Graduation Year

2013

Document Type

Thesis

Degree

M.S.E.V.

Degree Granting Department

Civil and Environmental Engineering

Major Professor

Jeffrey A. Cunningham

Keywords

Catalysis, Hydrodehalogenation, Hydrogenation, Palladium, Remediation, Rhodium

Abstract

Halogenated hydrophobic organic compounds (HHOCs) such as 1,2,4,5-tetrachlorobenzene (TeCB) present a threat to both human health and the environment. The common occurrence and recalcitrant nature of HHOCs as soil contaminants necessitate an effective soil remediation method. Wee and Cunningham (2008, 2011, 2013) proposed a clean-up technology called Remedial Extraction and Catalytic Hydrodehalogenation (REACH), which pairs solvent extraction of HHOC contaminants from soil with catalytic hydrodehalogenation to destroy contaminants. Wee and Cunningham (2008, 2011, 2013) utilized a palladium (Pd) catalyst to hydrodehalogenate TeCB to benzene. However, benzene is still a toxic contaminant. Prior research has demonstrated that Pd-catalyzed hydrodehalogenation (HDH) can be paired with Rh-catalyzed hydrogenation to transform TeCB to cyclohexane, which is a less toxic end product (Osborn 2011; Ticknor 2012). However, there remains a need to quantify the effects of different operating conditions on the catalytic reaction rates upon which the technology relies.

It was hypothesized that (1) an increased ratio of water to ethanol in water/ethanol solvents would increase the reaction rates of both Pd-catalyzed HDH and Rh-catalyzed hydrogenation, and (2) catalytic reaction rates would be constant above a hydrogen pressure threshold, but would decrease with decreasing hydrogen pressure beneath the threshold. Thus, the objective of this thesis was to contribute to the development of optimal operating parameters for the REACH technology by quantifying the effects of solvent composition and hydrogen pressure on the catalytic conversion of TeCB to cyclohexane in water/ethanol solvents in a batch reactor.

Complete conversion of TeCB to cyclohexane was achieved at all experimental conditions tested. The data were consistent with an apparent first-order kinetics model where Pd-catalyzed HDH and Rh-catalyzed hydrogenation occur in series. The effects of three water/ethanol solvent compositions (33:67, 50:50, 67:33) were investigated at 50 psi hydrogen pressure. HDH rate coefficients increased monotonically with an increasing fraction of water in the solvent. When the water fraction in the solvent was increased from 50% to 67%, a larger HDH rate coefficient increase was observed than when the water fraction was increased from 33% to 50%. In both cases, the observed increases were statistically significant at a 95% confidence level. For hydrogenation, rate coefficients at 33% and 50% water were approximately equal. The hydrogenation rate coefficient at 67% water was much greater than the rate coefficients at 50% and 33% water, but the increase was not statistically significant at a 95% confidence level. The observed time for complete conversion of TeCB to cyclohexane decreased with an increasing fraction of water in the solvent, from 12-18 hours with a 33% water solvent to 8-12 hours with a 50% water solvent, and to 1-1.5 hours with a 67% water solvent.

The effects of three hydrogen pressures (50 psi, 30 psi, 10 psi) were investigated with a 50:50 water/ethanol solvent. HDH rate coefficients increased monotonically with decreasing hydrogen pressure, though the trend was not statistically significant at a 95% confidence level until the pressure was decreased from 30 psi to 10 psi. This trend can be attributed to the displacement of TeCB by hydrogen on the catalyst surface at higher hydrogen pressures. For hydrogenation, the data suggest that rate coefficients are independent of hydrogen pressure in the pressure range of 10-50 psi, since no statistically significant hydrogen pressure effect was observed. Complete conversion of TeCB to cyclohexane was achieved at hydrogen pressures as low as 5 psi.

These findings suggest that a greater fraction of water in the solvent should be utilized in the REACH system when feasible to maximize catalytic reaction rates. These findings also suggest that the REACH system could be operated at hydrogen pressures as low as 5 psi, which would further improve the safety of the technology.

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