HIGH PRESSURE/HIGH TEMPERATURE VAPOR LIQUID EQUILIBRIUM STUDY OF LIGHT GASES IN HYDROGEN-COAL LIQUID MODEL COMPOUND SYSTEMS USING PERTURBATION CHROMATOGRAPHY (GLPC)
KRAGAS, TOR KRISTIAN
Doctor of Philosophy
Perturbation chromatography or gas-liquid partition chromatography (GLPC) provides a powerful tool for making physicochemical measurements. In this investigation GLPC was applied to study the vapor-liquid equilibrium behavior of light gases in nonvolatile coal liquid model compound solvents at high temperatures and high pressures. Improvements made in existing GLPC techniques include: the use of a high pressure tandem proportioning pump to give precise control of the carrier gas flow rate and low pressure drops; a high pressure ionization chamber to detect the injection of very dilute radioactive sample gases; and the use of a microcomputer to provide instantaneous integration and very precise retention times of the chromatographic peaks. Infinite dilution K-values for methane, ethane, propane, n-butane, carbon dioxide, and hydrogen sulfide in hydrogen-dibenzofuran systems were obtained at 100 and 125 C and up to 800 psia. Infinite dilution K-values for the same light gases in hydrogen-9-methylanthracene systems were obtained at 100, 125, 150, 175, and 200 C and up to 3000 psia. Henry's constants were determined for the light gases in 9-methylanthracene. Second cross virial coefficients and vapor phase infinite dilution fugacity coefficients were calculated for methane, ethane, propane, and n-butane in hydrogen. These results were combined with the experimental K-value measurements to obtain Henry's constants in hydrogen-9-methylanthracene mixtures of fixed liquid compositions. Infinite dilution heats of solution of the solute gases in the mixtures were calculated.