Lindsey R. Evans

Morphological families of self-assembled porphyrin structures and their photosensitization of hydrogen generation

Varying the solution growth conditions of cooperative binary ionic solids composed of anionic and cationic metalloporphyrins produces a series of families of self-assembled structures that efficiently and durably photosensitize the evolution of hydrogen.

The formation of active species for oxidative dehydrogenation of propane on magnesium molybdates

Pure and mixed magnesium molybdate phases (MoO3, MgMoO4, and MgMo2O7) have been examined for the oxidative dehydrogenation reaction of propane. The results are very sensitive to the stoichiometry and method of preparation. The catalysts exhibiting superior activity and selectivity are characterized by a unique temperature-programmed reduction peak that is not present for the poorly active or selective catalysts. Mixtures of MgMoO4 and MoO3 or MgMoO4 and MgMo2O7, materials that perform poorly by themselves, show significant improvements in performance upon heating. The solid-state interactions leading to these improvements correspond to the appearance of the characteristic reduction peak. The results suggest that the beneficial synergistic effects seen with mixtures of inactive phases are due to formation of a new phase or species, rather than remote communication between phases (e.g., oxygen spillover).

Materials development for the CR5 solar thermochemical heat engine.

The counter-rotating-ring receiver/reactor/recuperator (CR5) solar thermochemical heat engine is a new concept for production of hydrogen that allows for thermal recuperation between solids in an efficient counter-current arrangement. At the heart of the CR5 system are annular rings of a reactive solid ferrite that are thermally and chemically cycled to produce oxygen and hydrogen from water in separate and isolated steps. This design is very demanding from a materials point of view. The ferrite rings must maintain structural integrity and high reactivity after months of thermal cycling and exposure to temperatures in excess of 1100 °C. In addition, the design of the rings must have high geometric surface area for gas-solid contact and for adsorption of incident solar radiation. After performing a series of initial screenings, we chose Co0.67 Fe2.33 O4 as our baseline working material for a planned demonstration of CR5 and have begun additional characterization and development of this material. Our results to date with powders are consistent with the expectation that small particle sizes and the application of a support to inhibit ferrite sintering and enhance the chemistry are critical considerations for a practical operating device. Concurrent with the powder studies, we are using Robocasting, a Sandia-developed technique for free form processing of ceramics, to manufacture monolithic structures with complex three-dimensional geometries for chemical, physical, and mechanical evaluation. We have demonstrated that ferrite/zirconia mixtures can be fabricated into small three-dimensional monolithic lattice structures that give reproducible hydrogen yields over multiple cycles.Copyright

Batch Microreactor Studies of Lignin Depolymerization by Bases. 1. Alcohol Solvents

Biomass feedstocks contain roughly 10-30% lignin, a substance that can not be converted to fermentable sugars. Hence, most schemes for producing biofuels (ethanol) assume that the lignin coproduct will be utilized as boiler fuel to provide heat and power to the process. However, the chemical structure of lignin suggests that it will make an excellent high value fuel additive, if it can be broken down into smaller molecular units. From fiscal year 1997 through fiscal year 2001, Sandia National Laboratories was a participant in a cooperative effort with the National Renewable Energy Laboratory and the University of Utah to develop and scale a base catalyzed depolymerization (BCD) process for lignin conversion. SNLs primary role in the effort was to utilize rapidly heated batch microreactors to perform kinetic studies, examine the reaction chemistry, and to develop alternate catalyst systems for the BCD process. This report summarizes the work performed at Sandia during FY97 and FY98 with alcohol based systems. More recent work with aqueous based systems will be summarized in a second report.

Attrition-determining morphology changes on iron Fischer-Tropsch catalysts

Temperature programmed reduction and transmission electron microscopy were used to study the morphology changes of an iron Fischer-Tropsch catalyst during reaction, with an emphasis on potential attrition of the catalyst. In particular, the effect of potassium promotion was explored. Potassium appeared to minimize the formation of one type of carbide and, at low concentrations, limited graphitic carbon formation. At higher potassium levels (3%) graphitic carbon began to re-appear. Copper-promoted catalysts exposed to higher reaction temperatures (which is known to cause attrition) formed different carbides than those exposed to lower reaction temperatures. The potassium promoted catalysts investigated in this study did not produce the high temperature carbide present on catalysts that quickly attritted.

An Experimental Investigation of the Effect of Walls on Gas-Liquid Flows Through Fixed Particle Beds

The effect of particle diameter on downward co-current gas-liquid flow through a fixed bed of particles confined within a cylindrical column is investigated. Several hydrodynamic regimes that depend strongly on the properties of the gas stream, the liquid stream, and the packed particle bed are known to exist within these systems. This experimental study focuses on characterizing the effect of wall confinement on these hydrodynamic regimes as the diameter d of the spherical particles becomes comparable to the column diameter D (or D/d becomes order-unity). The packed bed consists of polished, solid, spherical, monodisperse particles (beads) with mean diameter in the range of 0.64–2.54 cm. These diameters yield D/d values between 15 and 3.75, so this range overlaps and extends the previously investigated range for two-phase flow. Measurements of the pressure drop across the bed and across the pulses are obtained for varying gas and liquid flow rates.Copyright

Advances in process intensification through multifunctional reactor engineering.

A multifunctional reactor is a chemical engineering device that exploits enhanced heat and mass transfer to promote production of a desired chemical, combining more than one unit operation in a single system. The main component of the reactor system under study here is a vertical column containing packing material through which liquid(s) and gas flow cocurrently downward. Under certain conditions, a range of hydrodynamic regimes can be achieved within the column that can either enhance or inhibit a desired chemical reaction. To study such reactors in a controlled laboratory environment, two experimental facilities were constructed at Sandia National Laboratories. One experiment, referred to as the Two-Phase Experiment, operates with two phases (air and water). The second experiment, referred to as the Three-Phase Experiment, operates with three phases (immiscible organic liquid and aqueous liquid, and nitrogen). This report describes the motivation, design, construction, operational hazards, and operation of the both of these experiments. Data and conclusions are included.

Preparation and Evaluation of Novel Hydrous Metal Oxide (HMO)-Supported Noble Metal Catalysts

Hydrous Metal Oxides (HMOs) are chemically synthesized materials that, because of their high cation exchange capacity, possess a unique ability to allow the preparation of highly dispersed supported-metal catalyst precursors with high metal loadings. This study evaluates high weight loading Rh/HMO catalysts with a wide range of HMO support compositions, including hydrous titanium oxide (HTO), silica-doped hydrous titanium oxide (HTO:Si), hydrous zirconium oxide (HZO), and silica-doped hydrous zirconium oxide (HZO:Si), against conventional oxide-supported Rh catalysts with similar weight loadings and support chemistries. Catalyst activity measurements for a structure-sensitive model reaction (n-butane hydrogenolysis) as a function of catalyst activation conditions show superior activity and stability for the ZrO{sub 2}, HZO, and HZO:Si supports, although all of the Rh/HMO catalysts have high ethane selectivity indicative of high Rh dispersion. For the TiO{sub 2}-, HTO-, and HTO:Si supported Rh catalysts, a significant loss of both catalyst activity and Rh dispersion is observed at more aggressive activation conditions, consistent with TiO{sub x} migration associated with SMSI phenomena. Of all the Rh/HMO catalysts, the Rh/HZO:Si catalysts appear to offer the best tradeoff in terms of high Rh dispersion, high activity, and high selectivity.