Phase Relationships - Phase Equilibria in Hydrocarbon-Water Systems

Since water is present in natural gas and petroleum reservoirs, it is of engineering value to have accurate experimental data regarding the behavior of water in hydro-carbon systems. Since experimental data of this nature are so scarce in literature, a program is under way at the University of Texas to obtain experimental data regarding the distribution of water in petroleum hydrocarbons. This initial paper is subdivided into three parts: A. The apparatus and analytical procedure are discussed. B. The equipment has been checked by comparing the experimental data with data of literature on the solubility of methane in water at 77°F and pressures to 10,000 psia. C. Experimental data are presented at 100, 160, 220, 280, and 340°F on the solubility of ethane in water at pressures to 1200 psia. As the temperature is increased the solubility of ethane in water first exhibits a minimum and then a maximum solubility. The range of applicability of Henry's Law is discussed. INTRODUCTION Although considerable experimental data have been published on water-hydrocarbon systems in the hydrate region, the information on these systems in the vapor-liquid and the vapor-liquid- 'References are given at end of paper. Manuscript received at the office of the Petroleum Branch August 31. 1949. liquid regions at elevated pressures is extremely scarce. A survey of the literature on hydrocarbon-water systems at elevated pressures was presented by McKetta and Katz12,13,14 showing the systems and phases investigated. In addition to these existing published data, Poettman and Dean" have reported the water content of propane in the three-phase region (only the propane-rich liquid and the vapor phases were studied) and Michels, et al.15 have reported the solubility of methane in water at pressures to 6800 pounds per square inch at 77°F and at pressures to 1500 psia at temperatures to 300°F. It has been shown12,14 that the presence of water will materially affect the phase equilibrium of hydrocarbon systems. In order to make experimental studies on the quantitative effect of the presence of water in naturally-occurring hydrocarbon systems, it is desirable to have data available on binary hydrocarbon-water systems. A program is underway at this laboratory to determine the phase relations of the hydrocarbon-water systems. Initially the investigation will be limited to binary systems with water as one of the components. Later ternary and complex systems will be investigated and reported. EQUIPMENT AND ANALYTICAL PROCEDURE Apparatus In order to avoid a description of the methods employed in each subsequent paper, a description of the apparatus and the analytical procedure will be given here. The apparatus is shown schematically in Fig. 1. The numbered items in Fig. 1 represent the high pressure valves. The equilibrium cell is of the totally enclosed type, with a volume of 550 cubic centimeters. The cell is mounted in an air bath which in turn is mounted on pillow blocks and connected to a rocking mechanism so that the cell and bath will oscillate approximately 30 degrees above and below the horizontal at 35 oscillations per minute. The air bath is heated by two resistance heaters. The first or primary heater is 250 watts and is controlled by a thermoregulator; the second heater is of 500-watt size and is manually controlled to aid in bringing the cell to equilibrium temperature. Air circulation in the bath is accomplished by means of a fan. the shaft of which is concentric to the heaters. The walls of the bath are insulated with 2-in. thick blocks of 85 per cent magnesia. Temperature observations are made with three calibrated thermocouples. One couple is sealed in a well provided within the equilibrium cell, and is used as the criterion of the cell being at the equilibrium temperature. The other two thermocouples are located on opposite sides of the cell to indicate temperature uniformity within the air bath. The thermoregulator, used in conjunction with a relay, gives a variation in the temperature of the air in the bath of plus or minus one degree Fahrenheit. However, since the equilibrium cell weighs approximately 55 pounds, the