Ralph D. Gillespie

Solid base catalysts for mercaptan oxidation

Abstract Aqueous alkali can be completely replaced in the mercaptan oxidation reaction by incorporating solid basic materials into the catalyst formulation. The ability to use a solid oxide base to replace aqueous alkali will have a positive environmental impact because aqueous alkalis, such as caustic, are becoming a serious disposal problems for petroleum refiners and chemical manufacturers. The basic oxide system used contains cobalt phthalocyanine (CoPc) supported on a metal oxide solid solution (MOSS). Although active for mercaptan oxidation, this catalyst does not meet the lifetime requirements for commercial application. Three deactivation mechanisms have been identified: rehydration of the MOSS back to the layered double hydroxide (LDH) (because this rehydration causes a reduction in the basicity of these materials), deactivation by adsorption of heavy hydrocarbon species in the feed, and irreversible adsorption of acidic species from the feed. Knowledge of the deactivation mechanisms has allowed the design of a process that meets the required catalyst lifetime requirements. This process represents one of the first applications of solid base catalysis to a commercial process. Catalyst performance, factors affecting deactivation, and methods of preventing deactivation are discussed.

Strategies and applications of combinatorial methods and high throughput screening to the discovery of non-noble metal catalyst

Abstract The integrated End-to-End™ combinatorial process for catalyst preparation and screening, with emphasis on its capability to vary both process and compositional parameters will be demonstrated. Additionally, each step of the combinatorial screening process has been validated against results from traditional screening methods. The greatest challenge of all has been the adherence to the core concepts of the combinatorial approach. Catalyst libraries have been made and tested for naphthalene dehydrogenation chemistry. The preparation of these libraries has included the application of high throughput techniques for: 1. metal impregnation; 2. catalyst finishing; 3. catalyst screening. The catalyst screening system has been used to find a non-noble metal catalyst system that can replace Pt in dehydrogenation applications in the petroleum industry. A proprietary catalytic composition was developed for the dehydrogenation of methylcyclohexane (MCH) to toluene starting with four non-noble metals of different proportions and four different supports (alumina, titania, zirconia and silica) prepared in different ways and applying a statistical design of experiments. These data demonstrate that all steps of catalyst preparation and screening are performed in a rapid, useful, high throughput manner. Data will be presented from the catalyst screening efforts will demonstrate that optimized metal composition is dependent on the support type.

Scaling Up of Catalysts Discovered from Small-Scale Experiments

The chemical industry faces a challenging business climate due to difficult economic conditions in much of the world, strong international competition, and worldwide environmental concern. In addition, innovation in this industry has slowed as catalyst and process technology has matured. The need for a methodology that can increase catalyst innovation while continuing to decrease cycle times has been recognized by the Council for Chemical Research (Catalysis Roadmap, Vision 2020) [1]. In the 1980s, the pharmaceutical industry faced similar circumstances. Downward pressure on drug prices became incompatible with the high cost of drug discovery. Combinatorial chemistry, based on advances in laboratory automation, high-throughput synthesis, and activity screening, allowed the pharmaceutical companies to break the innovation impasse [2, 3].