Pd–Pt/YSZ composite membranes for hydrogen separation from synthetic water–gas shift streams

Abstract Palladium–platinum (Pd–Pt) alloy membranes have been fabricated by sequential, electroless deposition onto porous yttria-stablized zirconia supports manufactured by Praxair, Inc. Membranes were synthesized with thicknesses of 4–12 μm that contained up to 27 wt% Pt. Pd–Pt alloy membranes had lower pure-gas hydrogen flux compared with pure Pd membranes of equal thickness. However, when tested at 673 K under an identical synthetic water–gas shift feed gas mixture composed of H 2 , H 2 O, CO 2 , and CO at 689.5 kPa total pressure, the Pd–Pt alloy membranes had over 25% higher hydrogen fluxes than a pure Pd membrane of similar thickness. Membrane films were analyzed after testing with SEM, EDS, and ICP-AES to corroborate membrane thickness and alloy compositions estimated by mass gain. SEM thickness estimates on membrane cross sections were similar to those estimated by mass gain. ICP-AES analysis was performed on two membranes and confirmed the composition estimated by gravimetric analysis. In five of six membranes the film composition estimated by gravimetric analysis was consistent with the surface composition estimated by EDS which indicated that the membranes had been adequately annealed.

[1]  Eiichi Kikuchi,et al.  Membrane reactor application to hydrogen production , 2000 .

[2]  J. Way,et al.  High flux palladium–copper composite membranes for hydrogen separations , 2006 .

[3]  P. Steinmetz,et al.  Electroless deposition of pure nickel, palladium and platinum , 1990 .

[4]  B. Morreale,et al.  The permeability of hydrogen in bulk palladium at elevated temperatures and pressures , 2003 .

[5]  J. Falconer,et al.  Effects of Water Gas Shift Gases on Pd−Cu Alloy Membrane Surface Morphology and Separation Properties , 2004 .

[6]  Bernard P. A. Grandjean,et al.  Simultaneous deposition of Pd and Ag on porous stainless steel by electroless plating , 1993 .

[7]  T. Kojima,et al.  Hydrogen permeation properties through composite membranes of platinum supported on porous alumina , 2000 .

[8]  J. N. Armor,et al.  Catalysis and the hydrogen economy , 2005 .

[9]  J. Way,et al.  Physical characterization of 0.5 μm cut-off sintered stainless steel membranes , 2003 .

[10]  J. Way,et al.  Effects of heat treatment in air on hydrogen sorption over Pd–Ag and Pd–Au membrane surfaces , 2012 .

[11]  D. Jansen,et al.  Towards full-scale demonstration of hydrogen-selective membranes for CO2 capture: Inhibition effect of WGS-components on the H2 permeation through three Pd membranes of 44 cm long , 2010 .

[12]  G. Capannelli,et al.  Evaluation of the water gas shift reaction in a palladium membrane reactor , 2010 .

[13]  Jianli Hu,et al.  An overview of hydrogen production technologies , 2009 .

[14]  A. F. Sammells,et al.  Dense inorganic membranes for production of hydrogen from methane and coal with carbon dioxide sequestration , 2006 .

[15]  F. A. Lewis,et al.  The Palladium-Hydrogen System , 1967, Platinum Metals Review.

[16]  S. Ted Oyama,et al.  Correlations in palladium membranes for hydrogen separation: A review , 2011 .

[17]  A. B. Zakharov,et al.  Alloys of palladium with metals of the platinum group as hydrogen-permeable membrane components at high temperatures of gas separation , 1993 .

[18]  H. Yoshida,et al.  Metallurgical Considerations on Pd, Pd-Alloy and Their Metal-Hydrogen Systems , 1985 .

[19]  Robert M. Enick,et al.  Hydrogen permeance of palladium–copper alloy membranes over a wide range of temperatures and pressures , 2004 .

[20]  E. A. Payzant,et al.  The effects of fabrication and annealing on the structure and hydrogen permeation of Pd-Au binary alloy membranes , 2009 .

[21]  A. Varma,et al.  Palladium composite membranes by electroless plating technique: Relationships between plating kinetics, film microstructure and membrane performance , 1999 .

[22]  R. Cortès,et al.  Pd–Pt alloys: correlation between electronic structure and hydrogenation properties , 2001 .

[23]  B. Baranowski Stress-induced diffusion in hydrogen permeation through Pd81Pt19 membranes , 1989 .

[24]  Y. Cheng,et al.  Effects of electroless plating chemistry on the synthesis of palladium membranes , 2001 .

[25]  Saurabh Chaudhari,et al.  Sulfur tolerant PdAu and PdAuPt alloy hydrogen separation membranes , 2012 .

[26]  J. Way,et al.  Palladium–ruthenium membranes for hydrogen separation fabricated by electroless co-deposition , 2009 .

[27]  J. Way,et al.  INNOVATIONS IN PALLADIUM MEMBRANE RESEARCH , 2002 .

[28]  M. Yoshihara,et al.  The diffusivity of hydrogen through Pd-based solid solutions containing rhodium and platinum , 1986 .

[29]  Muhammad Sahimi,et al.  Hydrogen production from coal-derived syngas using a catalytic membrane reactor based process , 2010 .

[30]  Thijs Peters,et al.  High pressure performance of thin Pd–23%Ag/stainless steel composite membranes in water gas shift gas mixtures; influence of dilution, mass transfer and surface effects on the hydrogen flux , 2008 .

[31]  John P. Collins,et al.  Catalytic decomposition of ammonia in a membrane reactor , 1994 .

[32]  Y. Mi,et al.  Theoretical study on concentration polarization in gas separation membrane processes , 1999 .

[33]  J. Way,et al.  Unsupported palladium alloy foil membranes fabricated by electroless plating , 2008 .

[34]  W. A. Pledger,et al.  Catalytic platinum-based membrane reactor for removal of H2S from natural gas streams , 1994 .

[35]  K. Y. Foo,et al.  A New Preparation Technique for Pd/Alumina Membranes with Enhanced High-Temperature Stability , 1999 .

[36]  E. Kikuchi,et al.  Preparation of supported thin palladium-silver alloy membranes and their characteristics for hydrogen separation , 1991 .

[37]  Shigeyuki Uemiya,et al.  Brief Review of Steam Reforming Using a Metal Membrane Reactor , 2004 .

[38]  Fernando Roa,et al.  The effect of air exposure on palladium–copper composite membranes , 2005 .

[39]  J. Way,et al.  Palladium–gold membranes in mixed gas streams with hydrogen sulfide: Effect of alloy content and fabrication technique , 2011 .

[40]  T. Flanagan,et al.  Enhanced rates of hydrogen absorption resulting from oxidation of Pd or internal oxidation of Pd-Al alloys , 2000 .

[41]  Sushil Adhikari,et al.  Hydrogen Membrane Separation Techniques , 2006 .

[42]  Y. Ma,et al.  Pd–Ag membrane synthesis: The electroless and electro-plating conditions and their effect on the deposits morphology , 2009 .

[43]  Arun C. Bose,et al.  Inorganic Membranes for Energy and Environmental Applications , 2009 .

[44]  Hengyong Xu,et al.  On alloying and low-temperature stability of thin, supported PdAg membranes , 2012 .

[45]  R. Bredesen,et al.  Hydrogen permeation of thin, free-standing Pd/Ag23% membranes before and after heat treatment in air , 2008 .

[46]  Hengyong Xu,et al.  Experimental and simulation studies on concentration polarization in H2 enrichment by highly permeable and selective Pd membranes , 2006 .

[47]  John P. Collins,et al.  Catalytic Dehydrogenation of Propane in Hydrogen Permselective Membrane Reactors , 1996 .

[48]  T. Kojima,et al.  Stability and hydrogen permeation behavior of supported platinum membranes in presence of hydrogen sulfide , 1999 .

[49]  John L. Falconer,et al.  Pd and Pd–Cu membranes: inhibition of H2 permeation by H2S , 2005 .

[50]  J. Wilcox,et al.  Achieving optimum hydrogen permeability in PdAg and PdAu alloys. , 2006, The Journal of chemical physics.

[51]  B. Morreale,et al.  Effect of H2S on performance of Pd4Pt alloy membranes , 2008 .