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Properties of Hydrocarbon Mixtures As Related to Production Problems

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Properties of Hydrocarbon Mixtures As Related to Production Problems Chapter I. Production Engineering and Engineering Research Properties of Hydrocarbon Mixtures as Related to Production Problems By W. K. LEWIS, * CAMBRIDGE, MASS. (Dallas Meeting, October, 1934) DURING the last decade the petroleum refinery engineer has made great progress in achieving a better understanding of the physical behavior of hydrocarbon mixtures, with particular reference to their pressure-temperature-volume relationships, the mechanism of the evaporation of liquids, the condensation of vapors, including the changes in composition, and the heat effects accompanying them. With the new insight into the mechanism of movement of oil and gas through the formations in which they occur, achieved by the production engineer, Downloaded from http://onepetro.org/trans/article-pdf/107/01/11/2178452/spe-934011-g.pdf by guest on 27 September 2021 it is clear that the latter will need to utilize in the solution of his own problems much of the information outlined above. It is the purpose of this paper to outline the portions of that information that seem most certain to prove of importance in production work. PROPERTIES. OF PURE HYDROCARBONS While it is true that petroleum always consists of highly complex mixtures of hydrocarbons, none the less understanding of the behavior of the mixture must be based upon a knowledge of the properties of the pure components. However, in view of the tremendous number of hydrocarbons existing in petroleum, the determination and formulation of the properties of all of them would seem a discouraging task. The difficulty of the situation is increased by the undoubted facts that the overwhelming majority of chemical individuals in petroleum have never been isolated as pure compounds, none of their physical properties have been determined and even their chemical constitution is unknown. The situation would be hopeless were it not for the fact that certain extra­ ordinary correlations of important properties of various hydrocarbons have been discovered which make it possible to predict those properties for a given chemical individual on the basis of a very limited character­ ization of it. Thus one can predict the vapor-pressure curve of an unknown hydrocarbon over a considerable range from the knowledge of a • Professor of Chemical Engineering, Massachusetts Institute of Technology. 11 12 PROPERTIES OF HYDROCARBON MIXTURES single point on that curve, with no other information whatsoever as to the nature of the hydrocarbon; if, in addition to this one point, one knows the molecular weight and the density of the hydrocarbon, one can esti­ mate the whole vapor-pressure curve with reasonable precision from these three bits of information and nothing else. Indeed, it is not impossible that a knowledge of three characteristics of an unknown hydrocarbon, properly chosen, may turn out to be sufficient to determine all its more important physical properties. Clearly, therefore, one must start with a knowledge of the properties of individual hydrocarbons, interpreted and generalized in the light of these correlations. TEMP " '40 0.,220 ZIG - 100 I -------- ---------- --- ---- Downloaded from http://onepetro.org/trans/article-pdf/107/01/11/2178452/spe-934011-g.pdf by guest on 27 September 2021 -._ .. /--- . _.- _._- - - - -- -- -----j -- ~~ J t p/ 0.01-- --_ ... -- - ------ ----I D ---t- -- D a: 1---- IS r 'fI ~ f., 8 I 0 :=I ". :=I I( r ./ ~ i!; i!; f i;! / / ..a: i i.. ..'" 0.00,,L-i / I. O-YDUN~ I I' X-WORIN.,. y-wUNOCL 7 I ,t,-LANDOLTIe6RNlTtiN TAKL.I'&a J i • - RIC.HARDS AND JUSE " 0.0001 , 0.1 ... ... ...0 4&0 4'0 ... ..0 TEMP. ·K. - FIG. I.-VAPOR PRESSURE OF n OC'l'ANE (CSH18). It must be emphasized that these correlations are not absolute. They are approximations only. However, many of them are remarkably close, almost always amply within the requirements of engineering work and in some cases probably better than the accuracy of the best existing data. Vapor Pressures The vapor pressures of all hydrocarbons rise rapidly with increase in temperature, so rapidly that when plotting them on ordinary coordinate Downloaded from http://onepetro.org/trans/article-pdf/107/01/11/2178452/spe-934011-g.pdf by guest on 27 September 2021 p - A63Ol.1/T'[ ~t!SUR£ MM, >4, N N 0:5 g g8~gg8 0 " . - " . N 0 . - N . - N . - , " • I":" 4 2 ,. ~ r.... ...... '\. 20 • 2. 30 "'" ~" >0 40 '0 .......7 '0 .. .0 70 70 .0 .0 • 0 .. ....... 00. " r--... ~ "- r-.. .......... ~ :l '20 '20 ....... -....;: r-... :-;: "- ~ t'-. " '40 t--- . ... ,eo ... , '.0 ,.. 0 200 :::::::: ,. k ........ ~ 220 "- ,. r-.... ~O 240 -- '- .. ~ 2. '. ....... ZOO 2.0 200 30 ~- ~O 32 32~ 3 '" ,.0 3 - .... 380 ~ 4 - ..... 450 Y-1'iL I:'.~ t-'~ , .... 500 -- ~ :A' - !b eo g . .. - ~ ~ ~ ~ ~ ~ 5l t:' " ~ !! N ... g U ~ N ~ . ,;::.- P - AeSOl..UTf PRESSUR£ MM 1"4, "'" FIG. 2.-VAPOR PRESSURES OF NORMAL PARAFFIN HYDROCARBONS. Original article by Cox: Ind. & Eng. Chem. (1923) 16,592. Data of Wilson and Bahlke: Ind. & Eng. Chem. (1924) 16, 115. Extended ranges, Calingaert and Davis: Ind. & Eng. Chem. (1925) 17, 1287. Key numbers are values of Cn H 2n + 2. Steam indicated by broken line. Benzene 6B. Equations of scales: Ordinates. Y = 3910 [_1_ - __I__ = inches; abscissas, x = 4.03 log12 P = inches. 230230+1 J 14 PROPERTIES OF HYDROCARBON MIXTURES paper interpolation is inaccurate and all precision is lost at low pressures. This difficulty can be met by the use of a semilogarithmic plot such as that of Fig. 1, which shows the vapor-pressure curve of n-octane. On this curve are indicated the data points of individual investigators, so that the correlation between their results is immediately apparent. All vapor-pressure data are of this general type and are probably best pre­ sented in this or some equivalent way. Numerous methods of correlation of the vapor-pressure relationships of various hydrocarbons have been suggested. One of the most conveni­ ent is that of Cox, or one of its modifications, as shown in Fig. 2. The pressure scale is logarithmic and the temperature scale arbitrarily drawn. It is found that on such a chart the vapor-pressure curves of all pure hydrocarbons plot as substantially straight lines, converging to a common point. Consequently, a single point on the vapor-pressure curve of a hydrocarbon, such as its boiling point at atmospheric pressure, or at any Downloaded from http://onepetro.org/trans/article-pdf/107/01/11/2178452/spe-934011-g.pdf by guest on 27 September 2021 other known pressure, enables one to construct the complete curve for the hydrocarbon in question. There is no doubt that this correlation is not perfect. The lines for individual hydrocarbons are certainly not always straight. Indeed, the vapor-pressure curves of some hydro­ carbons cross each other, a fact incompatible with the chart. Further­ more, there are more dependable correlations, but' these are also more complicated and since it is uncertain that they are more dependable when extrapolated to higher hydrocarbons, direct data on which are non­ existent, Fig. 2 is perhaps preferable for engineering work. Critical Conditions When hydrocarbon liquids are heated they expand. However, the vapor pressure increases rapidly and, on account of this fact, despite the rise in temperature, the density of the saturated vapor in equilibrium with the liquid increases. Finally, a point is reached at which the densities of liquid and of saturated vapor become identical and differences in physical properties disappear. This is called the critical point of the material in question, the temperature being the critical temperature T e, the pressure, the critical pressure Pc, and the volume, the critical volume, Ve. The critical temperature and pressure are shown for octane at the right-hand end of the curve of Fig. 1, marked Cr. The correlations of critical conditions are somewhat less satisfactory than those of vapor pressures. However, the value of the so-called critical ratio, RTe/PeV e, is remarkably constant for all hydrocarbons investigated. Its average is about 3.79. For hydrocarbons with less than four carbon atoms per molecule the value is definitely lower, being about 3.59 for ethylene and ethane and 3.46 for methane. However, for hydrocarbons with four carbon atoms and above per molecule, the deviations apparently never lie outside the range 3.7 to 3.85, a variation W. K. LEWIS 15 from the mean of only 2 per cent. While it is true that within this range the values for paraffin hydrocarbons average high and those for the aromatics low, it seems allowable, until more accurate data are available, to use the average figure, 3.79, for the critical ratio. It has also been shown that at the critical point the density of all paraffin hydrocarbons containing more than three carbon atoms per molecule on which data are available is practically the same, 0.236. It is readily shown that this is equivalent to the statement that for these hydrocarbons the value of the ratio MPc/Tc is equal to 5.0 within the experimental error. Appar­ ently for aromatic hydrocarbons with no side chains this ratio has a value of approximately 6.9, and for naphthenic ring compounds without side chains about 6. Granting that the vapor-pressure curves can be repre­ sented by Fig. 2, this relationship immediately makes it possible to construct the critical curves for these three classes of compounds. The corresponding curves are shown on the figure. Downloaded from http://onepetro.org/trans/article-pdf/107/01/11/2178452/spe-934011-g.pdf by guest on 27 September 2021 100 80 / 60 / V 40 -r- / V +20 / o V V I'-~ -20 o 100 200 300 400 500 600 700 800 ·K. FIG. 3.-DELTA CORRECTION FACTOR. Another method of prediction of critical temperatures is that of Watson.
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