Chemical Engineering Science, Vol.62, No.15, 3962-3969, 2007
Soret-'shifted' dew-point temperatures for surfaces exposed to hydrocarbon vapors dilute in compressed nitrogen
Soret-driven species transport causes concentration non-uniformities in the immediate vicinity of 'cold' surfaces immersed in undersaturated vapor-containing streams. These concentration non-uniformities, in turn, alter corresponding condensation onset temperatures, often by as much as 30K (i.e., ca. 3%) in previously studied, near-atmospheric pressure combustion systems [see, e.g., Rosner, D.E. and Nagarajan, R., 1985. Chemical Engineering Science 40 (2), 177]. Because high-pressures often cause remarkable increases in the relevant binary Soret factor, alpha(T,12), we investigate here the importance of these vapor phase 'transport' effects for 'compressed' N-2 streams containing dilute quantities of an alkane: C12H26 (n-dodecane) or C8H18 (n-octane). We invoke the virial equation of state (VES) to predict gas phase non-ideality, and its appreciable effect on previously available ideal gas Soret factors. Our illustrative numerical results, valid for, say, nominally 1000 K N2 streams up to pressures of over 100 atm, reveal that high-pressure Soret 'shifts' in T-dp can amount to ca. 80%, even at surface temperatures above the equilibrium freezing points of these condensates. We conclude that these high-pressure vapor phase transport phenomena will not only influence the interpretation of such hot gas/'cold' surface 'dew-point' measurements, they will significantly raise the temperatures at which containment or immersed surfaces must be maintained to avoid the ravages of corrosive or insulating inorganic condensates [Rosner, D.E., Chen, B.K., Fryburg, G.C., Kohl, F.J., 1979. Combustion Science and Technology 20, 87; Rosner, D.E., 1988a. Invited paper, Benjamin G. Levich Memorial Issue of Journal of Physico-Chemical Hydrodynamics 10 (5/6), 663]. In principle, the present theory could itself be used to study the pressure dependence of the binary Soret factor-at least for systems with well-characterized saturation vapor pressures. (c) 2007 Published by Elsevier Ltd.
Keywords:dew-point temperature;compressed gases;binary Soret coefficient;thermodynamics of irreversible processes;local phase equilibria;deposition from supercritical vapor solvents;wall deposition onset temperature;hot corrosion