Combined NMR and Theoretical Investigation of Alkylation Reactions on Solid Acids

EPA Grant Number: R826122
Title: Combined NMR and Theoretical Investigation of Alkylation Reactions on Solid Acids
Investigators: Haw, James F. , Nicholas, John B.
Institution: University of Southern California
EPA Project Officer: Karn, Barbara
Project Period: November 1, 1997 through October 31, 2000 (Extended to December 31, 2000)
Project Amount: $150,000
RFA: Technology for a Sustainable Environment (1997) RFA Text |  Recipients Lists
Research Category: Nanotechnology , Sustainability , Pollution Prevention/Sustainable Development


Public health concerns have motivated the reformulation of gasolines utilizing ever decreasing levels of aromatic hydrocarbons. The resulting deficit in octane rating is made up by allcylate (trimethylpentanes) which is produced using toxic hydrofluoric acid (HF) as the catalyst. HF units are potential hazards to public health, and their replacement by environmentally benign solid acid catalysts requires a significant amount of basic research. The central hypothesis motivating this project is that alkylation catalysis can be understood by the aggressive and skilled application of cutting-edge experimental and theoretical methods of chemical research. The principal investigators have used this approach to great success in other areas of solid acid chemistry. We feel that our approach will allow quick progress to be made in understanding the fundamental aspects of solid acid alkylation catalysts. A second, implicit hypothesis in this project is that a much better fundamental understanding of HF replacement catalysts will "catalyze" the replacement of HF units.

Environmental catalysis is an emerging research area that has so far emphasized NOx abatement from mobile emitters and the use of catalysis for the destruction of chlorinated organic wastes. The proposed research focuses on an important environmental problem, HF replacement in alkylation units, that is under represented in relation to other recent work in the broader area of environmental catalysis.


The approach used here to understand alkylation will embody our combined experimental-theoretical strategy that has proven to be successful for other problems. We will use solid state magic angle spinning nuclear magnetic resonance (NMR) techniques to characterize the three most promising HF -replacement catalysts, zeolite Beta, BF3/alumina and sulfonated zirconia. We will use in-situ NMR will be used to determine the nature of intermediates under true conditions of catalysis. Simultaneously, we will make extensive use of computational chemistry methods to verify experimental data, determine transition states, and predict how modification of the catalyst will effect the reaction mechanism.

Expected Results:

Should the regulations or economics of refining change with restrictions on the use or transport of HF, the need for replacement processes will be urgent. This EPA/NSF Technology for a Sustainable Environment project will use cutting edge experimental and theoretical methods to address many of the fundamental chemical problems that will arise where solid acid catalysts replace HF in alkylation units. We will establish the fundamental science base needed to support a sudden transition from HF to solid acid alkylation catalysts. Given the losses of research competence at essentially all US oil companies and many catalyst manufacturers. expertise housed in academic and federal laboratories may provide the best resource for basic science needed in the event of a rapid switch-over to a solid acid based alkylation technology. Even without the motivation of an environmental accident, HF units will certainly be phased out. and the petroleum industry might act sooner if there was greater confidence in replacement catalysts.

Publications and Presentations:

Publications have been submitted on this project: View all 15 publications for this project

Journal Articles:

Journal Articles have been submitted on this project: View all 5 journal articles for this project

Supplemental Keywords:

pollution prevention, green chemistry, waste minimization., RFA, Scientific Discipline, Sustainable Industry/Business, Sustainable Environment, Environmental Chemistry, Technology for Sustainable Environment, chlorinated organic wastes, nuclear magnetic resonance, waste reduction, solid-catalyzed reactions, catalysts, alkalides, alkylation reaction, reformulation of gasoline, aromatic hydrocarbons, innovative technology, environmentally benign catalysts, catalysis, pollution prevention, toxic reagents

Progress and Final Reports:

Final Report