… using in-situ kinetic and spectroscopic techniques.
Copper oxide is a widely used adsorptive material that removes trace amounts of H2S from various process streams via chemical reaction to form copper sulfide. At room temperature the thermodynamics favor a near complete conversion of CuO to copper sulfide in the presence of H2S. However, in application, the extent of conversion of the CuO to copper sulfide during reaction can be influenced by many factors, including the initial crystalline state of the CuO, and the rate at which solid products accumulate on the reactive surfaces or within pores of the CuO particles. This incomplete utilization of CuO is problematic for industrial applications because it typically leads to oversized equipment and/or frequent process shutdowns. Developing fundamental insight at the atomic scale for this reaction could overcome these limitations by providing a rational basis for the design of new materials and by leading to predictive models that allow for current materials to be operated toward their thermodynamic limits. Thus, experiments that combine reaction kinetic testing while also simultaneously capturing chemical and structural changes in the solid phase at multiple length scales are necessary to elucidate the fundamentals of these reactions at various length scales.
Previous studies were successful in semi-quantitatively relating properties of materials to performance in fixed-bed systems, however, differences in performance were often attributed to physical properties at the >10 mm scale (e.g., surface area, pore volume, bulk density). The effects of molecular scale material characteristics (e.g., microscopic shape, metal oxide crystallite size, and surface composition) were rarely investigated, thus, it is difficult to extend the conclusions from these studies across a broad range of conditions and materials.
Image (extract): (A) CuO and CuS concentration maps derived from XANES analysis of TXM images of individual CuO particle during reaction with 1000 ppm H2S. (B) Fractional conversion versus time (derived from linear combination fitting of Cu K-edge XANES) of fixed beds of CuO particles consisting of 2 different crystallite sizes (red circles are 2.8 nm and blue squares are 28 nm) and of individual CuO particles. See the entire figure here.