Chloromethane to olefins over H-SAPO-34: Probing the hydrocarbon pool mechanism
Abstract
In this paper, by means of in situ FTIR and ex situ13C NMR studies, the initial periods of the chloromethane-to-olefins (CTO) reaction over SAPO-34 were probed in order to investigate the activation period of the reaction and to elucidate the formation of the catalyst active site. A methylated benzene species has been observed to form during the initial activation period of the reaction, and a direct positive correlation was constructed between the formation of this species and the catalytic activity. The data thus indicate that these methylated benzene species contribute to the formation of active sites within SAPO-34 for the CTO reaction. This is the first known report identifying a direct semi-quantitative correlation between the catalyst activity and growth of a methylated benzene active species, during the activation period of the chloromethane to olefins reaction. Finally, the findings here in correspond well to those reported for the methanol to olefins reaction, suggesting that a similar ‘hydrocarbon pool’ mechanism may be responsible for the formation of light olefins in CTO chemistry as well.
- Authors:
-
- SABIC Technology Center, Sugar Land, TX (United States)
- Columbia Univ., New York, NY (United States). Dept. of Chemical Engineering
- Brookhaven National Lab. (BNL), Upton, NY (United States). Chemistry Dept.
- Columbia Univ., New York, NY (United States). Dept. of Chemical Engineering; Brookhaven National Lab. (BNL), Upton, NY (United States). Chemistry Dept.
- Publication Date:
- Research Org.:
- Brookhaven National Laboratory (BNL), Upton, NY (United States); SABIC Technology Center, Sugar Land, TX (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES)
- Contributing Org.:
- Columbia Univ., New York, NY (United States)
- OSTI Identifier:
- 1341680
- Report Number(s):
- BNL-113408-2017-JA
Journal ID: ISSN 0926-860X; R&D Project: CO035; KC0302010
- Grant/Contract Number:
- SC0012704
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Applied Catalysis. A, General
- Additional Journal Information:
- Journal Volume: 527; Journal ID: ISSN 0926-860X
- Publisher:
- Elsevier
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; SAPO-34; Hydrocarbon pool; Chloromethane; Induction period; 13C NMR
Citation Formats
Fickel, Dustin W., Sabnis, Kaiwalya D., Li, Luanyi, Kulkarni, Neeta, Winter, Lea R., Yan, Binhang, and Chen, Jingguang G. Chloromethane to olefins over H-SAPO-34: Probing the hydrocarbon pool mechanism. United States: N. p., 2016.
Web. doi:10.1016/j.apcata.2016.09.004.
Fickel, Dustin W., Sabnis, Kaiwalya D., Li, Luanyi, Kulkarni, Neeta, Winter, Lea R., Yan, Binhang, & Chen, Jingguang G. Chloromethane to olefins over H-SAPO-34: Probing the hydrocarbon pool mechanism. United States. https://doi.org/10.1016/j.apcata.2016.09.004
Fickel, Dustin W., Sabnis, Kaiwalya D., Li, Luanyi, Kulkarni, Neeta, Winter, Lea R., Yan, Binhang, and Chen, Jingguang G. Fri .
"Chloromethane to olefins over H-SAPO-34: Probing the hydrocarbon pool mechanism". United States. https://doi.org/10.1016/j.apcata.2016.09.004. https://www.osti.gov/servlets/purl/1341680.
@article{osti_1341680,
title = {Chloromethane to olefins over H-SAPO-34: Probing the hydrocarbon pool mechanism},
author = {Fickel, Dustin W. and Sabnis, Kaiwalya D. and Li, Luanyi and Kulkarni, Neeta and Winter, Lea R. and Yan, Binhang and Chen, Jingguang G.},
abstractNote = {In this paper, by means of in situ FTIR and ex situ13C NMR studies, the initial periods of the chloromethane-to-olefins (CTO) reaction over SAPO-34 were probed in order to investigate the activation period of the reaction and to elucidate the formation of the catalyst active site. A methylated benzene species has been observed to form during the initial activation period of the reaction, and a direct positive correlation was constructed between the formation of this species and the catalytic activity. The data thus indicate that these methylated benzene species contribute to the formation of active sites within SAPO-34 for the CTO reaction. This is the first known report identifying a direct semi-quantitative correlation between the catalyst activity and growth of a methylated benzene active species, during the activation period of the chloromethane to olefins reaction. Finally, the findings here in correspond well to those reported for the methanol to olefins reaction, suggesting that a similar ‘hydrocarbon pool’ mechanism may be responsible for the formation of light olefins in CTO chemistry as well.},
doi = {10.1016/j.apcata.2016.09.004},
journal = {Applied Catalysis. A, General},
number = ,
volume = 527,
place = {United States},
year = {Fri Sep 09 00:00:00 EDT 2016},
month = {Fri Sep 09 00:00:00 EDT 2016}
}
Free Publicly Available Full Text
Publisher's Version of Record
Other availability
Search WorldCat to find libraries that may hold this journal
Cited by: 14 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:
Conversion of chloromethane to light olefins catalyzed by ZSM-5 zeolites
journal, March 2005
- Noronha, Leandro A.; Souza-Aguiar, E. Falabella; Mota, Claudio J. A.
- Catalysis Today, Vol. 101, Issue 1
Ultra-short contact time conversion of chloromethane to olefins over pre-coked SAPO-34: direct insight into the primary conversion with coke deposition
journal, January 2009
- Wei, Yingxu; Zhang, Dazhi; Chang, Fuxiang
- Chemical Communications, Issue 40
Methane steam reforming, methanation and water-gas shift: I. Intrinsic kinetics
journal, January 1989
- Xu, Jianguo; Froment, Gilbert F.
- AIChE Journal, Vol. 35, Issue 1
Fischer–Tropsch synthesis: A review of the effect of CO conversion on methane selectivity
journal, January 2014
- Yang, Jia; Ma, Wenping; Chen, De
- Applied Catalysis A: General, Vol. 470
Comments about the causes of deviations from the Anderson–Schulz–Flory distribution of the Fischer–Tropsch reaction products
journal, August 2003
- Puskas, I.; Hurlbut, R. S.
- Catalysis Today, Vol. 84, Issue 1-2
Selective conversion of syngas to light olefins
journal, March 2016
- Jiao, F.; Li, J.; Pan, X.
- Science, Vol. 351, Issue 6277
Methanol to Olefins (MTO): From Fundamentals to Commercialization
journal, February 2015
- Tian, Peng; Wei, Yingxu; Ye, Mao
- ACS Catalysis, Vol. 5, Issue 3
Direct Observation of Cyclic Carbenium Ions and Their Role in the Catalytic Cycle of the Methanol-to-Olefin Reaction over Chabazite Zeolites
journal, September 2013
- Xu, Shutao; Zheng, Anmin; Wei, Yingxu
- Angewandte Chemie International Edition, Vol. 52, Issue 44
The characteristics of SAPO-34 which influence the conversion of methanol to light olefins
journal, June 1999
- Wilson, Stephen; Barger, Paul
- Microporous and Mesoporous Materials, Vol. 29, Issue 1-2
The methyl halide to hydrocarbon reaction over H-SAPO-34
journal, July 2006
- Svelle, S.; Aravinthan, S.; Bjorgen, M.
- Journal of Catalysis, Vol. 241, Issue 2
Comparative Study on the Chloromethane to Olefins Reaction over SAPO-34 and HZSM-22
journal, October 2014
- Kong, Ling-tao; Shen, Ben-xian; Zhao, Ji-gang
- Industrial & Engineering Chemistry Research, Vol. 53, Issue 42
On the reaction mechanism for propene formation in the MTO reaction over SAPO-34
journal, January 1993
- Dahl, Ivar M.; Kolboe, Stein
- Catalysis Letters, Vol. 20, Issue 3-4
On the Reaction Mechanism for Hydrocarbon Formation from Methanol over SAPO-34
journal, October 1994
- Dahl, I. M.; Kolboe, S.
- Journal of Catalysis, Vol. 149, Issue 2
Methane conversion to light olefins—How does the methyl halide route differ from the methanol to olefins (MTO) route?
journal, August 2011
- Olsbye, Unni; Saure, Ole Vaaland; Muddada, Naresh Babu
- Catalysis Today, Vol. 171, Issue 1
Unraveling the Reaction Mechanisms Governing Methanol-to-Olefins Catalysis by Theory and Experiment
journal, April 2013
- Hemelsoet, Karen; Van der Mynsbrugge, Jeroen; De Wispelaere, Kristof
- ChemPhysChem, Vol. 14, Issue 8
Methanol-to-hydrocarbons: catalytic materials and their behavior
journal, June 1999
- Stöcker, Michael
- Microporous and Mesoporous Materials, Vol. 29, Issue 1-2
Conversion of Methanol to Hydrocarbons: How Zeolite Cavity and Pore Size Controls Product Selectivity
journal, April 2012
- Olsbye, Unni; Svelle, Stian; Bjørgen, Morten
- Angewandte Chemie International Edition, Vol. 51, Issue 24, p. 5810-5831
Effect of crystallite size of SAPO-34 catalysts on their induction period and deactivation in methanol-to-olefin reactions
journal, November 2009
- Lee, Kwang Young; Chae, Ho-Jeong; Jeong, Soon-Yong
- Applied Catalysis A: General, Vol. 369, Issue 1-2
Correlating extent of Pt–Ni bond formation with low-temperature hydrogenation of benzene and 1,3-butadiene over supported Pt/Ni bimetallic catalysts
journal, May 2010
- Lonergan, William W.; Vlachos, Dionisios G.; Chen, Jingguang G.
- Journal of Catalysis, Vol. 271, Issue 2
Long-induction period in the oxidation of ethylene over a silver catalyst
journal, November 1984
- Kobayashi, M.
- Journal of Catalysis, Vol. 90, Issue 1
Reaction Behaviors and Kinetics during Induction Period of Methanol Conversion on HZSM-5 Zeolite
journal, June 2015
- Qi, Liang; Wei, Yingxu; Xu, Lei
- ACS Catalysis, Vol. 5, Issue 7
Methylbenzenes Are the Organic Reaction Centers for Methanol-to-Olefin Catalysis on HSAPO-34
journal, November 2000
- Song, Weiguo; Haw, James F.; Nicholas, John B.
- Journal of the American Chemical Society, Vol. 122, Issue 43
Well-defined (supra)molecular structures in zeolite methanol-to-olefin catalysis
journal, May 2005
- Haw, James F.; Marcus, David M.
- Topics in Catalysis, Vol. 34, Issue 1-4
In situ FTIR studies of methanol and dimethyl ether in ZSM-5
journal, August 1987
- Forester, T. R.; Howe, R. F.
- Journal of the American Chemical Society, Vol. 109, Issue 17
Studies of the Adsorption Geometry and Decomposition Mechanisms of Benzene on Clean and Carbide-Modified Mo(110) Surfaces Using Vibrational Spectroscopy
journal, May 1997
- Eng, Joseph; Bent, Brian E.; Frühberger, Bernd
- The Journal of Physical Chemistry B, Vol. 101, Issue 20
Vibrational Study of the Interaction of Acetylene and Benzene on Clean and Carbide-Modified W(211) Surfaces
journal, November 1998
- Eng, J.; Chen, J. G.; Abdelrehim, I. M.
- The Journal of Physical Chemistry B, Vol. 102, Issue 48
Mechanism of the Catalytic Conversion of Methanol to Hydrocarbons
journal, December 2012
- Ilias, Samia; Bhan, Aditya
- ACS Catalysis, Vol. 3, Issue 1, p. 18-31
Highly efficient catalytic conversion of chloromethane to light olefins over HSAPO-34 as studied by catalytic testing and in situ FTIR
journal, February 2006
- Wei, Y.; Zhang, D.; Liu, Z.
- Journal of Catalysis, Vol. 238, Issue 1
The Mechanism of Methanol to Hydrocarbon Catalysis
journal, May 2003
- Haw, James F.; Song, Weiguo; Marcus, David M.
- Accounts of Chemical Research, Vol. 36, Issue 5
In situ MAS NMR spectroscopic investigation of the conversion of methanol to olefins on silicoaluminophosphates SAPO-34 and SAPO-18 under continuous flow conditions
journal, January 2001
- Hunger, Michael; Seiler, Michael; Buchholz, Andreas
- Catalysis Letters, Vol. 74, Issue 1/2, p. 61-68
In situ MAS NMR–UV/Vis investigation of H-SAPO-34 catalysts partially coked in the methanol-to-olefin conversion under continuous-flow conditions and of their regeneration
journal, September 2007
- Jiang, Yijiao; Huang, Jun; Reddy Marthala, V. R.
- Microporous and Mesoporous Materials, Vol. 105, Issue 1-2
Solid-State13C MAS NMR Study of Methanol-to-Hydrocarbon Chemistry over H-SAPO-34
journal, December 1996
- Salehirad, Fathollah; Anderson, Michael W.
- Journal of Catalysis, Vol. 164, Issue 2
Methanol-to-hydrocarbons conversion: The alkene methylation pathway
journal, May 2014
- Brogaard, Rasmus Y.; Henry, Reynald; Schuurman, Yves
- Journal of Catalysis, Vol. 314
Towards molecular control of elementary reactions in zeolite catalysis by advanced molecular simulations mimicking operating conditions
journal, January 2016
- De Wispelaere, Kristof; Bailleul, Simon; Van Speybroeck, Veronique
- Catalysis Science & Technology, Vol. 6, Issue 8
Kinetic, Spectroscopic, and Theoretical Assessment of Associative and Dissociative Methanol Dehydration Routes in Zeolites
journal, September 2014
- Jones, Andrew J.; Iglesia, Enrique
- Angewandte Chemie International Edition, Vol. 53, Issue 45
The Effect of Acid Strength on the Conversion of Methanol to Olefins Over Acidic Microporous Catalysts with the CHA Topology
journal, January 2009
- Bleken, Francesca; Bjørgen, Morten; Palumbo, Luisa
- Topics in Catalysis, Vol. 52, Issue 3
Influence of adsorption thermodynamics on guest diffusivities in nanoporous crystalline materials
journal, January 2013
- Krishna, Rajamani; van Baten, Jasper M.
- Physical Chemistry Chemical Physics, Vol. 15, Issue 21
Unit cell expansion upon coke formation in a SAPO-34 catalyst: A combined experimental and computational study
journal, January 2013
- Zokaie, Mahsa; Wragg, David S.; Grønvold, Arne
- Microporous and Mesoporous Materials, Vol. 165
Works referencing / citing this record:
Selective monochlorination of methane via elimination of dichloromethane from the oxychlorination product stream
journal, March 2019
- Sabnis, Kaiwalya D.; Fickel, Dustin W.; Shou, Heng
- Reaction Kinetics, Mechanisms and Catalysis, Vol. 127, Issue 1
Kinetic and Deactivation Differences Among Methanol, Dimethyl Ether and Chloromethane as Stock for Hydrocarbons
journal, October 2019
- Valecillos, José; Manzano, Hegoi; Aguayo, Andrés T.
- ChemCatChem, Vol. 11, Issue 22
Kinetic and Deactivation Differences Among Methanol, Dimethyl Ether and Chloromethane as Stock for Hydrocarbons
journal, October 2019
- Valecillos, José; Manzano, Hegoi; Aguayo, Andrés T.
- ChemCatChem, Vol. 11, Issue 22