrogen and carbon nanofibers over supported Pd–Ni catalysts
journal, December 2003
- Takenaka, Sakae; Shigeta, Yukio; Tanabe, Eishi
- Journal of Catalysis, Vol. 220, Issue 2
The effects of boron and silver on the oxygen-free conversion of methane over Mo/H-ZSM-5 catalysts
journal, June 2009
- Ngobeni, M. W.; Carley, A. F.; Scurrell, M. S.
- Journal of Molecular Catalysis A: Chemical, Vol. 305, Issue 1-2
Thermodynamic Analysis of Nonoxidative Dehydroaromatization of Methane
journal, June 2012
- Moghimpour Bijani, P.; Sohrabi, M.; Sahebdelfar, S.
- Chemical Engineering & Technology, Vol. 35, Issue 10
Carbon capacious Ni-Cu-Al2O3 catalysts for high-temperature methane decomposition
journal, July 2003
- Reshetenko, Tatyana V.; Avdeeva, Lyudmila B.; Ismagilov, Zinfer R.
- Applied Catalysis A: General, Vol. 247, Issue 1
Mass production of high-quality multi-walled carbon nanotube bundles on a Ni/Mo/MgO catalyst
journal, January 2005
- Li, Y.; Zhang, X. B.; Tao, X. Y.
- Carbon, Vol. 43, Issue 2
Remarkable non-oxidative conversion of methane to naphthalene and benzene on Co and Fe modified Mo/HZSM-5 catalysts
journal, January 1997
- Liu, Shetian; Dong, Qun; Ohnishi, Ryuichiro
- Chemical Communications, Issue 15
Dehydroaromatization of methane over doped Pt/Mo/H-ZSM-5 zeolite catalysts: The promotional effect of tin
journal, September 2014
- Tshabalala, Themba E.; Coville, Neil J.; Scurrell, Michael S.
- Applied Catalysis A: General, Vol. 485
The effect of dopants on the activity of MoO3/ZSM-5 catalysts for the dehydroaromatisation of methane
journal, May 2006
- Burns, S.; Hargreaves, J. S. J.; Pal, P.
- Catalysis Today, Vol. 114, Issue 4
Quantitative Measurement of the Brönsted Acid Sites in Solid Acids: Toward a Single-Site Design of Mo-Modified ZSM-5 Zeolite
journal, June 2006
- Tessonnier, Jean-Philippe; Louis, Benoît; Walspurger, Stephane
- The Journal of Physical Chemistry B, Vol. 110, Issue 21
Understanding and Breaking Scaling Relations in Single-Site Catalysis: Methane to Methanol Conversion by Fe IV ═O
journal, January 2018
- Gani, Terry Z. H.; Kulik, Heather J.
- ACS Catalysis, Vol. 8, Issue 2
Realumination of dealuminated HZSM-5 zeolites by acid treatment: a reexamination
journal, August 2001
- Omegna, Anna; Haouas, Mohamed; Kogelbauer, Andreas
- Microporous and Mesoporous Materials, Vol. 46, Issue 2-3
Molybdenum Speciation and its Impact on Catalytic Activity during Methane Dehydroaromatization in Zeolite ZSM-5 as Revealed by Operando X-Ray Methods
journal, March 2016
- Lezcano-González, Inés; Oord, Ramon; Rovezzi, Mauro
- Angewandte Chemie International Edition, Vol. 55, Issue 17
Stability and deactivation of Fe-ZSM-5 zeolite catalyst for catalytic wet peroxide oxidation of phenol in a membrane reactor
journal, January 2015
- Jiang, Songshan; Zhang, Huiping; Yan, Ying
- RSC Advances, Vol. 5, Issue 51
A corrected procedure and consistent interpretation for temperature programmed reduction of supported MoO3
journal, January 1994
- Regalbuto, John R.; Ha, Jin -Wook
- Catalysis Letters, Vol. 29, Issue 1-2
Catalytic aromatization of methane
journal, January 2014
- Spivey, James J.; Hutchings, Graham
- Chem. Soc. Rev., Vol. 43, Issue 3
On the dynamic nature of Mo sites for methane dehydroaromatization
journal, January 2018
- Vollmer, Ina; van der Linden, Bart; Ould-Chikh, Samy
- Chemical Science, Vol. 9, Issue 21
Enhancement of Molybdenum/ZSM-5 Catalysts in Methane Aromatization by the Addition of Iron Promoters and by Reduction/Carburization Pretreatment
journal, May 2018
- Sridhar, Apoorva; Rahman, Mustafizur; Khatib, Sheima J.
- ChemCatChem, Vol. 10, Issue 12
Genesis of methane activation sites in Mo-exchanged H–ZSM-5 catalysts
journal, April 2000
- Kim, Young-Ho; Borry, Richard W.; Iglesia, Enrique
- Microporous and Mesoporous Materials, Vol. 35-36
Methane Dehydroaromatization by Mo/HZSM-5: Mono- or Bifunctional Catalysis?
journal, December 2016
- Kosinov, Nikolay; Coumans, Ferdy J. A. G.; Uslamin, Evgeny A.
- ACS Catalysis, Vol. 7, Issue 1
Incorporation of molybdenum into Pd and Pt catalysts supported on commercial silica for hydrodeoxygenation reaction of dibenzofuran
journal, October 2017
- Ballesteros-Plata, D.; Infantes-Molina, A.; Rodríguez-Cuadrado, M.
- Applied Catalysis A: General, Vol. 547
Aluminum siting in mordenite and dealumination mechanism
journal, October 1986
- Bodart, Philippe; Nagy, Janos B.; Debras, Guy
- The Journal of Physical Chemistry, Vol. 90, Issue 21
Effect of Pd or Ir on the catalytic performance of Mo/H-ZSM-5 during the non-oxidative conversion of natural gas to petrochemicals
journal, December 2008
- Aboul-Gheit, Ahmed K.; Awadallah, Ahmed E.; El-Kossy, Salah M.
- Journal of Natural Gas Chemistry, Vol. 17, Issue 4
Oxygen free conversion of natural gas to useful hydrocarbons and hydrogen over monometallic Mo and bimetallic Mo–Fe, Mo–Co or Mo–Ni/HZSM-5 catalysts prepared by mechanical mixing
journal, October 2012
- Aboul-Gheit, Ahmed K.; El-Masry, Mohamed S.; Awadallah, Ahmed E.
- Fuel Processing Technology, Vol. 102
Stable Mo/HZSM-5 methane dehydroaromatization catalysts optimized for high-temperature calcination-regeneration
journal, February 2017
- Kosinov, Nikolay; Coumans, Ferdy J. A. G.; Li, Guanna
- Journal of Catalysis, Vol. 346
Non-oxidative dehydroaromatization of methane over Ga-promoted Mo/HZSM-5-based catalysts
journal, June 2001
- Liu, Bingsi; Yang, Yong; Sayari, Abdelhamid
- Applied Catalysis A: General, Vol. 214, Issue 1
Methane Conversion to Aromatics on Mo/H-ZSM5: Structure of Molybdenum Species in Working Catalysts
journal, January 2001
- Ding, Weiping; Li, Senzi; D. Meitzner, George
- The Journal of Physical Chemistry B, Vol. 105, Issue 2
The function of Cu(II) ions in the Mo/CuH-ZSM-5 catalyst for methane conversion under non-oxidative condition
journal, October 1999
- Li, Shuang; Zhang, Chunlei; Kan, Qiubin
- Applied Catalysis A: General, Vol. 187, Issue 2
Identification of molybdenum oxide nanostructures on zeolites for natural gas conversion
journal, April 2015
- Gao, J.; Zheng, Y.; Jehng, J. -M.
- Science, Vol. 348, Issue 6235
Catalytic Methane Dehydroaromatization with Stable Nano Fe Doped on Mo/HZSM-5 Synthesized with a Simple and Environmentally Friendly Method and Clarification of a Perplexing Catalysis Mechanism Dilemma in This Field for a Period of Time
journal, September 2017
- Sun, Kaidi; Gong, Weibo; Gasem, Khaled
- Industrial & Engineering Chemistry Research, Vol. 56, Issue 40
Non-oxidative methane dehydroaromatization on Mo/HZSM-5 catalysts: Tuning the acidic and catalytic properties through partial exchange of zeolite protons with alkali and alkaline-earth cations
journal, April 2016
- Martínez, Agustín; Peris, Ernest
- Applied Catalysis A: General, Vol. 515
A hollow Mo/HZSM-5 zeolite capsule catalyst: preparation and enhanced catalytic properties in methane dehydroaromatization
journal, January 2017
- Zhu, Pengfei; Yang, Guohui; Sun, Jian
- Journal of Materials Chemistry A, Vol. 5, Issue 18