Properties of Black Oils—Correlations 299 Solution gas-oil ratio, Pressure, ss psia scf/STB 2685 768 2414 676 2165 594 1915 513 1665 434 1415 358 1165 284 915 214 665 147 415 86 465 31 Density of a Liquid ‘The petroleum engineer needs to be able to estimate the density of the reservoir liquid at reservoir conditions. Then the shrinkage in volume that a reservoir liquid undergoes while progressing from the reservoir to the stock tank can be estimated. There are several methods of calculating the volume occupied by a given mass of liquid at elevated pressures and temperatures. We will consider only one method: the method most applicable to the liquids encountered in the oil fields. This method is based on ideal-solution principles. We will study three different applications of ideal solution theory to the calculation of density of a liquid. Each application will depend on the amount of information available. The first applies when the composition of the reservoir liquid is known. The second applies when solution gas- oil ratio, gas composition, and stock-tank oil gravity are known. The third is used when solution gas-oil ratio, gas specific gravity, and stock- tank oi] gravity are known. Calculation of Liquid Density Using Ideal-Sotution Principles An ideal liquid solution is a hypothetical mixture of liquids in which there is no special force of attraction between the components of the solution and for which no change in internal energy occurs on mixing. Under these circumstances no change in the character of the liquids is caused by mixing, merely a dilution of one liquid by the other. When liguids are mixed to give an ideal solution, there is no heat effect and the properties are strictly additive. The volume of the ideal300 PETROLEUM FLUIDS solution is the sum of the volumes of the liquid components. There is no shrinkage nor expansion when the liquids are mixed. Other physical properties of the solution (such as refractive index, viscosity, and vapor pressure) can be calculated directly by averaging the properties of the components which make up the ideal solution. There are no ideal liquid solutions, just as there are no ideal gas mixtures. However, when liquids of similar chemical and physical characteristics are mixed, the behavior of the resulting solution is very much like the behavior of an ideal solution. Fortunately, most of the liquid mixtures encountered by petroleum engineers are mixtures of hydrocarbons with similar characteristics. Thus, ideal-solution principles can be applied to the calculation of the densities of these liquids. The application of ideal-solution principles to the calculation of the density of a liquid is very ‘easy. One simply calculates the mass and volume of each of the components of the mixture. Then these quantities are added to determine the mass and volume of the mixture. Density is simply mass divided by volume. Calculations of this type usually are made for a temperature of 60°F and a pressure of 14.696 psia. The densities of typical pure hydrocarbons at these conditions may be obtained from Appendix A. A standard pressure of 14.696 psia is used here because the data in Appendix A are based on that value. The value of standard pressure used in liquid volume calculations is not as important as for gas calculations. Liquid is not as compressible as gas, so the difference of a few tenths of a psi in standard pressure has a negligible effect on liquid density. Later we will see how density at standard conditions can be used to calculate density at reservoir conditions. EXAMPLE 11-3: Use ideal-solution principles to calculate the density at 14.696 psia and 60°F of a hydrocarbon liquid of the following composition. Component Mole fraction n-Butane 0.270 n-Pentane 0.310 n-Hexane 0.420 1.000 Solution Determine the volume and mass of each component at 14.696 psia and 60°F. Divide the total volume into the total mass of the mixture to obtain density.Properties of Black Oils— Correlations 301 Component Liquid density Liquid volume Mole Molecular at 60°F and at 60°F and fraction, weight, Mass, 14.696 psia, 14.696 psia, Jb mol Ib/lb mol Ib Ib/cu ft cu ft x My xh Pos MP n-C,4 0.270 58.1 15.69 36.42 0.4307 n-Cs 0.310 72.2 22.38 39.36 0.5686 n-Cg 0.420 86.2 36.20 41,40 0.8745 1.000 74.27 Ib 1.8738 cu ft 74.27 Th_ _ 39 64 Ib/eu ft at 60°F and 14.696 psia Po = 7.8738 cu ft Calculation of Reservoir Liquid Density at Saturation Pressure Using Ideal- Solution Principles Now we will examine the methods of estimating the density of a reservoir liquid at reservoir conditions. First, we will consider liquids at their bubble points or liquids in contact with gas; in either case, we will call these saturated liquids. The first step in the calculation procedure is to determine the density of the liquid at standard conditions. The next step is to adjust this density to reservoir conditions. There are two problems associated with this procedure. First, methane and ethane are not liquid at standard conditions, so a liquid density at standard conditions does not exist for either of these two components. Second, a hydrocarbon mixture which is liquid at reservoir conditions will partially vaporize at standard conditions. The solution to the first problem is to use apparent liquid densities for methane and ethane. These apparent liquid densitics were derived through a study of mixtures containing methane and other heavier hydrocarbons and mix- tures of ethane and other heavier hydrocarbons.” The experimentally determined densities of these mixtures at numer- ous elevated pressures and temperatures were adjusted to atmospheric psia and 60°F using suitable compressibility and thermal expansion factors. Then the mass and volume contributed by the heavier compo- nents were subtracted. This left the contribution due to methane or ethane, i.e., their apparent liquid densities. Thus, the apparent liquid densities are fictitious. However, they represent the contribution of methane and ethane to the density of the liquid mixture.