Robert A. Marriott

Selective Adsorption of Thiols Using Gold Nanoparticles Supported on Metal Oxides

Selective capture of thiols from a synthetic hydrogen sulfide containing mixture using supported nanogold materials has been explored for the potential removal of thiols from sour gas production fluids. In this research, TiO2-, Al2O3-, SiO2-, and ZnO-supported gold nanoparticles have been studied for their usage as regeneratable adsorbents to capture CH3SH, C2H5SH, and i-C3H7SH. Au/TiO2 and Au/Al2O3 showed promising properties for removing the thiols efficiently from a gas-phase mixture; however, Au/Al2O3 did catalyze some undesirable side reactions, e.g., carbonyl sulfide formation. It was found that a mild temperature of T = 200 °C was sufficient for regeneration of either Au/TiO2 or Au/Al2O3 adsorbent. The metal oxide mesopores played an important role for accommodating gold particles and chemisorption of the thiols, where smaller pore sizes were found to inhibit the agglomeration/growth of gold particles. The nature of thiol adsorption and the impact of multiple adsorption-desorption cycles on the adsorbents have been studied using electron microscopy, XPS, XRD, GC, and physi/chemiadsorption analyses.

Experimental and theoretical investigation of the kinetics of the reaction of atomic chlorine with 1,4-dioxane.

The rate coefficients for the reaction of 1,4-dioxane with atomic chlorine were measured from T = 292-360 K using the relative rate method. The reference reactant was isobutane and the experiments were made in argon with atomic chlorine produced by photolysis of small concentrations of Cl2. The rate coefficients were put on an absolute basis by using the published temperature dependence of the absolute rate coefficients for the reference reaction. The rate coefficients for the reaction of Cl with 1,4-dioxane were found to be independent of total pressure from p = 290 to 782 Torr. The experimentally measured rate coefficients showed a weak temperature dependence, given by k(exp)(T) = (8.4(-2.3)(+3.1)) × 10(-10) exp(-(470 ± 110)/(T/K)) cm3 molecule (-1) s(-1). The experimental results are rationalized in terms of statistical rate theory on the basis of molecular data obtained from quantum-chemical calculations. Molecular geometries and frequencies were obtained from MP2/aug-cc-pVDZ calculations, while single-point energies of the stationary points were computed at CCSD(T) level of theory. The calculations indicate that the reaction proceeds by an overall exothermic addition-elimination mechanism via two intermediates, where the rate-determining step is the initial barrier-less association reaction between the chlorine atom and the chair conformer of 1,4-dioxane. This is in contrast to the Br plus 1,4-dioxane reaction studied earlier, where the rate-determining step is a chair-to-boat conformational change of the bromine-dioxane adduct, which is necessary for this reaction to proceed. The remarkable difference in the kinetic behavior of the reactions of 1,4-dioxane with these two halogen atoms can be consistently explained by this change in the reaction mechanism.

A theoretical analysis of the kinetics of the reaction of atomic bromine with tetrahydrofuran

The kinetic behaviour for the reaction of atomic bromine with tetrahydrofuran has been analysed using the information from quantum chemical calculations. Structures and energy profiles were first o...

The rheology of liquid elemental sulfur across the λ-transition

Seventy million tons of sulfur were produced worldwide in 2016. Much of the transportation and handling of molten sulfur require sulfur pumps which are challenging to operate due to the anomalous behavior of sulfurs liquid viscosity at temperatures near its λ-transition region. Sulfurs viscosity decreases from ca. 30 × 10−2 to ca. 7 × 10−2 Pa s when heating from the melt at T = 115 °C and then increases dramatically at T > 160 °C to a maximum of 93 000 × 10−2 Pa s at T = 187 °C. While the temperature of this viscosity transition is well known, no shear related information can be found in the literature and previous low-shear data do not address thermal hysteresis behavior (viscosity differences for cooling or heating) when sulfur is heated beyond 210 °C. This work is focused on reinvestigating the low-shear viscosity of molten sulfur which was initially studied by Bacon and Fanelli [J. Am. Chem. Soc. 65, 639–648 (1943)] and the effects of high-shear. The rheology of molten sulfur was studied using an An...

Organosulfur adsorbents by self-assembly of titania based ternary metal oxide nanofibers

By doping with secondary and tertiary species, the electron configuration of titanium oxide can be tuned for the selective adsorption of natural gas contaminants such as thiols. In this study, we attempted to co-incorporate copper group metals/oxides and lanthanum oxide within titania nanofibers via linear poly-condensations of multiple metal acetate complexes. In all cases, a sol–gel synthesis in heptane allowed the nanofibers to randomly pack, forming 3 dimensional network bundles. The resulting nanostructures were characterized using electron microscopy, mass spectrometry, X-ray diffraction, X-ray photoelectron spectroscopy, N2 physisorption and Raman spectroscopy. Multicomponent breakthrough studies with three thiols, H2S, CO2 and CH4 show that doping a TiO2 matrix with copper group metals/oxides and La2O3 increased the thermal stability of anatase crystallites and nanostructures. We note that Au and Ag2O accumulated on the surfaces of the doped materials, where the La2O3 doping contributed more to the materials thermal stability. The Cu and La doped material was found to be the best adsorbent for thiols with remarkably high selectivity, demonstrating potential applications in industrial gas treatment. In addition, xerogel adsorbents through the random packing of linear structures provide the advantage of a macro-porous bulk material, which is less susceptible to fouling.