PALLADIUM/COPPER ALLOY COMPOSITE MEMBRANES FOR HIGH TEMPERATURE HYDROGEN SEPARATION

Abstract

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 500 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.