You are here:
GREEN CATALYZED OXIDATION OF HYDROCARBONS IN ALTERNATIVE SOLVENT SYSTEMS GENERATED BY PARIS II
Citation:
Gonzalez*, M A., T Becker**, AND P F. Harten*. GREEN CATALYZED OXIDATION OF HYDROCARBONS IN ALTERNATIVE SOLVENT SYSTEMS GENERATED BY PARIS II. Presented at AIChE, Indianapolis, IN, November 03 - 08, 2002.
Impact/Purpose:
To inform the public.
Description:
Green Catalyzed Oxidation of Hydrocarbons in Alternative Solvent Systems Generated by PARIS II
Michael A. Gonzalez*, Thomas M. Becker, and Paul F. Harten; Sustainable Technology Division, Office of Research and Development; United States Environmental Protection Agency, 26 West Martin Luther King Drive, Mail Stop 443, Cincinnati, OH 45268, USA
gonzalez.michael@epa.gov
The US EPA is in pursuit of green oxidation processes as a means of developing new, cost-effective, environmentally benign systems to produce desired products and eliminate/reduce unwanted by-products and wastes. One area of interest is the design of new catalysts for the oxidation of hydrocarbons that employ environmentally friendly oxidants such as H2O2 or molecular oxygen. We have successfully designed a series of new catalytic precursors, green oxidants, which assist in the oxidization of hydrocarbons in acetonitrile. One can further enhance the benign nature of this oxidation by exploring the use of alternative solvents.
Industrial solvents, whose continued use raises concern for worker health and toxins in the environment, need to be replaced in a cost-effective manner. PARIS II is a software tool created by the US EPA to address this need. The acronym, PARIS II, represents Program for Assisting the Replacement of Industrial Solvents, Version 2. This software tool identifies pure chemicals or designs mixtures that can serve as alternatives to more hazardous substances currently in use. The greener solvents formulated by PARIS II have improved environmental properties, but can perform as well as the solvents they were designed to replace.
Attempts to replace acetonitrile in the catalyzed oxidation of cyclohexane are ongoing. One sample solvent replacement system provided by PARIS II, is an 85% n-propyl formate, 10% 1,4-dioxane, and 5% propionic acid mixture. Although the total conversion of this difficult oxidation to cyclohexanol and cyclohexanone using hydrogen peroxide (8 hr, 100°C) is lower than that in acetonitrile, the selectivity distribution of the products remains comparable. Presumably, the low conversion is a result of a competition for partial oxidation of the solvent mixture rather than the substrate. Currently, other solvent systems proposed by PARIS II to replace acetonitrile, which are less likely to undergo solvent oxidation, are underway and results will be presented.