dc.contributor.advisor | Chaudhari, Raghunath V | |
dc.contributor.author | Li, Yuanchun | |
dc.date.accessioned | 2010-12-31T04:27:43Z | |
dc.date.available | 2010-12-31T04:27:43Z | |
dc.date.issued | 2010-07-15 | |
dc.date.submitted | 2010 | |
dc.identifier.other | http://dissertations.umi.com/ku:11061 | |
dc.identifier.uri | http://hdl.handle.net/1808/6959 | |
dc.description.abstract | Carbonylation of aryl olefins and alcohols using homogeneous Pd catalysts has gained considerable interest due to their important applications in the synthesis the non-steroidal anti-inflammatory drugs consisting of 2-arylpropionic acids (e.g. Ibuprofen®, Naproxen®). In this work, different homogeneous palladium catalysts were compared for their performances in the hydrocarboxylation of styrene to identify the best performing catalyst system using Pd(pyca)(PPh3)(OTs) as a precursor, which shows above 99% regio-selectivity to 2-phenylpropionic acid as well as high activity. Therefore, this work mainly investigated the kinetics of hydrocarboxylation of styrene using Pd(pyca)(PPh3)(OTs)/PPh3/TsOH/LiCl catalyst system. Particularly, parametric study was carried out to understand the effects of different reaction parameters on the rate of hydrocarboxylation in a batch reactor as well as the concentration-time profiles. For interpretation of the reaction kinetics, a molecular level description of the reaction mechanism (catalytic cycle) was proposed to explain the unique observation of induction period at lower pressures of CO. The experimental concentration-time data for styrene, water and acid products were used to simulate the intrinsic rate parameters using an optimization program. The proposed reaction mechanism based on a Pd-hydride complex as an intermediate active species well explains the experimental data at different temperatures. The approach of micro-kinetic modeling does not require assumption of a rate determining step and provides good description of the complex trends with respect to reaction and catalyst parameters over a wide range of conditions. The approach is also useful to discriminate different reaction mechanisms and obtain intrinsic kinetic parameters for design and scale-up of reactors. | |
dc.format.extent | 123 pages | |
dc.language.iso | EN | |
dc.publisher | University of Kansas | |
dc.rights | This item is protected by copyright and unless otherwise specified the copyright of this thesis/dissertation is held by the author. | |
dc.subject | Chemical engineering | |
dc.title | Studies in hydrocarboxylation of styrene and derivatives using palladium complex catalysts | |
dc.type | Thesis | |
dc.contributor.cmtemember | Subramaniam, Bala | |
dc.contributor.cmtemember | Busch, Daryle | |
dc.thesis.degreeDiscipline | Chemical & Petroleum Engineering | |
dc.thesis.degreeLevel | M.F.A. | |
kusw.oastatus | na | |
kusw.oapolicy | This item does not meet KU Open Access policy criteria. | |
dc.rights.accessrights | openAccess | |