Year of Publication

2006

Document Type

Thesis

College

Engineering

Department

Chemical Engineering

First Advisor

Bhattacharyya

Second Advisor

Dibakar

Abstract

Zero-valent metals such as bulk iron and zinc are known to dechlorinate toxicorganic compounds. Enhancement in reaction rates has been achieved through bimetallicnanosized particles such as nickel/iron (Ni/Fe) and palladium/iron (Pd/Fe). Batchdegradation of model compounds, trichlroethylene (TCE) and 2,2'-dichlorobiphenyls(DCB), were conducted using bimetallic Ni/Fe and Pd/Fe nanoparticles. Completedegradation of TCE and DCB is achieved at room temperature. Zero-valent iron, as themajor element, undergoes corrosion to provide hydrogen and electrons for the reductivecatalytic hydrodechlorination reaction. The second dopant metals of nickel and palladium(in nanoscale) act as catalyst for hydrogenation through metal hydride formation thatproduces completely dechlorinated final product. Different compositions of bimetallicNi/Fe and Pd/Fe nanoparticles were synthesized and their reactivity was characterized interms of reaction rate constants, hydrogen generation through iron corrosion, andproducts formation. The observed TCE degradation rate constant was two orders ofmagnitude higher than the bulk iron and nanoiron, indicating that the bimetallicnanoparticles are better materials compared to the monometallic iron systems. Longevitystudy through repeated cycle experiments showed minimum loss of activity. The surfacearea-normalized rate constant was found to have a strong correlation with the hydrogengeneration by iron corrosion reaction. A mathematical model was derived thatincorporates the reaction and Langmuirian-type sorption terms to estimate the intrinsicreaction rate constant and rate-limiting step in the degradation process. Bimetallicnanoparticles were also immobilized into the chitosan matrix for the synthesis of ananocomposite membrane reactor to achieve membrane-phase destruction of chlorinatedorganics under convective flow condition. Formation of uniformly distributed nanosizedparticles is confirmed by high resolution transmission electron microscopy. Themembrane-phase degradation results demonstrated similar trends with the previoussolution phase analysis with the observed enhanced reaction rates. The advantage of themembrane system is its ability to prevent the agglomeration of the nanoparticles in themembrane matrix, to minimize the loss of precious metals into the bulk solution phase,and to prevent the formation of precipitated Fe(III) hydroxide. These are due to thechelating effect of the amine and hydroxyl functional groups in the chitosan backbones.

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