Graduation Year

2012

Document Type

Thesis

Degree

M.S.E.V.

Degree Granting Department

Civil and Environmental Engineering

Major Professor

Jeffrey Cunningham

Keywords

catalysis, chlorinated organics, FID, response factor, tetrachlorobenzene

Abstract

The two objectives of this work were to develop a simplified method for the analysis of chlorinated organics in water samples and to improve an existing soil remediation technology. The contaminants considered for these studies were chlorinated hydrocarbons because of their relative frequency of appearance at contaminated sites. The first half of this study involved the analysis of chlorinated ethenes by gas chromatography with flame ionization detection (GC-FID). I tested the hypothesis that the FID response factor is the same for all chlorinated ethene compounds. The rationale for this investigation is that if the hypothesis is correct, a single calibration curve can be used for GC/FID analysis of all chlorinated ethene compounds, saving time and money during sample analysis. Based on my measurements, a single calibration curve fits PCE, TCE, and cis-DCE (R2=0.998). However, the apparent slope of the calibration curve for vinyl chloride is approximately 45% lower, indicating that a separate calibration curve must be used to quantify vinyl chloride. I believe this difference in vinyl chloride is due to loss of analyte mass due to volatilization.

The second half of the study considered the effect of solvent composition for a soil remediation technology, entitled remedial extraction and catalytic hydrodehalogenation (REACH), developed by Dr. Hun Young Wee and Dr. Jeff Cunningham (Wee and Cunningham, 2008). The objective of this thesis is to convert 1,2,4,5-tetrachlorobenzene (TeCB) to cyclohexane, thus improving on the work of Wee (2007). Recent work by Osborn (2011) tested successfully the use of palladium and rhodium catalysts for this conversion, though it took twelve hours for full conversion. Osborn (2011) performed her experiments in a 50:50 water-ethanol solvent; previous work by Wee and Cunningham (2008) suggests that using a 67:33 water-ethanol composition may dramatically reduce the reaction time. Therefore, the goal of this research was to use palladium and rhodium catalysts with a 67:33 water-ethanol solvent composition, with an aim of reducing the reaction time required to fully convert benzene to cyclohexane.

The data suggest that the time required for conversion of the analyte to its product was improved dramatically compared to previous experiments. However, powdered palladium catalyst was used in this study instead of pellet form as in previous studies. The powdered palladium allowed for full conversion of the target chemical, TeCB, to benzene in less than 5 minutes. Benzene was fully converted to cyclohexane within 45 minutes in the batch reactor when a rhodium catalyst was used jointly with palladium. This study suggests that the 67:33 water-ethanol solvent composition be utilized in continuous flow tests in the future to improve the efficiency of the REACH system. The results also suggest that powdered palladium catalyst be considered because of its ability to force the reaction to completion in significantly less time than previous experiments.

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