First-principles microkinetic study of methane and hydrogen sulfide catalytic conversion to methanethiol/dimethyl sulfide on Mo6S8 clusters: activity/selectivity of different promoters

Arvidsson, Adam A.; Taifan, William; Hellman, Anders; Baltrusaitis, Jonas

doi:10.1039/C9CY00375D

Title: First-principles microkinetic study of methane and hydrogen sulfide catalytic conversion to methanethiol/dimethyl sulfide on Mo₆S₈ clusters: activity/selectivity of different promoters

Abstract

A large fraction of the global natural gas reserves is in the form of sour gas, i.e. contains hydrogen sulfide (H₂S) and carbon dioxide (CO₂), and needs to be sweetened before utilization. The traditional amine-based separation process is energy-intensive, thereby lowering the value of the sour gas. Thus, there is a need to find alternative processes to remove, e.g., hydrogen sulfide. Mo₆S₈ clusters are promising candidates for transforming methane (CH₄) and hydrogen sulfide into methanethiol (CH₃SH) and dimethyl sulfide (CH₃SCH₃), which are high-value sulfur-containing products that can be further used in the chemical industry. Here first-principles microkinetics is used to investigate the activity and selectivity of bare and promoted (K, Ni, Cl) Mo₆S₈. The results show that methanethiol is produced via two different pathways (direct and stepwise), while dimethyl sulfide is formed via a competing pathway in the stepwise formation of methanethiol. Moreover, there is an increase in activity and a decrease in selectivity when adding an electropositive promoter (K), whereas the reverse behaviour is observed when adding an electronegative promoter (Cl). When adding Ni there is also a decrease in activity and an increase in selectivity; however, Ni is acting as an electron donor. The results provide insights andmore »« less

Authors:

^[1]; Taifan, William ^[2];

^[1];

^[2]

Department of Physics, Chalmers University of Technology, 412 96 Gothenburg, Sweden
Department of Chemical and Biomolecular Engineering, Lehigh University, Bethlehem, USA

Publication Date:: Wed Jul 17 00:00:00 EDT 2019

Research Org.:: Energy Frontier Research Centers (EFRC) (United States). Center for Understanding and Control of Acid Gas-Induced Evolution of Materials for Energy (UNCAGE-ME); Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States). National Energy Research Scientific Computing Center (NERSC); Univ. of California, Oakland, CA (United States); Georgia Institute of Technology, Atlanta, GA (United States)

Sponsoring Org.:: Swedish Research Council (VR); Knut and Alice Wallenberg Foundation; USDOE Office of Science (SC), Basic Energy Sciences (BES)

OSTI Identifier:: 1545940

Alternate Identifier(s):: OSTI ID: 1577570

Grant/Contract Number:: AC02-05CH11231; SC0012577

Resource Type:: Published Article

Journal Name:: Catalysis Science and Technology

Additional Journal Information:: Journal Name: Catalysis Science and Technology Journal Volume: 9 Journal Issue: 17; Journal ID: ISSN 2044-4753

Publisher:: Royal Society of Chemistry

Country of Publication:: United Kingdom

Language:: English

Subject:: 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; Chemistry

Citation Formats


                    Arvidsson, Adam A., Taifan, William, Hellman, Anders, and Baltrusaitis, Jonas. First-principles microkinetic study of methane and hydrogen sulfide catalytic conversion to methanethiol/dimethyl sulfide on Mo6S8 clusters: activity/selectivity of different promoters.  United Kingdom: N. p., 2019. 
Web.  doi:10.1039/C9CY00375D.

Copy to clipboard


                    Arvidsson, Adam A., Taifan, William, Hellman, Anders, & Baltrusaitis, Jonas. First-principles microkinetic study of methane and hydrogen sulfide catalytic conversion to methanethiol/dimethyl sulfide on Mo6S8 clusters: activity/selectivity of different promoters.  United Kingdom.  https://doi.org/10.1039/C9CY00375D

Copy to clipboard


                    Arvidsson, Adam A., Taifan, William, Hellman, Anders, and Baltrusaitis, Jonas. Wed .  
"First-principles microkinetic study of methane and hydrogen sulfide catalytic conversion to methanethiol/dimethyl sulfide on Mo6S8 clusters: activity/selectivity of different promoters".  United Kingdom.  https://doi.org/10.1039/C9CY00375D.

Copy to clipboard


                    
@article{osti_1545940,

  title        = {First-principles microkinetic study of methane and hydrogen sulfide catalytic conversion to methanethiol/dimethyl sulfide on Mo6S8 clusters: activity/selectivity of different promoters},

  author       = {Arvidsson, Adam A. and Taifan, William and Hellman, Anders and Baltrusaitis, Jonas},

  abstractNote = {A large fraction of the global natural gas reserves is in the form of sour gas, i.e. contains hydrogen sulfide (H2S) and carbon dioxide (CO2), and needs to be sweetened before utilization. The traditional amine-based separation process is energy-intensive, thereby lowering the value of the sour gas. Thus, there is a need to find alternative processes to remove, e.g., hydrogen sulfide. Mo6S8 clusters are promising candidates for transforming methane (CH4) and hydrogen sulfide into methanethiol (CH3SH) and dimethyl sulfide (CH3SCH3), which are high-value sulfur-containing products that can be further used in the chemical industry. Here first-principles microkinetics is used to investigate the activity and selectivity of bare and promoted (K, Ni, Cl) Mo6S8. The results show that methanethiol is produced via two different pathways (direct and stepwise), while dimethyl sulfide is formed via a competing pathway in the stepwise formation of methanethiol. Moreover, there is an increase in activity and a decrease in selectivity when adding an electropositive promoter (K), whereas the reverse behaviour is observed when adding an electronegative promoter (Cl). When adding Ni there is also a decrease in activity and an increase in selectivity; however, Ni is acting as an electron donor. The results provide insights and guidance as to what catalyst formulation is preferred for the removal of hydrogen sulfide in sour gas.},

  doi          = {10.1039/C9CY00375D},

  journal      = {Catalysis Science and Technology},

  number       = 17,

  volume       = 9,

  place        = {United Kingdom},

  year         = {Wed Jul 17 00:00:00 EDT 2019},

  month        = {Wed Jul 17 00:00:00 EDT 2019}

}

Copy to clipboard

Journal Article:

Free Publicly Available Full Text

Publisher's Version of Record
https://doi.org/10.1039/C9CY00375D

Other availability

Search WorldCat to find libraries that may hold this journal

Citation Metrics:

Cited by: 4 works

Citation information provided by
Web of Science

Save / Share:

Export Metadata

Save to My Library

Works referenced in this record:

On the integration of CO2 capture with coal-fired power plants: A methodology to assess and optimise solvent-based post-combustion capture systems
journal, September 2011

Lucquiaud, Mathieu; Gibbins, Jon
Chemical Engineering Research and Design, Vol. 89, Issue 9
DOI: 10.1016/j.cherd.2011.03.003

Generalized Gradient Approximation Made Simple
journal, October 1996

Perdew, John P.; Burke, Kieron; Ernzerhof, Matthias
Physical Review Letters, Vol. 77, Issue 18, p. 3865-3868
DOI: 10.1103/PhysRevLett.77.3865

Projector augmented-wave method
journal, December 1994

Blöchl, P. E.
Physical Review B, Vol. 50, Issue 24, p. 17953-17979
DOI: 10.1103/PhysRevB.50.17953

Selective transformation of methyl and ethyl mercaptans mixture to hydrocarbons and H2S on solid acid catalysts
journal, September 2014

Cammarano, Claudia; Huguet, Edouard; Cadours, Renaud
Applied Catalysis B: Environmental, Vol. 156-157
DOI: 10.1016/j.apcatb.2014.03.026

OLEFIN METATHESIS: BIG-DEAL REACTION: A boon to organic synthetic chemists, olefin metathesis also promises cleaner, cheaper, and more efficient industrial processes
journal, December 2002

Rouhi, A. Maureen
Chemical & Engineering News Archive, Vol. 80, Issue 51
DOI: 10.1021/cen-v080n051.p029

Catalytic methyl mercaptan coupling to ethylene in chabazite: DFT study of the first C C bond formation
journal, June 2016

Baltrusaitis, J.; Bučko, T.; Michaels, W.
Applied Catalysis B: Environmental, Vol. 187
DOI: 10.1016/j.apcatb.2016.01.021

Alumina Catalysts in Low-Temperature Claus Process
journal, June 1977

Pearson, Michael J.
Industrial & Engineering Chemistry Product Research and Development, Vol. 16, Issue 2
DOI: 10.1021/i360062a009

Structural and textural properties of Fe 2 O 3 /γ-Al 2 O 3 catalysts and their importance in the catalytic reforming of CH 4 with H 2 S for hydrogen production
journal, August 2015

Galindo-Hernández, Félix; Domínguez, J. M.; Portales, Benjamín
Journal of Power Sources, Vol. 287
DOI: 10.1016/j.jpowsour.2015.04.015

From ultrasoft pseudopotentials to the projector augmented-wave method
journal, January 1999

Kresse, G.; Joubert, D.
Physical Review B, Vol. 59, Issue 3, p. 1758-1775
DOI: 10.1103/PhysRevB.59.1758

NIST Chemistry WebBook, NIST Standard Reference Database 69
dataset, January 1997

Linstrom, Peter
National Institute of Standards and Technology
DOI: 10.18434/T4D303

A fast and robust algorithm for Bader decomposition of charge density
journal, June 2006

Henkelman, Graeme; Arnaldsson, Andri; Jónsson, Hannes
Computational Materials Science, Vol. 36, Issue 3
DOI: 10.1016/j.commatsci.2005.04.010

Kinetics of catalytic reaction of methane and hydrogen sulphide over MoS2
journal, December 1997

Megalofonos, S. K.; Papayannakos, N. G.
Applied Catalysis A: General, Vol. 165, Issue 1-2
DOI: 10.1016/S0926-860X(97)00206-8

Crystal orbital Hamilton populations (COHP): energy-resolved visualization of chemical bonding in solids based on density-functional calculations
journal, August 1993

Dronskowski, Richard; Bloechl, Peter E.
The Journal of Physical Chemistry, Vol. 97, Issue 33
DOI: 10.1021/j100135a014

Methanol Synthesis from H ₂ and CO ₂ on a Mo ₆ S ₈ Cluster: A Density Functional Study ^†
journal, March 2010

Liu, Ping; Choi, YongMan; Yang, Yixiong
The Journal of Physical Chemistry A, Vol. 114, Issue 11
DOI: 10.1021/jp906780a

Analytic projection from plane-wave and PAW wavefunctions and application to chemical-bonding analysis in solids
journal, September 2013

Maintz, Stefan; Deringer, Volker L.; Tchougréeff, Andrei L.
Journal of Computational Chemistry, Vol. 34, Issue 29
DOI: 10.1002/jcc.23424

Pilot plant experiments for post combustion carbon dioxide capture by reactive absorption with novel solvents
journal, January 2011

Mangalapally, Hari Prasad; Hasse, Hans
Energy Procedia, Vol. 4
DOI: 10.1016/j.egypro.2011.01.015

CH ₄ and H ₂ S reforming to CH ₃ SH and H ₂ catalyzed by metal-promoted Mo ₆ S ₈ clusters: a first-principles micro-kinetic study
journal, January 2017

Taifan, William; Arvidsson, Adam A.; Nelson, Eric
Catalysis Science & Technology, Vol. 7, Issue 16
DOI: 10.1039/C7CY00857K

Synthesis of methyl mercaptan from carbonyl sulfide over sulfide K2MoO4/SiO2
journal, June 2011

Gutiérrez, Oliver Y.; Kaufmann, Christoph; Hrabar, Ana
Journal of Catalysis, Vol. 280, Issue 2
DOI: 10.1016/j.jcat.2011.03.027

Conversion of methyl mercaptan and methanol to hydrocarbons over solid acid catalysts – A comparative study
journal, January 2014

Hulea, Vasile; Huguet, Edouard; Cammarano, Claudia
Applied Catalysis B: Environmental, Vol. 144
DOI: 10.1016/j.apcatb.2013.07.056

Minireview: direct catalytic conversion of sour natural gas (CH ₄ + H ₂ S + CO ₂ ) components to high value chemicals and fuels
journal, January 2017

Taifan, William; Baltrusaitis, Jonas
Catalysis Science & Technology, Vol. 7, Issue 14
DOI: 10.1039/C7CY00272F

A dimer method for finding saddle points on high dimensional potential surfaces using only first derivatives
journal, October 1999

Henkelman, Graeme; Jónsson, Hannes
The Journal of Chemical Physics, Vol. 111, Issue 15
DOI: 10.1063/1.480097

CH 4 conversion to value added products: Potential, limitations and extensions of a single step heterogeneous catalysis
journal, December 2016

Taifan, William; Baltrusaitis, Jonas
Applied Catalysis B: Environmental, Vol. 198
DOI: 10.1016/j.apcatb.2016.05.081

The path of chemical reactions - the IRC approach
journal, December 1981

Fukui, Kenichi
Accounts of Chemical Research, Vol. 14, Issue 12
DOI: 10.1021/ar00072a001

Experimental and modeling study of hydrogen production from catalytic steam reforming of methane mixture with hydrogen sulfide
journal, September 2015

Sadooghi, Parham; Rauch, Reinhard
International Journal of Hydrogen Energy, Vol. 40, Issue 33
DOI: 10.1016/j.ijhydene.2015.06.143

Reactivity of the <mml:math altimg="si14.gif" display="inline" overflow="scroll" xmlns:xocs="http://www.elsevier.com/xml/xocs/dtd" xmlns:xs="http://www.w3.org/2001/XMLSchema" xmlns:xsi="http://www.w3.org/2001/XMLSchema-instance" xmlns="http://www.elsevier.com/xml/ja/dtd" xmlns:ja="http://www.elsevier.com/xml/ja/dtd" xmlns:mml="http://www.w3.org/1998/Math/MathML" xmlns:tb="http://www.elsevier.com/xml/common/table/dtd" xmlns:sb="http://www.elsevier.com/xml/common/struct-bib/dtd" xmlns:ce="http://www.elsevier.com/xml/common/dtd" xmlns:xlink="http://www.w3.org/1999/xlink" xmlns:cals="http://www.elsevier.com/xml/common/cals/dtd"><mml:mrow><mml:msub><mml:mrow><mml:mi mathvariant="normal">M</mml:mi></mml:mrow><mml:mrow><mml:mn>4</mml:mn></mml:mrow></mml:msub><mml:msubsup><mml:mrow><mml:mi mathvariant="normal">S</mml:mi></mml:mrow><mml:mrow><mml:mn>6</mml:mn></mml:mrow><mml:mrow><mml:mo>+</mml:mo></mml:mrow></mml:msubsup></mml:mrow></mml:math> (M=Mo, W) cluster with CO and NH3 in the gas-phase: An experimental and DFT study
journal, September 2005

Lightstone, James M.; Patterson, Melissa J.; White, Michael G.
Chemical Physics Letters, Vol. 413, Issue 4-6
DOI: 10.1016/j.cplett.2005.07.109

Atomic structures and magnetism in small ${MoS}_{2}$ and ${WS}_{2}$ clusters
journal, June 2005

Murugan, P.; Kumar, Vijay; Kawazoe, Yoshiyuki
Physical Review A, Vol. 71, Issue 6
DOI: 10.1103/PhysRevA.71.063203

Electronic charging of non-metallic clusters: size-selected MoxSy clusters supported on an ultrathin alumina film on NiAl(110)
journal, January 2012

Zhou, Jing; Zhou, Jia; Camillone, Nicholas
Physical Chemistry Chemical Physics, Vol. 14, Issue 22
DOI: 10.1039/c2cp40921f

An object-oriented scripting interface to a legacy electronic structure code
journal, January 2002

Bahn, S. R.; Jacobsen, K. W.
Computing in Science & Engineering, Vol. 4, Issue 3
DOI: 10.1109/5992.998641

Efficient methods for finding transition states in chemical reactions: Comparison of improved dimer method and partitioned rational function optimization method
journal, December 2005

Heyden, Andreas; Bell, Alexis T.; Keil, Frerich J.
The Journal of Chemical Physics, Vol. 123, Issue 22
DOI: 10.1063/1.2104507

Insight into the Mechanism of Reverse Water-gas Shift Reaction and Ethanol Formation Catalyzed by Mo 6 S 8 -TM Clusters
journal, October 2017

Zheng, Xiaoli; Guo, Ling; Li, Wenli
Molecular Catalysis, Vol. 439
DOI: 10.1016/j.mcat.2017.06.030

Formulation of the reaction coordinate
journal, November 1970

Fukui, Kenichi
The Journal of Physical Chemistry, Vol. 74, Issue 23
DOI: 10.1021/j100717a029

Accurate and efficient algorithm for Bader charge integration
journal, February 2011

Yu, Min; Trinkle, Dallas R.
The Journal of Chemical Physics, Vol. 134, Issue 6
DOI: 10.1063/1.3553716

Conversion of Methyl Mercaptan to Hydrocarbons over H-ZSM-5 Zeolite: DFT/BOMD Study
journal, August 2017

Reina, Miguel; Martinez, Ana; Cammarano, Claudia
ACS Omega, Vol. 2, Issue 8
DOI: 10.1021/acsomega.7b00756

Hydrogen production from natural gas and hydrogen sulphide
journal, January 1991

Megalofonos, S.; Papayannakos, N.
International Journal of Hydrogen Energy, Vol. 16, Issue 5
DOI: 10.1016/0360-3199(91)90168-I

Influence of Potassium on the Synthesis of Methanethiol from Carbonyl Sulfide on Sulfided Mo/Al2O3 Catalyst
journal, July 2011

Gutiérrez, Oliver Y.; Kaufmann, Christoph; Lercher, Johannes A.
ChemCatChem, Vol. 3, Issue 9
DOI: 10.1002/cctc.201100124

Efficiency of ab-initio total energy calculations for metals and semiconductors using a plane-wave basis set
journal, July 1996

Kresse, G.; Furthmüller, J.
Computational Materials Science, Vol. 6, Issue 1, p. 15-50
DOI: 10.1016/0927-0256(96)00008-0

A highly efficient process for transforming methyl mercaptan into hydrocarbons and H2S on solid acid catalysts
journal, May 2013

Huguet, Edouard; Coq, Bernard; Durand, Robert
Applied Catalysis B: Environmental, Vol. 134-135
DOI: 10.1016/j.apcatb.2013.01.037

Structure of Molybdenum and Tungsten Sulfide M _x S _y ⁺ Clusters: Experiment and DFT Calculations
journal, November 2008

Patterson, Melissa J.; Lightstone, James M.; White, Michael G.
The Journal of Physical Chemistry A, Vol. 112, Issue 47
DOI: 10.1021/jp807318c

LOBSTER: A tool to extract chemical bonding from plane-wave based DFT: Tool to Extract Chemical Bonding
journal, February 2016

Maintz, Stefan; Deringer, Volker L.; Tchougréeff, Andrei L.
Journal of Computational Chemistry, Vol. 37, Issue 11
DOI: 10.1002/jcc.24300

Synthesis of Methanethiol from CS ₂ on Ni-, Co-, and K-Doped MoS ₂ /SiO ₂ Catalysts
journal, June 2013

Gutiérrez, Oliver Y.; Zhong, Liangshu; Zhu, Yongzhong
ChemCatChem, Vol. 5, Issue 11
DOI: 10.1002/cctc.201300210

Following Reaction Pathways Using a Damped Classical Trajectory Algorithm
journal, January 2002

Hratchian, H. P.; Schlegel, H. B.
The Journal of Physical Chemistry A, Vol. 106, Issue 1
DOI: 10.1021/jp012125b

Ab initio molecular dynamics for open-shell transition metals
journal, November 1993

Kresse, G.; Hafner, J.
Physical Review B, Vol. 48, Issue 17
DOI: 10.1103/PhysRevB.48.13115

H ₂ S-Mediated Thermal and Photochemical Methane Activation
journal, October 2013

Baltrusaitis, Jonas; de Graaf, Coen; Broer, Ria
ChemPhysChem, Vol. 14, Issue 17
DOI: 10.1002/cphc.201300828

Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set
journal, October 1996

Kresse, G.; Furthmüller, J.
Physical Review B, Vol. 54, Issue 16, p. 11169-11186
DOI: 10.1103/PhysRevB.54.11169

Ab initio molecular-dynamics simulation of the liquid-metal–amorphous-semiconductor transition in germanium
journal, May 1994

Kresse, G.; Hafner, J.
Physical Review B, Vol. 49, Issue 20, p. 14251-14269
DOI: 10.1103/PhysRevB.49.14251

Effects of methylating agent and Brønsted acidity on methylation activity of olefins in CHA-structured zeolites: A periodic DFT study
journal, February 2018

Li, Qing-Ming; Zhang, Min; Wang, Chuan-Ming
Molecular Catalysis, Vol. 446
DOI: 10.1016/j.mcat.2017.12.034

Synthesis of Methanethiol from Methanol over Reduced Molybdenum Sulfide Catalysts Based on the Mo6S8 Cluster
journal, October 2002

Paskach, T.
Journal of Catalysis, Vol. 211, Issue 2
DOI: 10.1016/S0021-9517(02)93684-5

Thermodynamic analyses of hydrogen production from sub-quality natural gas
journal, January 2007

Huang, Cunping; T-Raissi, Ali
Journal of Power Sources, Vol. 163, Issue 2
DOI: 10.1016/j.jpowsour.2006.02.081

Kinetic study of decomposition of H 2 S and CH 4 for H 2 production using detailed mechanism
journal, December 2017

Li, Yang; Yu, Xinlei; Guo, Qinghua
Energy Procedia, Vol. 142
DOI: 10.1016/j.egypro.2017.12.357

Olefin Metathesis by Supported Metal Oxide Catalysts
journal, June 2014

Lwin, Soe; Wachs, Israel E.
ACS Catalysis, Vol. 4, Issue 8
DOI: 10.1021/cs500528h

Pilot plant experimental studies of post combustion CO2 capture by reactive absorption with MEA and new solvents
journal, February 2009

Mangalapally, Hari Prasad; Notz, Ralf; Hoch, Sebastian
Energy Procedia, Vol. 1, Issue 1
DOI: 10.1016/j.egypro.2009.01.128

Crystal Orbital Hamilton Population (COHP) Analysis As Projected from Plane-Wave Basis Sets
journal, June 2011

Deringer, Volker L.; Tchougréeff, Andrei L.; Dronskowski, Richard
The Journal of Physical Chemistry A, Vol. 115, Issue 21
DOI: 10.1021/jp202489s

Improved grid-based algorithm for Bader charge allocation
journal, January 2007

Sanville, Edward; Kenny, Steven D.; Smith, Roger
Journal of Computational Chemistry, Vol. 28, Issue 5
DOI: 10.1002/jcc.20575

Synthesis of Methanethiol from Carbonyl Sulfide and Carbon Disulfide on (Co)K-Promoted Sulfide Mo/SiO ₂ Catalysts
journal, October 2011

Gutiérrez, Oliver Y.; Kaufmann, Christoph; Lercher, Johannes A.
ACS Catalysis, Vol. 1, Issue 11
DOI: 10.1021/cs200455k

Decomposition of alkanethiols to dialkyl sulfides and hydrogen sulfide
journal, May 1990

Mashkina, A. V.; Grunvald, V. R.; Nasteka, V. I.
Reaction Kinetics & Catalysis Letters, Vol. 41, Issue 2
DOI: 10.1007/BF02097894

Electrophilic methane conversion
journal, November 1987

Olah, George A.
Accounts of Chemical Research, Vol. 20, Issue 11
DOI: 10.1021/ar00143a006

Mechanistic Study of Methanol Synthesis from CO ₂ and H ₂ on a Modified Model Mo ₆ S ₈ Cluster
journal, January 2015

Liu, Cheng; Liu, Ping
ACS Catalysis, Vol. 5, Issue 2
DOI: 10.1021/cs501354b

Hydrogen production by methane reforming with H2S using Mo,Cr/ZrO2–SBA15 and Mo,Cr/ZrO2–La2O3 catalysts
journal, December 2015

Martínez-Salazar, A. L.; Melo-Banda, J. A.; Reyes de la Torre, A. I.
International Journal of Hydrogen Energy, Vol. 40, Issue 48
DOI: 10.1016/j.ijhydene.2015.09.154

The conversion of methanol and other O-compounds to hydrocarbons over zeolite catalysts
journal, May 1977

Chang, C.
Journal of Catalysis, Vol. 47, Issue 2
DOI: 10.1016/0021-9517(77)90172-5

Kinetics of the catalytic reaction of methane and hydrogen sulphide over a PtAl2O3 catalyst
journal, April 1996

Megalofonos, S. K.; Papayannakos, N. G.
Applied Catalysis A: General, Vol. 138, Issue 1
DOI: 10.1016/0926-860X(95)00227-8

Similar Records in DOE PAGES and OSTI.GOV collections:

Photooxidation of methyl sulfide, ethyl sulfide, and methanethiol

Journal Article Grosjean, D - Environ. Sci. Technol.; (United States)

Products of sunlight-irradiated mixtures of oxides of nitrogen and alkyl sulfides (RSR, R = CH/sub 3/, C/sub 2/H/sub 5/) and methanethiol (CH/sub 3/SH) in air include formaldehyde (R = CH/sub 3/), acetaldehyde and PAN (R = C/sub 2/H/sub 5/), sulfur dioxide, and alkyl nitrates (RONO/sub 2/) as well as particulate alkanesulfonic acids (RSO/sub 2/OH) and inorganic sulfate. The nature and yields of gaseous and particulate products are discussed in terms of OH-initiated reaction pathways, including C-S bond scission, and subsequent reactions of alkythiyl radicals (RS), including those leading to photolabile RSNO and stable RSNO/sub 2/ products for which indirect evidencemore »« less
https://doi.org/10.1021/es00124a013
Mechanistic study of the hydrodesulfurization of methanethiol over tungsten disulfide; a survey of rare earth sulfides for hydrodesulfurization activity

Technical Report Dowd, D Q

Hydrodesulfurization is a process whereby sulfur bound in organic compounds is removed as hydrogen sulfide, and is important to the control of sulfur dioxide emissions in the combustion of petroleum and coal fuels. It involves the cleavage of carbon sulfur bonds, and is catalyzed by layered disulfides such as molybdenum and tungsten disulfide. The simplest example is the reaction CH/sub 3/SH + H/sub 2/ ..-->.. CH/sub 4/ + H/sub 2/S. The mechanism of even this protypical reaction is unclear. In an effort to clarify it, the kinetics of methanethiol hydrodesulfurization over tungsten disulfide at low pressures was established, with partialmore »« less
Mechanistic study of the hydrodesulfurization of methanethiol over tungsten disulfide. II. A survey of rare earth sulfides for hydrodesulfurization activity

Thesis/Dissertation Dowd, D Q

I. Hydrodesulfurization is a process whereby sulfur bound in organic compounds is removed as hydrogen sulfide, and is important to the control of sulfur dioxide emissions in the combustion of petroleum and coal fuels. It involves the cleavage of carbon sulfur bonds, and is catalyzed by layered disulfides such as molybdenum and tungsten disulfide. The simplest example is the reaction CH/sub 3/SH + H/sub 2/ ..-->.. CH/sub 4/ + H/sub 2/S. The mechanism of even this prototypical reaction is unclear. In an effort to clarify it, the kinetics of methanethiol hydro desulfurization over tungsten disulfide at low pressures was established,more »« less
Refinery hydrogen sulfide emissions cut 99. 9% with chelated catalyst

Journal Article Leicht, R K ; Regan, J T ; Toy, D A - Chem. Process. (Chicago); (United States)

Fletcher Oil and Refining Company is a small to medium sized refinery located in Carson, CA, producing gasoline and fuel oils for sale to the open market. In 1981, the company initiated a major plant expansion and overhaul. In addition to a new catalytic cracking unit, two 49 MM Btu/hr steam boilers, a 15 MM and a 32 MM Btu/hr process heater were added. Because of the increased capacity generated by the catalytic cracking unit and the four new combustion sources, Fletcher had to reckon with increased hydrogen sulfide (H/sub 2/S) emissions, an undesirable byproduct of petroleum refining. The researchmore »« less
Removal of methanethiol, dimethyl sulfide, dimethyl disulfide, and hydrogen sulfide from contaminated air by Thiobacillus thioparus TK-m

Journal Article Kanagawa, T ; Mikami, E - Appl. Environ. Microbiol.; (United States)

Methanethiol, dimethyl sulfide, dimethyl disulfide, and hydrogen sulfide were efficiently removed from contaminated air by Thiobacillus thioparus TK-m and oxidized to sulfate stoichiometrically. More than 99.99% of dimethyl sulfide was removed when the load was less than 4.0 g of dimethyl sulfide per g (dry cell weight) per day.

Similar Records

Title: First-principles microkinetic study of methane and hydrogen sulfide catalytic conversion to methanethiol/dimethyl sulfide on Mo6S8 clusters: activity/selectivity of different promoters

Abstract

Citation Formats

On the integration of CO2 capture with coal-fired power plants: A methodology to assess and optimise solvent-based post-combustion capture systems journal, September 2011

Generalized Gradient Approximation Made Simple journal, October 1996

Projector augmented-wave method journal, December 1994

Selective transformation of methyl and ethyl mercaptans mixture to hydrocarbons and H2S on solid acid catalysts journal, September 2014

OLEFIN METATHESIS: BIG-DEAL REACTION: A boon to organic synthetic chemists, olefin metathesis also promises cleaner, cheaper, and more efficient industrial processes journal, December 2002

Catalytic methyl mercaptan coupling to ethylene in chabazite: DFT study of the first C C bond formation journal, June 2016

Alumina Catalysts in Low-Temperature Claus Process journal, June 1977

Structural and textural properties of Fe 2 O 3 /γ-Al 2 O 3 catalysts and their importance in the catalytic reforming of CH 4 with H 2 S for hydrogen production journal, August 2015

From ultrasoft pseudopotentials to the projector augmented-wave method journal, January 1999

NIST Chemistry WebBook, NIST Standard Reference Database 69 dataset, January 1997

A fast and robust algorithm for Bader decomposition of charge density journal, June 2006

Kinetics of catalytic reaction of methane and hydrogen sulphide over MoS2 journal, December 1997

Crystal orbital Hamilton populations (COHP): energy-resolved visualization of chemical bonding in solids based on density-functional calculations journal, August 1993

Methanol Synthesis from H 2 and CO 2 on a Mo 6 S 8 Cluster: A Density Functional Study † journal, March 2010

Analytic projection from plane-wave and PAW wavefunctions and application to chemical-bonding analysis in solids journal, September 2013

Pilot plant experiments for post combustion carbon dioxide capture by reactive absorption with novel solvents journal, January 2011

CH 4 and H 2 S reforming to CH 3 SH and H 2 catalyzed by metal-promoted Mo 6 S 8 clusters: a first-principles micro-kinetic study journal, January 2017

Synthesis of methyl mercaptan from carbonyl sulfide over sulfide K2MoO4/SiO2 journal, June 2011

Conversion of methyl mercaptan and methanol to hydrocarbons over solid acid catalysts – A comparative study journal, January 2014

Minireview: direct catalytic conversion of sour natural gas (CH 4 + H 2 S + CO 2 ) components to high value chemicals and fuels journal, January 2017

A dimer method for finding saddle points on high dimensional potential surfaces using only first derivatives journal, October 1999

CH 4 conversion to value added products: Potential, limitations and extensions of a single step heterogeneous catalysis journal, December 2016

The path of chemical reactions - the IRC approach journal, December 1981

Experimental and modeling study of hydrogen production from catalytic steam reforming of methane mixture with hydrogen sulfide journal, September 2015

Atomic structures and magnetism in small MoS 2 and WS 2 clusters journal, June 2005

Electronic charging of non-metallic clusters: size-selected MoxSy clusters supported on an ultrathin alumina film on NiAl(110) journal, January 2012

An object-oriented scripting interface to a legacy electronic structure code journal, January 2002

Efficient methods for finding transition states in chemical reactions: Comparison of improved dimer method and partitioned rational function optimization method journal, December 2005

Insight into the Mechanism of Reverse Water-gas Shift Reaction and Ethanol Formation Catalyzed by Mo 6 S 8 -TM Clusters journal, October 2017

Formulation of the reaction coordinate journal, November 1970

Accurate and efficient algorithm for Bader charge integration journal, February 2011

Conversion of Methyl Mercaptan to Hydrocarbons over H-ZSM-5 Zeolite: DFT/BOMD Study journal, August 2017

Hydrogen production from natural gas and hydrogen sulphide journal, January 1991

Influence of Potassium on the Synthesis of Methanethiol from Carbonyl Sulfide on Sulfided Mo/Al2O3 Catalyst journal, July 2011

Efficiency of ab-initio total energy calculations for metals and semiconductors using a plane-wave basis set journal, July 1996

A highly efficient process for transforming methyl mercaptan into hydrocarbons and H2S on solid acid catalysts journal, May 2013

Structure of Molybdenum and Tungsten Sulfide M x S y + Clusters: Experiment and DFT Calculations journal, November 2008

LOBSTER: A tool to extract chemical bonding from plane-wave based DFT: Tool to Extract Chemical Bonding journal, February 2016

Synthesis of Methanethiol from CS 2 on Ni-, Co-, and K-Doped MoS 2 /SiO 2 Catalysts journal, June 2013

Following Reaction Pathways Using a Damped Classical Trajectory Algorithm journal, January 2002

Ab initio molecular dynamics for open-shell transition metals journal, November 1993

H 2 S-Mediated Thermal and Photochemical Methane Activation journal, October 2013

Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set journal, October 1996

Ab initio molecular-dynamics simulation of the liquid-metal–amorphous-semiconductor transition in germanium journal, May 1994

Effects of methylating agent and Brønsted acidity on methylation activity of olefins in CHA-structured zeolites: A periodic DFT study journal, February 2018

Synthesis of Methanethiol from Methanol over Reduced Molybdenum Sulfide Catalysts Based on the Mo6S8 Cluster journal, October 2002

Thermodynamic analyses of hydrogen production from sub-quality natural gas journal, January 2007

Kinetic study of decomposition of H 2 S and CH 4 for H 2 production using detailed mechanism journal, December 2017

Olefin Metathesis by Supported Metal Oxide Catalysts journal, June 2014

Pilot plant experimental studies of post combustion CO2 capture by reactive absorption with MEA and new solvents journal, February 2009

Crystal Orbital Hamilton Population (COHP) Analysis As Projected from Plane-Wave Basis Sets journal, June 2011

Improved grid-based algorithm for Bader charge allocation journal, January 2007

Synthesis of Methanethiol from Carbonyl Sulfide and Carbon Disulfide on (Co)K-Promoted Sulfide Mo/SiO 2 Catalysts journal, October 2011

Decomposition of alkanethiols to dialkyl sulfides and hydrogen sulfide journal, May 1990

Electrophilic methane conversion journal, November 1987

Mechanistic Study of Methanol Synthesis from CO 2 and H 2 on a Modified Model Mo 6 S 8 Cluster journal, January 2015

Hydrogen production by methane reforming with H2S using Mo,Cr/ZrO2–SBA15 and Mo,Cr/ZrO2–La2O3 catalysts journal, December 2015

The conversion of methanol and other O-compounds to hydrocarbons over zeolite catalysts journal, May 1977

Kinetics of the catalytic reaction of methane and hydrogen sulphide over a PtAl2O3 catalyst journal, April 1996

Title: First-principles microkinetic study of methane and hydrogen sulfide catalytic conversion to methanethiol/dimethyl sulfide on Mo₆S₈ clusters: activity/selectivity of different promoters

On the integration of CO2 capture with coal-fired power plants: A methodology to assess and optimise solvent-based post-combustion capture systems
journal, September 2011

Generalized Gradient Approximation Made Simple
journal, October 1996

Projector augmented-wave method
journal, December 1994

Selective transformation of methyl and ethyl mercaptans mixture to hydrocarbons and H2S on solid acid catalysts
journal, September 2014

OLEFIN METATHESIS: BIG-DEAL REACTION: A boon to organic synthetic chemists, olefin metathesis also promises cleaner, cheaper, and more efficient industrial processes
journal, December 2002

Catalytic methyl mercaptan coupling to ethylene in chabazite: DFT study of the first C C bond formation
journal, June 2016

Alumina Catalysts in Low-Temperature Claus Process
journal, June 1977

Structural and textural properties of Fe 2 O 3 /γ-Al 2 O 3 catalysts and their importance in the catalytic reforming of CH 4 with H 2 S for hydrogen production
journal, August 2015

From ultrasoft pseudopotentials to the projector augmented-wave method
journal, January 1999

NIST Chemistry WebBook, NIST Standard Reference Database 69
dataset, January 1997

A fast and robust algorithm for Bader decomposition of charge density
journal, June 2006

Kinetics of catalytic reaction of methane and hydrogen sulphide over MoS2
journal, December 1997

Crystal orbital Hamilton populations (COHP): energy-resolved visualization of chemical bonding in solids based on density-functional calculations
journal, August 1993

Methanol Synthesis from H ₂ and CO ₂ on a Mo ₆ S ₈ Cluster: A Density Functional Study ^†
journal, March 2010

Analytic projection from plane-wave and PAW wavefunctions and application to chemical-bonding analysis in solids
journal, September 2013

Pilot plant experiments for post combustion carbon dioxide capture by reactive absorption with novel solvents
journal, January 2011

CH ₄ and H ₂ S reforming to CH ₃ SH and H ₂ catalyzed by metal-promoted Mo ₆ S ₈ clusters: a first-principles micro-kinetic study
journal, January 2017

Synthesis of methyl mercaptan from carbonyl sulfide over sulfide K2MoO4/SiO2
journal, June 2011

Conversion of methyl mercaptan and methanol to hydrocarbons over solid acid catalysts – A comparative study
journal, January 2014

Minireview: direct catalytic conversion of sour natural gas (CH ₄ + H ₂ S + CO ₂ ) components to high value chemicals and fuels
journal, January 2017

A dimer method for finding saddle points on high dimensional potential surfaces using only first derivatives
journal, October 1999

CH 4 conversion to value added products: Potential, limitations and extensions of a single step heterogeneous catalysis
journal, December 2016

The path of chemical reactions - the IRC approach
journal, December 1981

Experimental and modeling study of hydrogen production from catalytic steam reforming of methane mixture with hydrogen sulfide
journal, September 2015

Atomic structures and magnetism in small ${MoS}_{2}$ and ${WS}_{2}$ clusters
journal, June 2005

Electronic charging of non-metallic clusters: size-selected MoxSy clusters supported on an ultrathin alumina film on NiAl(110)
journal, January 2012

An object-oriented scripting interface to a legacy electronic structure code
journal, January 2002

Efficient methods for finding transition states in chemical reactions: Comparison of improved dimer method and partitioned rational function optimization method
journal, December 2005

Insight into the Mechanism of Reverse Water-gas Shift Reaction and Ethanol Formation Catalyzed by Mo 6 S 8 -TM Clusters
journal, October 2017

Formulation of the reaction coordinate
journal, November 1970

Accurate and efficient algorithm for Bader charge integration
journal, February 2011

Conversion of Methyl Mercaptan to Hydrocarbons over H-ZSM-5 Zeolite: DFT/BOMD Study
journal, August 2017

Hydrogen production from natural gas and hydrogen sulphide
journal, January 1991

Influence of Potassium on the Synthesis of Methanethiol from Carbonyl Sulfide on Sulfided Mo/Al2O3 Catalyst
journal, July 2011

Efficiency of ab-initio total energy calculations for metals and semiconductors using a plane-wave basis set
journal, July 1996

A highly efficient process for transforming methyl mercaptan into hydrocarbons and H2S on solid acid catalysts
journal, May 2013

Structure of Molybdenum and Tungsten Sulfide M _x S _y ⁺ Clusters: Experiment and DFT Calculations
journal, November 2008

LOBSTER: A tool to extract chemical bonding from plane-wave based DFT: Tool to Extract Chemical Bonding
journal, February 2016

Synthesis of Methanethiol from CS ₂ on Ni-, Co-, and K-Doped MoS ₂ /SiO ₂ Catalysts
journal, June 2013

Following Reaction Pathways Using a Damped Classical Trajectory Algorithm
journal, January 2002

Ab initio molecular dynamics for open-shell transition metals
journal, November 1993

H ₂ S-Mediated Thermal and Photochemical Methane Activation
journal, October 2013

Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set
journal, October 1996

Ab initio molecular-dynamics simulation of the liquid-metal–amorphous-semiconductor transition in germanium
journal, May 1994

Effects of methylating agent and Brønsted acidity on methylation activity of olefins in CHA-structured zeolites: A periodic DFT study
journal, February 2018

Synthesis of Methanethiol from Methanol over Reduced Molybdenum Sulfide Catalysts Based on the Mo6S8 Cluster
journal, October 2002

Thermodynamic analyses of hydrogen production from sub-quality natural gas
journal, January 2007

Kinetic study of decomposition of H 2 S and CH 4 for H 2 production using detailed mechanism
journal, December 2017

Olefin Metathesis by Supported Metal Oxide Catalysts
journal, June 2014

Pilot plant experimental studies of post combustion CO2 capture by reactive absorption with MEA and new solvents
journal, February 2009

Crystal Orbital Hamilton Population (COHP) Analysis As Projected from Plane-Wave Basis Sets
journal, June 2011

Improved grid-based algorithm for Bader charge allocation
journal, January 2007

Synthesis of Methanethiol from Carbonyl Sulfide and Carbon Disulfide on (Co)K-Promoted Sulfide Mo/SiO ₂ Catalysts
journal, October 2011

Decomposition of alkanethiols to dialkyl sulfides and hydrogen sulfide
journal, May 1990

Electrophilic methane conversion
journal, November 1987

Mechanistic Study of Methanol Synthesis from CO ₂ and H ₂ on a Modified Model Mo ₆ S ₈ Cluster
journal, January 2015

Hydrogen production by methane reforming with H2S using Mo,Cr/ZrO2–SBA15 and Mo,Cr/ZrO2–La2O3 catalysts
journal, December 2015

The conversion of methanol and other O-compounds to hydrocarbons over zeolite catalysts
journal, May 1977

Kinetics of the catalytic reaction of methane and hydrogen sulphide over a PtAl2O3 catalyst
journal, April 1996