Sulfur Tolerant Pd/Cu and Pd/Au Alloy Membranes for H2 Separation with High Pressure CO2 for Sequestration

摘要

The effect of H{sub 2}S poisoning on Pd, Pd/Cu, and Pd/Au alloy composite membranes prepared by the electroless deposition method on porous Inconel supports was investigated to provide a fundamental understanding of the durability and preparation of sulfur tolerant membranes. X-ray photoelectron spectroscopy (XPS) studies showed that the exposure of pure Pd to 50 ppm H{sub 2}S/H{sub 2} mixtures caused bulk sulfide formation at lower temperatures and surface sulfide formation at higher temperatures. Lower temperatures, longer exposure times, and higher H{sub 2}S concentrations resulted in a higher degree of sulfidation. In a Pd membrane, the bulk sulfide formation caused a drastic irrecoverable H{sub 2} permeance decline and an irreparable loss in selectivity. Pd/Cu and Pd/Au alloy membranes exhibited permeance declines due to surface sulfide formation upon exposure to 50 ppm H{sub 2}S/H{sub 2} gas mixtures. However in contrast to the pure Pd membrane, the permeances of the Pd/Cu and Pd/Au alloy membranes were mostly recovered in pure H{sub 2} and the selectivity of the Pd alloy layers remained essentially intact throughout the characterization in H{sub 2}, He and H{sub 2}S/H{sub 2} mixtures which lasted several thousand hours. The amount of irreversible sulfur poisoning decreased with increasing temperature due to the exothermicity of H{sub 2}S adsorption. Longer exposure times increased the amount of irreversible poisoning of the Pd/Cu membrane but not the Pd/Au membrane. Pd/Au coupon studies of the galvanic displacement method showed that higher Au{sup 3+} concentrations, lower pH values, higher bath temperatures and stirring the bath at a rate of 200 rpm yielded faster displacement rates, more uniform depositions, and a higher Au content within the layers. While 400 C was found to be sufficient to form a Pd/Au alloy on the surface, high temperature X-ray diffraction (HTXRD) studies showed that even after annealing between 500-600 C, the Pd/Cu alloys could have part or all of the surface in the less sulfur resistant {beta} phase.