Date of Award

12-14-2015

Document Type

Open Access Dissertation

Department

Chemical Engineering

First Advisor

John R. Monnier

Second Advisor

Christopher T. Williams

Abstract

Ethylene is the building block for many chemical intermediates in the petrochemical industry. The current worldwide ethylene production is over 150 million tons per year and demand increases by 3-5% annually. However, ethylene produced from steam cracking of light naptha contains up to 2% acetylene which acts as a poison for the downstream ethylene polymerization catalysts. Selective hydrogenation of acetylene in the ethylene stream using supported Pd catalysts is the industrially preferred method of lowering acetylene to acceptable ppm levels (< 5 ppm). Due to inferior selectivity at high acetylene conversion and the formation of “green oil”, or ethylene/acetylene oligomers, during reaction, small amounts of Group IB metals have been added to improve the performance of current generation catalysts. However, the bimetallic effects of the above additives have not been experimentally confirmed, possibly because the conventional methods of catalyst preparation result in both monometallic and bimetallic particles with varying compositions. This in turn makes it difficult to determine the position of the two metallic components, and bimetallic interactions typically occur only when the two metals form proximal contact instead of separate particles. In this study, a series of Ag- and Au-Pd/SiO2 bimetallic catalysts were prepared by electroless deposition (ED) with incremental and controlled coverages of Ag and Au on Pd. The selectivity of acetylene to ethylene and turnover frequencies of acetylene conversion were enhanced at high coverages of Ag and Au on Pd surfaces due to the transition of acetylene adsorption modes, which was further confirmed by the kinetics of acetylene hydrogenation. The similar performance trends for Ag- and Au-Pd/SiO2 suggest that the bimetallic effect for these catalysts was likely geometric and not electronic in nature. For comparison, a series of reverse Pd-Ag/SiO2 bimetallic catalysts where variable coverages of Pd were deposited onto Ag surfaces was prepared using galvanic displacement (GD) of Ago by Pd2+ to further explore the nature of bimetallic effects for selective acetylene hydrogenation. Unlike for the earlier case for Ag on Pd surfaces using ED, for samples prepared by GD there was considerably diffusion of Pd into the Ag lattice to give greater electronic interactions between these two metals, which limited selectivity of acetylene hydrogenation to form ethylene.

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