Modeling Sulfur Poisoning of Palladium Membranes Used for Hydrogen Separation

Gabitto, Jorge; Tsouris, Costas

doi:10.1155/2019/9825280

Title: Modeling Sulfur Poisoning of Palladium Membranes Used for Hydrogen Separation

Abstract

Hydrocarbons are the most important source for hydrogen production. A combined reaction-separation process using inorganic membranes can significantly increase the reaction conversion by shifting the equilibrium toward product formation. Sulfur poisoning is a significant problem as it deactivates the most commonly used metallic membranes. The relationship of the membrane activity and surface coverage with the surface structure has been recognized in the literature. A theoretical model to simulate hydrogen transport in the presence of sulfur compounds is presented. This model accounts for active site deactivation and permanent structural damage to the membrane. Transport and reaction rate parameters used in the model have been estimated from experimental data. Qualitatively, the model represents well the behavior of inorganic membranes, including partial membrane activity regeneration after the sulfur source is removed.

Authors:

^[1];

^[2]

Prairie View A&M Univ., Prairie View, TX (United States)
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)

Publication Date:: Sun Mar 03 00:00:00 EST 2019

Research Org.:: Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)

Sponsoring Org.:: USDOE

OSTI Identifier:: 1531239

Grant/Contract Number:: AC05-00OR22725

Resource Type:: Accepted Manuscript

Journal Name:: International Journal of Chemical Engineering

Additional Journal Information:: Journal Volume: 2019; Journal Issue: N/A; Journal ID: ISSN 1687-806X

Publisher:: Hindawi

Country of Publication:: United States

Language:: English

Subject:: 08 HYDROGEN; 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; 59 BASIC BIOLOGICAL SCIENCES

Citation Formats


                    Gabitto, Jorge, and Tsouris, Costas. Modeling Sulfur Poisoning of Palladium Membranes Used for Hydrogen Separation.  United States: N. p., 2019. 
Web.  doi:10.1155/2019/9825280.

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                    Gabitto, Jorge, & Tsouris, Costas. Modeling Sulfur Poisoning of Palladium Membranes Used for Hydrogen Separation.  United States.  https://doi.org/10.1155/2019/9825280

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                    Gabitto, Jorge, and Tsouris, Costas. Sun .  
"Modeling Sulfur Poisoning of Palladium Membranes Used for Hydrogen Separation".  United States.  https://doi.org/10.1155/2019/9825280.  https://www.osti.gov/servlets/purl/1531239.

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@article{osti_1531239,

  title        = {Modeling Sulfur Poisoning of Palladium Membranes Used for Hydrogen Separation},

  author       = {Gabitto, Jorge and Tsouris, Costas},

  abstractNote = {Hydrocarbons are the most important source for hydrogen production. A combined reaction-separation process using inorganic membranes can significantly increase the reaction conversion by shifting the equilibrium toward product formation. Sulfur poisoning is a significant problem as it deactivates the most commonly used metallic membranes. The relationship of the membrane activity and surface coverage with the surface structure has been recognized in the literature. A theoretical model to simulate hydrogen transport in the presence of sulfur compounds is presented. This model accounts for active site deactivation and permanent structural damage to the membrane. Transport and reaction rate parameters used in the model have been estimated from experimental data. Qualitatively, the model represents well the behavior of inorganic membranes, including partial membrane activity regeneration after the sulfur source is removed.},

  doi          = {10.1155/2019/9825280},

  journal      = {International Journal of Chemical Engineering},

  number       = N/A,

  volume       = 2019,

  place        = {United States},

  year         = {Sun Mar 03 00:00:00 EST 2019},

  month        = {Sun Mar 03 00:00:00 EST 2019}

}

Copy to clipboard

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Works referenced in this record:

Modern and prospective technologies for hydrogen production from fossil fuels
journal, January 1989

Steinberg, M.
International Journal of Hydrogen Energy, Vol. 14, Issue 11
DOI: 10.1016/0360-3199(89)90018-9

Modular Chemical Process Intensification: A Review
journal, June 2017

Kim, Yong-ha; Park, Lydia K.; Yiacoumi, Sotira
Annual Review of Chemical and Biomolecular Engineering, Vol. 8, Issue 1
DOI: 10.1146/annurev-chembioeng-060816-101354

Effect of hydrogen-sulfide on the hydrogen permeance of palladium?copper alloys at elevated temperatures
journal, October 2004

Morreale, B.
Journal of Membrane Science, Vol. 241, Issue 2
DOI: 10.1016/j.memsci.2004.04.033

Sulfur tolerance of zeolite beta-supported Pd−Pt catalysts for the isomerization of n-hexane
journal, July 1998

Lee, J.; Rhee, H.
Journal of Catalysis, Vol. 177, Issue 2
DOI: 10.1006/jcat.1998.2100

Experimental and Computational Prediction of the Hydrogen Transport Properties of Pd ₄ S
journal, September 2007

Morreale, Bryan D.; Howard, Bret H.; Iyoha, Osemwengie
Industrial & Engineering Chemistry Research, Vol. 46, Issue 19
DOI: 10.1021/ie070461u

Separation of hydrogen from gas mixtures using supported platinum-group metal membranes
journal, March 2001

Uemiya, S.
Separation and Purification Technology, Vol. 22-23, Issue 1-2
DOI: 10.1016/s1383-5866(00)00153-2

Hydrogen permeation through surface modified Pd and PdAg membranes
journal, October 2001

Amandusson, H.; Ekedahl, L.; Dannetun, H.
Journal of Membrane Science, Vol. 193, Issue 1
DOI: 10.1016/s0376-7388(01)00414-8

The performance of Pd–Ag alloy membrane films under exposure to trace amounts of H2S
journal, February 2016

Peters, T. A.; Stange, M.; Veenstra, P.
Journal of Membrane Science, Vol. 499
DOI: 10.1016/j.memsci.2015.10.031

Pd-Based Membranes for Hydrogen Separation: Review of Alloying Elements and Their Influence on Membrane Properties
journal, July 2016

Conde, Julio J.; Maroño, Marta; Sánchez-Hervás, José María
Separation & Purification Reviews, Vol. 46, Issue 2
DOI: 10.1080/15422119.2016.1212379

Bildung von Mischkristallen durch Ber�hrung fester Phasen
journal, September 1921

Vegard, L.
Zeitschrift f�r Physik, Vol. 5, Issue 5-6
DOI: 10.1007/bf01327675

Structural and Permeation Kinetic Correlations in PdCuAg Membranes
journal, December 2014

Zhao, Lingfang; Goldbach, Andreas; Bao, Chun
ACS Applied Materials & Interfaces, Vol. 6, Issue 24
DOI: 10.1021/am506439x

Hydrogen permeance of palladium?copper alloy membranes over a wide range of temperatures and pressures
journal, October 2004

Howard, B.
Journal of Membrane Science, Vol. 241, Issue 2
DOI: 10.1016/j.memsci.2004.04.031

Pd and Pd–Cu membranes: inhibition of H permeation by HS
journal, June 2005

Kulprathipanja, A.; Alptekin, G.; Falconer, J.
Journal of Membrane Science, Vol. 254, Issue 1-2
DOI: 10.1016/j.memsci.2004.11.031

Density functional theory studies of sulfur binding on Pd, Cu and Ag and their alloys
journal, November 2003

Alfonso, D.
Surface Science, Vol. 546, Issue 1
DOI: 10.1016/j.susc.2003.08.053

Effect of H ₂ S on the Performance and Long-Term Stability of Pd/Cu Membranes
journal, April 2009

Pomerantz, Natalie; Ma, Yi Hua
Industrial & Engineering Chemistry Research, Vol. 48, Issue 8
DOI: 10.1021/ie801947a

The effect of H2S on the performance of Pd and Pd/Au composite membrane
journal, October 2010

Chen, Chao-Huang; Ma, Yi Hua
Journal of Membrane Science, Vol. 362, Issue 1-2
DOI: 10.1016/j.memsci.2010.07.002

Sulfur resistant Pd and Pd alloy membranes by phosphidation
journal, April 2014

Khatib, Sheima J.; Yun, Samhun; Oyama, S. Ted
Journal of Membrane Science, Vol. 455
DOI: 10.1016/j.memsci.2013.12.074

Devlopment of palladium/ceramic membranes for hydrogen separation
journal, April 2011

David, E.; Kopac, J.
International Journal of Hydrogen Energy, Vol. 36, Issue 7
DOI: 10.1016/j.ijhydene.2010.12.032

Ultrathin palladium membranes prepared by a novel electric field assisted activation
journal, March 2011

Yun, Samhun; Ko, Joon Ho; Oyama, S. Ted
Journal of Membrane Science, Vol. 369, Issue 1-2
DOI: 10.1016/j.memsci.2010.12.015

Catalytic palladium-based membrane reactors: A review
journal, October 1991

Shu, J.; Grandjean, B. P. A.; Neste, A. Van
The Canadian Journal of Chemical Engineering, Vol. 69, Issue 5
DOI: 10.1002/cjce.5450690503

Hydrogen transport in composite inorganic membranes
journal, April 2008

Gabitto, Jorge; Tsouris, Costas
Journal of Membrane Science, Vol. 312, Issue 1-2
DOI: 10.1016/j.memsci.2007.12.061

Model of hydrogen permeation behavior in palladium membranes
journal, February 1999

Ward, Timothy L.; Dao, Tien
Journal of Membrane Science, Vol. 153, Issue 2
DOI: 10.1016/s0376-7388(98)00256-7

The influence of hydrogen sulfide-to-hydrogen partial pressure ratio on the sulfidization of Pd and 70mol% Pd–Cu membranes
journal, November 2007

Iyoha, Osemwengie; Enick, Robert; Killmeyer, Richard
Journal of Membrane Science, Vol. 305, Issue 1-2
DOI: 10.1016/j.memsci.2007.07.032

Adsorption and decomposition of H2S on Pd(111) surface: a first-principles study
journal, January 2005

Alfonso, Dominic R.; Cugini, Anthony V.; Sorescu, Dan C.
Catalysis Today, Vol. 99, Issue 3-4
DOI: 10.1016/j.cattod.2004.10.006

Model experiments on the poisoning of Pt catalysts by sulfur
journal, June 1978

Fischer, T.
Journal of Catalysis, Vol. 53, Issue 1
DOI: 10.1016/0021-9517(78)90004-0

Chemisorption of hydrogen sulfide on a supported nickel catalyst
journal, July 1968

Rostrupnielsen, J.
Journal of Catalysis, Vol. 11, Issue 3
DOI: 10.1016/0021-9517(68)90035-3

Chemisorption of hydrogen sulfide on nickel and ruthenium catalysts I. Desorption isotherms
journal, February 1978

Oliphant, J.
Journal of Catalysis, Vol. 51, Issue 2
DOI: 10.1016/0021-9517(78)90297-x

Hydrogen on Pd(100)-S: the effect of sulfur on precursor mediated adsorption and desorption
journal, November 1990

Burke, M. L.; Madix, R. J.
Surface Science, Vol. 237, Issue 1-3
DOI: 10.1016/0039-6028(90)90515-a

Surface structures of S on Pd(111)
journal, October 1999

Speller, S.; Rauch, T.; Bömermann, J.
Surface Science, Vol. 441, Issue 1
DOI: 10.1016/s0039-6028(99)00808-0

Local structure and dynamics of a segregated c (2×2) sulfur layer on Pd(001) studied by scanning tunneling microscopy
journal, April 1993

Bürgler, D.; Tarrach, G.; Schaub, T.
Physical Review B, Vol. 47, Issue 15
DOI: 10.1103/physrevb.47.9963

Phase relationships and thermodynamic properties of the Pd-S system
journal, December 1985

Taylor, Jeffrey R.
Metallurgical Transactions B, Vol. 16, Issue 1
DOI: 10.1007/bf02657499

Equilibria in the PdS–H ₂ –Pd ₄ S–H ₂ S and Pd ₄ S–H ₂ –Pd–H ₂ S Systems
journal, September 1962

Niwa, Kichizo; Yokokawa, Toshio; Isoya, Toshiro
Bulletin of the Chemical Society of Japan, Vol. 35, Issue 9
DOI: 10.1246/bcsj.35.1543

Poisoning of Pd(100) for the dissociation of H2: a theoretical study of co-adsorption of hydrogen and sulphur
journal, May 1995

Wilke, Steffen; Scheffler, Matthias
Surface Science, Vol. 329, Issue 1-2
DOI: 10.1016/0039-6028(95)00355-x

Auger electron spectroscopy investigations of segregation in AuPd and AgPd alloy thin films
journal, April 1993

Anton, R.; Eggers, H.; Veletas, J.
Thin Solid Films, Vol. 226, Issue 1
DOI: 10.1016/0040-6090(93)90203-2

Mechanism of the Poisoning Action Of Sulfur on Catalytically Active Pd(100)
text, January 2001

Rutkowski, M.; Wetzig, D.; Zacharias, H.
The American Physical Society
DOI: 10.17877/de290r-4623

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Similar Records

Title: Modeling Sulfur Poisoning of Palladium Membranes Used for Hydrogen Separation

Abstract

Citation Formats

Modern and prospective technologies for hydrogen production from fossil fuels journal, January 1989

Modular Chemical Process Intensification: A Review journal, June 2017

Effect of hydrogen-sulfide on the hydrogen permeance of palladium?copper alloys at elevated temperatures journal, October 2004

Sulfur tolerance of zeolite beta-supported Pd−Pt catalysts for the isomerization of n-hexane journal, July 1998

Experimental and Computational Prediction of the Hydrogen Transport Properties of Pd 4 S journal, September 2007

Separation of hydrogen from gas mixtures using supported platinum-group metal membranes journal, March 2001

Hydrogen permeation through surface modified Pd and PdAg membranes journal, October 2001

The performance of Pd–Ag alloy membrane films under exposure to trace amounts of H2S journal, February 2016

Pd-Based Membranes for Hydrogen Separation: Review of Alloying Elements and Their Influence on Membrane Properties journal, July 2016

Bildung von Mischkristallen durch Ber�hrung fester Phasen journal, September 1921

Structural and Permeation Kinetic Correlations in PdCuAg Membranes journal, December 2014

Hydrogen permeance of palladium?copper alloy membranes over a wide range of temperatures and pressures journal, October 2004

Pd and Pd–Cu membranes: inhibition of H permeation by HS journal, June 2005

Density functional theory studies of sulfur binding on Pd, Cu and Ag and their alloys journal, November 2003

Effect of H 2 S on the Performance and Long-Term Stability of Pd/Cu Membranes journal, April 2009

The effect of H2S on the performance of Pd and Pd/Au composite membrane journal, October 2010

Sulfur resistant Pd and Pd alloy membranes by phosphidation journal, April 2014

Devlopment of palladium/ceramic membranes for hydrogen separation journal, April 2011

Ultrathin palladium membranes prepared by a novel electric field assisted activation journal, March 2011

Catalytic palladium-based membrane reactors: A review journal, October 1991

Hydrogen transport in composite inorganic membranes journal, April 2008

Model of hydrogen permeation behavior in palladium membranes journal, February 1999

The influence of hydrogen sulfide-to-hydrogen partial pressure ratio on the sulfidization of Pd and 70mol% Pd–Cu membranes journal, November 2007

Adsorption and decomposition of H2S on Pd(111) surface: a first-principles study journal, January 2005

Model experiments on the poisoning of Pt catalysts by sulfur journal, June 1978

Chemisorption of hydrogen sulfide on a supported nickel catalyst journal, July 1968

Chemisorption of hydrogen sulfide on nickel and ruthenium catalysts I. Desorption isotherms journal, February 1978

Hydrogen on Pd(100)-S: the effect of sulfur on precursor mediated adsorption and desorption journal, November 1990

Surface structures of S on Pd(111) journal, October 1999

Local structure and dynamics of a segregated c (2×2) sulfur layer on Pd(001) studied by scanning tunneling microscopy journal, April 1993

Phase relationships and thermodynamic properties of the Pd-S system journal, December 1985

Equilibria in the PdS–H 2 –Pd 4 S–H 2 S and Pd 4 S–H 2 –Pd–H 2 S Systems journal, September 1962

Poisoning of Pd(100) for the dissociation of H2: a theoretical study of co-adsorption of hydrogen and sulphur journal, May 1995

Auger electron spectroscopy investigations of segregation in AuPd and AgPd alloy thin films journal, April 1993

Mechanism of the Poisoning Action Of Sulfur on Catalytically Active Pd(100) text, January 2001

Modern and prospective technologies for hydrogen production from fossil fuels
journal, January 1989

Modular Chemical Process Intensification: A Review
journal, June 2017

Effect of hydrogen-sulfide on the hydrogen permeance of palladium?copper alloys at elevated temperatures
journal, October 2004

Sulfur tolerance of zeolite beta-supported Pd−Pt catalysts for the isomerization of n-hexane
journal, July 1998

Experimental and Computational Prediction of the Hydrogen Transport Properties of Pd ₄ S
journal, September 2007

Separation of hydrogen from gas mixtures using supported platinum-group metal membranes
journal, March 2001

Hydrogen permeation through surface modified Pd and PdAg membranes
journal, October 2001

The performance of Pd–Ag alloy membrane films under exposure to trace amounts of H2S
journal, February 2016

Pd-Based Membranes for Hydrogen Separation: Review of Alloying Elements and Their Influence on Membrane Properties
journal, July 2016

Bildung von Mischkristallen durch Ber�hrung fester Phasen
journal, September 1921

Structural and Permeation Kinetic Correlations in PdCuAg Membranes
journal, December 2014

Hydrogen permeance of palladium?copper alloy membranes over a wide range of temperatures and pressures
journal, October 2004

Pd and Pd–Cu membranes: inhibition of H permeation by HS
journal, June 2005

Density functional theory studies of sulfur binding on Pd, Cu and Ag and their alloys
journal, November 2003

Effect of H ₂ S on the Performance and Long-Term Stability of Pd/Cu Membranes
journal, April 2009

The effect of H2S on the performance of Pd and Pd/Au composite membrane
journal, October 2010

Sulfur resistant Pd and Pd alloy membranes by phosphidation
journal, April 2014

Devlopment of palladium/ceramic membranes for hydrogen separation
journal, April 2011

Ultrathin palladium membranes prepared by a novel electric field assisted activation
journal, March 2011

Catalytic palladium-based membrane reactors: A review
journal, October 1991

Hydrogen transport in composite inorganic membranes
journal, April 2008

Model of hydrogen permeation behavior in palladium membranes
journal, February 1999

The influence of hydrogen sulfide-to-hydrogen partial pressure ratio on the sulfidization of Pd and 70mol% Pd–Cu membranes
journal, November 2007

Adsorption and decomposition of H2S on Pd(111) surface: a first-principles study
journal, January 2005

Model experiments on the poisoning of Pt catalysts by sulfur
journal, June 1978

Chemisorption of hydrogen sulfide on a supported nickel catalyst
journal, July 1968

Chemisorption of hydrogen sulfide on nickel and ruthenium catalysts I. Desorption isotherms
journal, February 1978

Hydrogen on Pd(100)-S: the effect of sulfur on precursor mediated adsorption and desorption
journal, November 1990

Surface structures of S on Pd(111)
journal, October 1999

Local structure and dynamics of a segregated c (2×2) sulfur layer on Pd(001) studied by scanning tunneling microscopy
journal, April 1993

Phase relationships and thermodynamic properties of the Pd-S system
journal, December 1985

Equilibria in the PdS–H ₂ –Pd ₄ S–H ₂ S and Pd ₄ S–H ₂ –Pd–H ₂ S Systems
journal, September 1962

Poisoning of Pd(100) for the dissociation of H2: a theoretical study of co-adsorption of hydrogen and sulphur
journal, May 1995

Auger electron spectroscopy investigations of segregation in AuPd and AgPd alloy thin films
journal, April 1993

Mechanism of the Poisoning Action Of Sulfur on Catalytically Active Pd(100)
text, January 2001