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Title: Palladium/Copper Alloy Composite Membranes for High Temperature Hydrogen Separation

Abstract

This report summarizes progress made during the a three year University Coal Research grant (DEFG26-03NT41792) at the Colorado School of Mines. The period of performance was September 1, 2003 through August of 2006. We made excellent progress toward our goal of contributing to the development of high productivity, sulfur tolerant composite metal membranes for hydrogen production and membrane reactors. Composite Pd and Pd alloy metal membranes with thin metal films (1-7 {micro}m) were prepared on porous stainless steel and ceramic supports that meet or exceed the DOE 2010 and 2015 pure hydrogen flux targets at differential pressure of only 20 psi. For example, a 2 {micro}m pure Pd membrane on a Pall AccuSep{reg_sign} substrate achieved an ideal H{sub 2}/N{sub 2} separation factor of over 6000, with a pure hydrogen flux of 210 SCFH/ft{sup 2} at only 20 psig feed pressure. Similar performance was achieved with a Pd{sub 80}Au{sub 20} composite membrane on a similar stainless steel substrate. Extrapolating the pure hydrogen flux of this PdAu membrane to the DOE Fossil Energy target conditions of 150 psia feed pressure and 50 psia permeate pressure gives a value of 508 SCFH/ft{sup 2}, exceeding the 2015 target. At these thicknesses, it is themore » support cost that will dominate the cost of a large scale module. In a direct comparison of FCC phase PdCu and PdAu alloys on identical supports, we showed that a Pd{sub 85}Au{sub 15} (mass %) alloy membrane is not inhibited by CO, CO{sub 2}, or steam present in a water-gas shift feed mixture at 400 C, has better resistance to sulfur than a Pd{sub 94}Cu{sub 6} membrane, and has over twice the hydrogen permeance.« less

Authors:
;
Publication Date:
Research Org.:
Trustees Of The Colorado School Of Mines
Sponsoring Org.:
USDOE
OSTI Identifier:
898816
DOE Contract Number:
FG26-03NT41792
Resource Type:
Technical Report
Country of Publication:
United States
Language:
English
Subject:
08 HYDROGEN; 36 MATERIALS SCIENCE; ALLOYS; HYDROGEN; HYDROGEN PRODUCTION; MEMBRANES; STAINLESS STEELS

Citation Formats

J. Douglas Way, and Paul M. Thoen. Palladium/Copper Alloy Composite Membranes for High Temperature Hydrogen Separation. United States: N. p., 2006. Web. doi:10.2172/898816.
J. Douglas Way, & Paul M. Thoen. Palladium/Copper Alloy Composite Membranes for High Temperature Hydrogen Separation. United States. doi:10.2172/898816.
J. Douglas Way, and Paul M. Thoen. Thu . "Palladium/Copper Alloy Composite Membranes for High Temperature Hydrogen Separation". United States. doi:10.2172/898816. https://www.osti.gov/servlets/purl/898816.
@article{osti_898816,
title = {Palladium/Copper Alloy Composite Membranes for High Temperature Hydrogen Separation},
author = {J. Douglas Way and Paul M. Thoen},
abstractNote = {This report summarizes progress made during the a three year University Coal Research grant (DEFG26-03NT41792) at the Colorado School of Mines. The period of performance was September 1, 2003 through August of 2006. We made excellent progress toward our goal of contributing to the development of high productivity, sulfur tolerant composite metal membranes for hydrogen production and membrane reactors. Composite Pd and Pd alloy metal membranes with thin metal films (1-7 {micro}m) were prepared on porous stainless steel and ceramic supports that meet or exceed the DOE 2010 and 2015 pure hydrogen flux targets at differential pressure of only 20 psi. For example, a 2 {micro}m pure Pd membrane on a Pall AccuSep{reg_sign} substrate achieved an ideal H{sub 2}/N{sub 2} separation factor of over 6000, with a pure hydrogen flux of 210 SCFH/ft{sup 2} at only 20 psig feed pressure. Similar performance was achieved with a Pd{sub 80}Au{sub 20} composite membrane on a similar stainless steel substrate. Extrapolating the pure hydrogen flux of this PdAu membrane to the DOE Fossil Energy target conditions of 150 psia feed pressure and 50 psia permeate pressure gives a value of 508 SCFH/ft{sup 2}, exceeding the 2015 target. At these thicknesses, it is the support cost that will dominate the cost of a large scale module. In a direct comparison of FCC phase PdCu and PdAu alloys on identical supports, we showed that a Pd{sub 85}Au{sub 15} (mass %) alloy membrane is not inhibited by CO, CO{sub 2}, or steam present in a water-gas shift feed mixture at 400 C, has better resistance to sulfur than a Pd{sub 94}Cu{sub 6} membrane, and has over twice the hydrogen permeance.},
doi = {10.2172/898816},
journal = {},
number = ,
volume = ,
place = {United States},
year = {Thu Aug 31 00:00:00 EDT 2006},
month = {Thu Aug 31 00:00:00 EDT 2006}
}

Technical Report:

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  • Recent advances have shown that Pd-Cu composite membranes are not susceptible to the mechanical, embrittlement, and poisoning problems that have prevented widespread industrial use of Pd for high temperature H2 separation. These membranes consist of a thin ({approx}1 mm) film of metal deposited on the inner surface of a porous metal or ceramic tube. Based on preliminary results, thin Pd{sub 60}Cu{sub 40} films are expected to exhibit hydrogen flux up to ten times larger than commercial polymer membranes for H2 separation, and resist poisoning by H{sub 2}S and other sulfur compounds typical of coal gas. Similar Pd-membranes have been operatedmore » at temperatures as high as 750 C. The overall objective of the proposed project is to demonstrate the feasibility of using sequential electroless plating to fabricate Pd{sub 60}Cu{sub 4}0 alloy membranes on porous supports for H{sub 2} separation. These following advantages of these membranes for processing of coal-derived gas will be demonstrated: High H{sub 2} flux; Sulfur tolerant, even at very high total sulfur levels (1000 ppm); Operation at temperatures well above 500 C; and Resistance to embrittlement and degradation by thermal cycling. The proposed research plan is designed to providing a fundamental understanding of: Factors important in membrane fabrication; Optimization of membrane structure and composition; Effect of temperature, pressure, and gas composition on H{sub 2} flux and membrane selectivity; and How this membrane technology can be integrated in coal gasification-fuel cell systems.« less
  • Recent advances have shown that Pd-Cu composite membranes are not susceptible to the mechanical, embrittlement, and poisoning problems that have prevented widespread industrial use of Pd for high temperature H{sub 2} separation. These membranes consist of a thin ({approx}10 {micro}m) film of metal deposited on the inner surface of a porous metal or ceramic tube. Based on preliminary results, thin Pd{sub 60}Cu{sub 40} films are expected to exhibit hydrogen flux up to ten times larger than commercial polymer membranes for H{sub 2} separation, and resist poisoning by H{sub 2}S and other sulfur compounds typical of coal gas. Similar Pd-membranes havemore » been operated at temperatures as high as 750 C. The overall objective of the proposed project is to demonstrate the feasibility of using sequential electroless plating to fabricate Pd{sub 60}Cu{sub 40} alloy membranes on porous supports for H{sub 2} separation. These following advantages of these membranes for processing of coal-derived gas will be demonstrated: High H{sub 2} flux; Sulfur tolerant, even at very high total sulfur levels (1000 ppm); Operation at temperatures well above 500 C; and Resistance to embrittlement and degradation by thermal cycling. The proposed research plan is designed to providing a fundamental understanding of: Factors important in membrane fabrication; Optimization of membrane structure and composition; Effect of temperature, pressure, and gas composition on H{sub 2} flux and membrane selectivity; and How this membrane technology can be integrated in coal gasification-fuel cell systems.« less
  • For hydrogen from coal gasification to be used economically, processing approaches that produce a high purity gas must be developed. Palladium and its alloys, nickel, platinum and the metals in Groups 3 to 5 of the Periodic Table are all permeable to hydrogen. Hydrogen permeable metal membranes made of palladium and its alloys are the most widely studied due to their high hydrogen permeability, chemical compatibility with many hydrocarbon containing gas streams, and infinite hydrogen selectivity. Our Pd composite membranes have demonstrated stable operation at 450 C for over 70 days. Coal derived synthesis gas will contain up to 15000more » ppm H{sub 2}S as well as CO, CO{sub 2}, N{sub 2} and other gases. Highly selectivity membranes are necessary to reduce the H{sub 2}S concentration to acceptable levels for solid oxide and other fuel cell systems. Pure Pd-membranes are poisoned by sulfur, and suffer from mechanical problems caused by thermal cycling and hydrogen embrittlement. Recent advances have shown that Pd-Cu composite membranes are not susceptible to the mechanical, embrittlement, and poisoning problems that have prevented widespread industrial use of Pd for high temperature H{sub 2} separation. These membranes consist of a thin ({le} 5 {micro}m) film of metal deposited on the inner surface of a porous metal or ceramic tube. With support from this DOE Grant, we have fabricated thin, high flux Pd-Cu alloy composite membranes using a sequential electroless plating approach. Thin, Pd{sub 60}Cu{sub 40} films exhibit a hydrogen flux more than ten times larger than commercial polymer membranes for H{sub 2} separation, resist poisoning by H{sub 2}S and other sulfur compounds typical of coal gas, and exceed the DOE Fossil Energy target hydrogen flux of 80 ml/cm{sup 2} {center_dot} min = 0.6 mol/m{sup 2} {center_dot} s for a feed pressure of 40 psig. Similar Pd-membranes have been operated at temperatures as high as 750 C. We have developed practical electroless plating procedures for fabrication of thin Pd-Cu composite membranes at any scale.« less
  • This report summarizes progress made during the first year of research funding from DOE Grant No. DE-FG26-03NT41792 at the Colorado School of Mines. The period of performance was September 1, 2003 through August of 2004. Composite membranes, consisting of a thin Pd alloy film supported on a porous substrate have been investigated as a means of reducing the membrane cost and improving H{sub 2} flux. An electroless plating technique was utilized to deposit subsequent layers of palladium and copper over zirconia and alumina-based microfilters. The composite membranes thus made were annealed and tested at temperatures ranging from 250 to 500more » C, under very high feed pressures (up to 450 psig) using pure gases and gaseous mixtures containing H{sub 2}, CO, CO{sub 2}, H{sub 2}O and H{sub 2}S, with the purpose of determining the effects these variables had on the H{sub 2} permeation rate, selectivity and percent recovery. The inhibition caused by CO/CO{sub 2} gases on a 7 {micro}m thick Pd-Cu composite membrane was less than 17% over a wide range of compositions at 350 C. H{sub 2}S caused a strong inhibition of the H{sub 2} flux of the same Pd-Cu composite membrane, which is accentuated at levels of 100 ppm or higher. The membrane was exposed to 50 ppm three times without permanent damage. At higher H{sub 2}S levels, above 100 ppm the membrane suffered some physical degradation and its performances was severely affected. The use of sweep gases improved the hydrogen flux and recovery of a Pd-Cu composite membrane. Recently, we have been able to dramatically reduce the thickness of these Pd alloy membranes to approximately one micron. This is significant because at this thickness, it is the cost of the porous support that controls the materials cost of a composite Pd alloy membrane, not the palladium inventory. Very recent results show that the productivity of our membranes is very high, essentially meeting the DOE pure hydrogen flux target value set by the DOE Hydrogen Program. These results were obtained when a 1.3-micron-thick Pd{sub 95}Cu{sub 5} (composition given in mass %) alloy film was coated on a Pall Corporation Membralox{reg_sign} T1-70 tubular ceramic substrate. The flux of this membrane would be even higher if the alloy composition was 40 wt. % Cu.« less
  • This report summarizes progress made during the second year of research funding from DOE Grant DE-FG26-03NT41792 at the Colorado School of Mines. The period of performance was September 1, 2004 through August of 2005. We have reformulated our Pd plating process to minimize the presence of carbon contamination in our membranes. This has improved durability and increased permeability. We have developed techniques for plating the outside diameter of ceramic and metal substrate tubes. This configuration has numerous advantages including a 40% increase in specific surface area, the ability to assay the alloy composition non-destructively, the ability to potentially repair defectsmore » in the plated surface, and the ability to visually examine the plated surfaces. These improvements have allowed us to already meet the 2007 DOE Fossil Energy pure H{sub 2} flux target of 100 SCFH/ft{sup 2} for a hydrogen partial pressure difference of 100 psi with several Pd-Cu alloy membranes on ceramic microfilter supports. Our highest pure H{sub 2} flux on inexpensive, porous alumina support tubes at the DOE target conditions is 215 SCFH/ft{sup 2}. Progress toward meeting the other DOE Fossil Energy performance targets is also summarized. Additionally, we have adapted our membrane fabrication procedure to apply Pd and Pd alloy films to commercially available porous stainless steel substrates. Stable performance of Pd-Cu films on stainless steel substrates was demonstrated over a three week period at 400 C. Finally, we have fabricated and tested Pd-Au alloy membranes. These membranes also exceed both the 2007 and 2010 DOE pure H{sub 2} flux targets and exhibit ideal H{sub 2}/N{sub 2} selectivities of over 1000 at partial pressure difference of 100 psi.« less