A chromatographicstudy of carbon monoxide adsorption in clinoptilolite

Abstract

Adsorption equilibrium and kinetic parameters for CO/clinoptilolite adsorbate/adsorbent pair were determined by perturbation gas chromatography. Chromatographic experiments were performed at temperatures in the 60-120°C range and at carrier gas flow rates in the range of 10.31-24.36 em/sec. The chromatographic response peaks were obtained by concentration pulse method. A packed column of 10 em length and 0.46 em inlet diameter which was packed with clinoptilolite particles with narrow size distribution (500-850 §) around mean diameter of301.9 § was used. The clinopti10lite particles were excavated from Gordes, Western Anatolia. The moments of the response peaks were calculated by integration of experimental chromatographic data and matched to the .model parameters in order to determine the equilibrium constants and diffusion coefficients. The dynamic model (Haynes and Sarma, 1973) was applied to describe the adsorption and diffusion processes in the packed column. This model includes axial dispersion, external mass transfer resistance, micropore and mesopore diffusion resistances. The equilibrium constants (Henry's law constants, K) were calculated in the range of 40 - 952 and were found to be in good agreement with the results in the literature. These constants were found to decrease with increasing temperature. The heats of adsorption were obtained in the range of 54.15 - 57.14 kl/mol from the slope of van't Hoff plots and compared with those in the literature. The heats of adsorption were found to be lower than those reported in the literature obtained for the same adsorbate/adsorbent pair. The higher heats of adsorption were explained by the smaller pore size, higher cation content of the clinoptilolite and more accessibility of the cations in the clinoptilolite framework by CO molecules. Heats of adsorption remained almost constant over the carrier gas velocity range studied. The contributions of axial dispersion and other mass transfer resistances Indiffusion of CO in clinoptilolite were also determined. The total dispersion exhibited slight change (average 0.035 see) with temperature implying that the micropore diffusional resistance was not dominant for diffusion of CO in clinoptilolite under the experimental conditions studied. The axial dispersion coefficient was determined in the range of 1.149.88 cm2/sec and the total mass transfer resistances were found between 0,02-0.06 sec. The results showed that the mesopore diffusion resistance was the controlling mechanism in CO diffusion in clinoptilolite. Mesopore diffusion coefficient was estimated as 2.98xlO-3 cm2/sec. This value was in good agreement with the theoretically determined value.