Water-hydrogen sulfide system, liquid-vapor

The solubility of gaseous weak electrolytes in aqueous solutions is encountered in many chemical and petrochemical processes. In comparison to vapory-liquid equilibria in non reacting systems the solubility of gaseous weak electrolytes like ammonia, carbondioxide, hydrogen sulfide and sulfur dioxide in water results not only from physical (vapor-liquid) equilibrium but also from chemical equilibrium in the liquid phase. 

A. System NH3 H S-H20. The dissociation of water (re-action 9) and the second dissociation of H2S (reaction 6) are neglected at given temperature and total molalities of NHo and H2S there remain four unknown molalities in the liquid phase (e.g. NH3, NH4+, H2S and HS ), the composition of the vapor phase and the total pressure, which are calculated from 8 equations The dissociation constants of ammonia and hydrogen sulfide (eqs.I and III) together with the phase equilibrium for hydrogen sulfide (eq. XII) are combined resulting in a equilibrium constant K 2... 

The remaining equations are phase equilibria for ammonia (eq. K4) and water (eq. K5), mass balances for ammonia (eq. XV) and hydrogen sulfide (eq. XVII), the condition of bulk electroneutrality (eq. XIX), the mole balance in the vapor phase (eq. XX), and the assumption that, for the ammonia-rich systems considered exclusively, in the mass balance for the liquid hydrogen sulfide may be neglected. The system of eight equations can easily be solved ... 

Until recently the ability to predict the vapor-liquid equilibrium of electrolyte systems was limited and only empirical or approximate methods using experimental data, such as that by Van Krevelen (7) for the ammonia-hydrogen sulfide-water system, were used to design sour water strippers. Recently several advances in the prediction and correlation of thermodynamic properties of electrolyte systems have been published by Pitzer (5), Meissner (4), and Bromley ). Edwards, Newman, and Prausnitz (2) established a similar framework for weak electrolyte systems. 

Hydrogen sulfide is conserved by returning depleted Hj S from the top of the cold tower to the bottom of the hot. Heat is conserved by heat exchange between hot and cold liquid and between hot and cold vapor. In principle, no materials other than feed water are consumed in the dual-temperature system energy consumption can be reduced by efficient heat exchange, with a lower bound set by the minimum required by thermodynamics for the separation. 

Edwards et al. (1975, 1978A, B) established a molecular-thermodynamic correlation for calculating vapor-liquid equilibria in aqueous solutions containing one or more volatile electrolytes, with special attention to the ternary systems, ammonia-carbon dioxide-water and ammonia-hydrogen sulfide-water. Their 1978 correlation was shown to give results in satisfactory agreement with the limited data then available for temperatures from 0° to 170°C (32° to 338° F) and ionic strengths of about 6 molal (equivalent to total concentrations of the electrolytes between 10 and 20 molal). 

Experimentally determined vapor-liquid equilibrium data for the system hydrogen sulfide-carbon dioxide-methane-water at pressures ranging from atmospheric to 1,014 psia and temperatures from 85° to 115°F have been reported by Froning et al. (1964). These authors found that the equilibrium constants K can be represented by the following equations ... 

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