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Jan 1, 1934

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The earliest record of production in this county is for drilling a salt well in 1809. Some scattered data are shown in the table; the total figures are estimated. Little coal could be shipped in this period on account of lack of transportation. [ ]

Jan 1, 1942

By John Birkinbine

A specimen of brown hematite, taken from an iron-ore mine near Anniston, Alabama, exhibits a metallic streak or thread running throngh it. This specimen having been sent to me, I have no personal knowledge of its occurrence; but Mr. Albert E. Noble

Jan 1, 1895

Jan 1, 1918

Jan 1, 1954

Jan 1, 1949

By R. Simon, D. J. Graue

This paper presents correlations for predicting the solu-lility, swelling and viscosity behavior of CO2-crude oil sys8i.m~. The correlations were developed from experimental data obtained by the authors. These data are also presented. The data were determined by measuring the properties of mixtures of CO, and nine different oils. Experiinental conditions covered a range of 100 to 250°F and pressures up to 2,300 psia. Properties predicted by the correlations have average deviations, expressed as per cent of experimental value, of 2 per cent for solubility, 0.5 per cent for swelling and 12 per cent for viscosity. INTRODUCTION Interest in CO2 injection as an oil recovery process has led to the development of performance prediction methods which can be applied to specific reservoirs.1 iS To use these performance prediction methods, it is necessary to know the solubility, swelling and viscosity properties of CO2-crude oil mixtures at reservoir conditions. Some information on these properties has appeared in the literature; however, this information did not cover the range of different oils and conditions needed to prepare generalized correlations for reservoir engineering purposes. Consequently, an experimental program was undertaken to collect the data needed. The data obtained and the correlations developed from the data are described in the following sections of this paper. SOLUBILITY OF CO2 IN CRUDE OILS CO2 solubility data in the literature come from six principal sources. The solubility prediction method of Welker and Dunlop3 is limited to 80F. The information in Ref. 4 is of two types: the first includes binary and ternary mixtures of CO, and light hydrocarbons (C1 to C6), and the second gives data for CO1 and heavy hydrocarbons for a temperature range of 40 to 90F. Ref. 5 contains a KCO2 chart for systems whose convergence pressure is 4,000 psia. The KCO2's are based mainly on CO2-natural gas mixtures. Poettmann's work covered CO2 solubility in one condensate and one crude oil6,7 Ja-coby and Rzasa measured CO? solubilities as a function of pressure and temperature for two natural gas-absorber oil mixtures and two natural gas-crude oil mixtures.'8 CO, concentration in these four systems was fixed at 5 mol per cent. The work reported in this paper extends CO, solubility data to a variety of different crude oil types in a temperature range from 110 to 250F and pressures up to 2,300 psia. The experimental procedure used by the authors to obtain the solubility data consisted of combining known amounts of pure CO, and crude oil in a visual cell at a fixed temperature and measuring the bubble point of the mixture. Measurements were made for a total of 40 different CO2-oil mixtures and the results are shown in Table 2. The mixtures included nine different oils (seven crude oils and two refined oils) whose properties are listed in Table 1. All nine oils had vapor pressures less than 1 atm at the experimental temperatures. Consequently, analysis of the bubble-point vapor showed a CO, concentration over 99 mol per cent. At no time during these experiments was a second, more dense, liquid phase observed. The solubility correlation which was developed from the data in Table 2 is presented in Figs. 1, 2 and 3. In these figures, solubility is expressed as xco2 the mol fraction of CO, in the CO2-oil mixture. Fig. 1 shows solubility as a function of CO2 fugacity6 and temperature. Fig. 2 shows the same solubility data expressed as a function of saturation pressure and temperature. The solubility shown in Figs. 1 and 2 is for an oil whose UOP characterization factor is 11.7. UOP characterization factors of crude oils can be determined from Ref. 10 if the viscosity and APT gravity of the oil are known. Fig. 3 gives the solubility correction factor for oils whose UOP characterization factors differ from 11.7. The solubility correlation in Figs. 1, 2 and 3 predicted

Jan 1, 1966

By A. Satter, J. M. Campbell

Reported herein are the results of a careful and detailed study of the non-ideal behavior of pure gases and their mixtures. Included are: (1) new data on five ternary systems composed of methane, ethane and H2 S; (2) a simple compressibility factor correlation that is inherently superior to present correlations, particularly for gases containing H2S and CO2; and(3) a detailed study of combination rules and the effect of system composition on the choice thereof. This study makes use of the rather large mass of data already available in the literature. A complete re-examination of the data and ideas presented in the last 25 years was considered desirable as a prelude to our basic concern — the effect of diluents on gas behavior. A consideration of both the macroscopic and microscopic properties of gases provides a better insight which, in turn, gives a firmer basis for improved correlation techniques. Such a study has shown that expressing the compressibility factor Z as a function of acentric factor w, as well as reduced temperature and pressure, yields a correlation that is broader in scope. The study of various combination rules has shown that better results are obtained by "tailoring" the rule used to the system composition. To do so improves the basic reality of results by overcoming some of the anomalies often found when using Kay's rule alone. Tentative recommendations are made regarding the most reliable combination rule for use with a given class of gas. The data presented are useful for estimating the direction and magnitude of the expected deviation when using a given rule. Although more work is needed, particularly around the critical region and with CO2 mixtures, the advantage of the classification scheme proposed is apparent. INTRODUCTION When one attempts to write a PVT equation to fit the data for actual gases, greater precision is obtained by the use of a multiple number of empirical constants. This has lead to multiple-constant equations such as Benedict-Webb-Rubin, Beattie-Bridgman, Keyes, etc., which are capable of yielding very precise results for pure gases in a range for which data to get the constants are available. As a matter of practicality, though, the use of such equations for gas mixtures is limited. Because of the infinite number of gas analyses available, any attempt to compile the constants needed requires a prohibitive amount of experimental data. This could be overcome by the use of a combination rule, but there is no real advantage in doing so because the end result offers no practical impovement over the Z factor correlation. The most widely used method of predicting the volumetric properties of pure gases is based upon the "theorem of corresponding states". According to this theorem, "all pure substances have corresponding molal volume at corresponding temperature and pressure if the reference point of correspondence is the critical point". Generalized compressibility charts for gases were prepared first by Cope and associates1 in 1931 and later by Brown and co-workers2 in 1932. However, the most commonly used charts are those of Dodge,3 Nelson and Obert,4 Hougen and atsson: and Standing and Katz.6 The work of Katz and co-workers has provided us with basic data for the hydrocarbons most widely used today. Their original chart6 was compared with a relatively large amount of multi-component data for gases consisting almost entirely of normal paraffin hydrocarbons. A deviation of only + 1.2 per cent was obtained.39 In the 20 years following publication of this work it has been found that the behavior of most mixtures of paraffin hydrocarbons could be predicted by this correlation within at least 5 per cent. Where difficulty has been encountered it has largely involved one or more of the following circumstances: pressures above 4,000 psig, mixtures containing large amounts of heavy ends and/or aromatics, systems in the critical region and mixtures containing polar compounds and/or CO2. The abnormal error sometimes found with such gases, not too unexpected for this method, is