Publications

Biomass feedstocks contain roughly 15-30% lignin, a substance that can not be converted to fermentable sugars. Hence, most schemes for producing biofuels assume that the lignin coproduct will be utilized as boiler fuel. Yet, the chemical structure of lignin suggests that it will make an excellent high value fuel additive, if it can be broken down into smaller compounds. From Fiscal year 1997 through Fiscal year 2001, Sandia National Laboratories participated 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. SNL's primary role in the effort was to perform kinetic studies, examine the reaction chemistry, and to develop alternate BCD catalyst systems. This report summarizes the work performed at Sandia during Fiscal Year 1999 through Fiscal Year 2001 with aqueous systems. Work with alcohol based systems is summarized in part 1 of this report. Our study of lignin depolymerization by aqueous NaOH showed that the primary factor governing the extent of lignin conversion is the NaOH:lignin ratio. NaOH concentration is at best a secondary issue. The maximum lignin conversion is achieved at NaOH:lignin mole ratios of 1.5-2. This is consistent with acidic compounds in the depolymerized lignin neutralizing the base catalyst. The addition of CaO to NaOH improves the reaction kinetics, but not the degree of lignin conversion. The combination of Na{sub 2}CO{sub 3} and CaO offers a cost saving alternative to NaOH that performs identically to NaOH on a per Na basis. A process where CaO is regenerated from CaCO{sub 3} could offer further advantages, as could recovering the Na as Na{sub 2}CO{sub 3} or NaHCO{sub 3} by neutralization of the product solution with CO2. Model compound studies show that two types of reactions involving methoxy substituents on the aromatic ring occur: methyl group migration between phenolic groups (making and breaking ether bonds) and the loss of methyl/methoxy groups from the aromatic ring (destruction of ether linkages). The migration reactions are significantly faster than the demethylation reactions, but ultimately demethylation processes predominates.

Carbon is an important support for heterogeneous catalysts, such as platinum supported on activated carbon (AC). An important property of these catalysts is that they decompose upon heating in air. Consequently, Pt/AC catalysts can be used in applications requiring rapid decomposition of a material, leaving little residue. This report describes the catalytic effects of platinum on carbon decomposition in an attempt to maximize decomposition rates. Catalysts were prepared by impregnating the AC with two different Pt precursors, Pt(NH{sub 3}){sub 4}(NO{sub 3}){sub 2} and H{sub 2}PtCl{sub 6}. Some catalysts were treated in flowing N{sub 2} or H{sub 2} at elevated temperatures to decompose the Pt precursor. The catalysts were analyzed for weight loss in air at temperatures ranging from 375 to 450 C, using thermogravimetric analysis (TGA). The following results were obtained: (1) Pt/AC decomposes much faster than pure carbon; (2) treatment of the as-prepared 1% Pt/AC samples in N{sub 2} or H{sub 2} enhances decomposition; (3) autocatalytic behavior is observed for 1% Pt/AC samples at temperatures {ge} 425 C; (4) oxygen is needed for decomposition to occur. Overall, the Pt/AC catalyst with the highest activity was impregnated with H{sub 2}PtCl{sub 6} dissolved in acetone, and then treated in H{sub 2}. However, further research and development should produce a more active Pt/AC material.

Magnesium vanadates are potentially important catalytic materials for the conversion of alkanes to alkenes via oxidative dehydrogenation. However, little is known about the active sites at which the catalytic reactions take place. It may be possible to obtain a significant increase in the catalytic efficiency if the effects of certain material properties on the surface reactions could be quantified and optimized through the use of appropriate preparation techniques. Given that surface reactivity is often dependent upon surface structure and that the atomic level structure of the active sites in these catalysts is virtually unknown, we desire thin film samples consisting of a single magnesium vanadate phase and a well defined crystallographic orientation in order to reduce complexity and simplify the study of active sites. This report describes the use of reactive RF sputter deposition to fabricate very highly oriented, stoichiometric Mg{sub 3}(VO{sub 4}){sub 2} thin films, and subsequent studies of the reactivity of these films under reaction conditions typically found during oxidative dehydrogenation. We demonstrate that the synthesis methods employed do in fact result in stoichiometric films with the desired crystallographic orientation, and that the chemical behavior of the films closely approximates that of bulk, high surface area Mg{sub 3}(VO{sub 4}){sub 2} powders. We further use these films to demonstrate the effects of oxygen vacancies on chemical behavior, demonstrate that surface composition can vary significantly under reaction conditions, and obtain the first evidence for structure sensitivity in Mg{sub 3}(VO{sub 4}){sub 2} catalysts.