Contributions in Petroleam Geology and Engineering Series Editor: George V. Chilingar, University of Southern California Volume 1: Geologie Analysis of Naturally Fractured Reservoirs Volume 2: Applied Open-Hole Log Analysis Volume 3: Underground Storage of Natural Gus Volume 4: Gas Production Engineering Volume 5: Properties of Oils and Natural Gases Volume 6: Introduction to Petroleum Reservoir Analysis Volume 7: Hydrocarbon Phase Behavior Volume 8: Well ‘Test Analysis Volume 9: Horizontal Drilling Gulf Publishing Company Houston, London, Paris, Zurich, Tokyo Contributions in Petroleum Geology & Engineering ($°7 DC Phase Behavior aContributions in Petroleum Geology and Engineering Yolume 7 ‘Hydrocarbon Phase Behavior Copyright © 1989 by Gulf Publishing Company, Houston, “Texas. All rights reserved. Printed in the United States of "America. This book, or parts thereof, may not be reproduced in any form without permission of the publisher. Printed on acid-free paper (%) Library of Congress Cataloging-in-Publication Data ‘Aled, Tarek H., 1946. Hydrocarbon phase behavior by Tarek Ahmed 1p. em.— (Contributions in petroleum geology and engineering; v. 7) Tneludes indes. 1, Petroleum—Migration. 2. Phase rule and equilibrium. I. Title. II. Series: Contributions in petroleum geology & engineering; 7 ‘TN870.5.A35 1989 89-1903 622" 1828 —de20 cP ISBN 0-87201-589-0 ISBN 0-87201-066-X (Series) 1 . Properties of Natural Gases ..+...+++ Contents Preface .. Basie Phase Behavior - Single-Component Systems, 1; TWwo-Component Systems, 15; Multi Component Systems, 21; Classification of Reservoirs and Reservoir Fluids, 23. Pure Component Physical Properties and Characterizing Undefined Petroleum Fractions .. eenaceers ae) Generalized Correlations for Estimating Physical Properties of Hj drocarbon Fractions, 36; Other Methods of Estimating Physical Properties of Petroleum Fractions, 42; Critical Compressibility Fac- tors, 46; Characterizing Hydrocarbon Heavy Fractions, 50; Methods Based on the PNA Determination, 51; Other Methods of Charac terizing the Hydrocarbon Heavy Fractions, 60; Determination of the Physical Properties of the Heavy Petroleum Fractions from Graphi- cal Correlations, 67, Behavior of Ideal Gases, 77; Ideal Gas Mixtures, 79; Properties of Ideal Gas Mixtures, 81; Behavior of Real Gases, 85; Elfect of Non- hydrocarbon Components on the Z-Factor, 95; Correetion for Non~ hydrocarbons, 95; Correction for High-Molecular-Weight Gases, 995 Direct Calculation of Compressbility Factors, 101; Compressibility oof Natural Gases, 106; Gas Formation Volume Factor, 111; Gas Vis- cosity, 113; Methods of Calculating the Viscosity of Natural Gases, 114; Engineering Applications of the Natural Gas PVT Properties, 123,4, Phase Behavior of Crude Oils .. 136 Crude Oil Density and Specific Gravity, 136; Methods for Determin- ing Density of Crude Oils of Unknown Composition, 137; Methods for Determining Density of Liquids of Unknown Composition, 151; Isothermal Compressibility Coefficient of Undersaturated Crude Oils, 156; Density of Undersaturated Crude Oils, 165; Gas Solubil- ity, 169; Oil Formation Volume Factor for Undersaturated Oils, 1925 ‘Total Formation Volume Factor, 198; Total System Isothermal Com- pressibility Coefficient, 199; Crude Oil Viscosity, 205; Methods of Caleulating the Viscosity of the Dead Oil, 207; Methods of Calculat ing the Viscosity ofthe Saturated Crude Oil, 209; Methods of Caleu- lating the Viscosity of the Undersaturated Crude Oil, 212; Caleulat- ing Viscosities of Crude Oils from their Composition, 2165 Bubble-point Pressure, 220; Surface Tension, 225; Application of the Crude Oil PVT Properties in Reservoir Engineering, 229; Radial Flow of Crude Oils, 229; The Material Balance Equation for Oil Res- ervoirs, 231 5. Vapor-Liquid Phase Equilibria . = 24 Equilibrium Ratios, 244; Flash Calculations, 247; Equilibrium Ra- tios for Real Solutions, 250; Equilibrium Ratios for the Plus-Frac- tions, 263; Applications of the Equilibrium Ratio in Petroleum Engi- neering, 270. 6. Equations of State ......60.0+ vee = 287 ‘The Generalized Form of Equations of State, 330; Applications of the Equation of State in Petroleum Engineering, 331; Three-Phase Equilibrium Caleulations, 339. 7. Splitting and Lumping Schemes of Petroleum Fractions ... 348 Splitting Schemes, 349; Lumping Schemes, 300. 8, Simulation of Laboratory PVT Data by Equations of State .. 378 406 Appent Index Equilibrium Ratio Curves .. 419 Preface “This book explains the fundamentals of hydrocarbon phase behavior and their practical application in reservoir and production enginee though the book was developed from notes prepared for hydrocarbon phase behavior courses given to senior petroleum students, it should be useful as a reference book to practicing petroleum engineers Chapter J reviews the principles of hydrocarbon phase behavior and il- lustrates the use of phase diagrams in describing the volumetric behavior of single-component, two-component, and multi-component systems. Chapter 2 presents numerous mathematical and graphical correlations for estimating the physical and critical properties of the undefined petroleum fractions; and Chapter 3 deals with evaluation of properties of natural gases and intro- ‘duces their applications in Darey’s equation and the material balance equa- tion, ‘A complete and cohesive independent unit, Chapter 4 focuses on methods ‘of determining the crude oil physical properties. Chapter 5 presents the con- cept and application of vapor-liquid phase equilibria. Chapter 6 reviews de- velopments and advances in the field of empirical “cubic” equations of state and demonstrates their applications in petroleum engineering. Schemes of splitting and lumping petroleum fractions are illustrated in Chapter 7, and Chapter 8 discusses the simulation of laboratory PVT data by equations of state. ‘Much of the material on which this book is based was drawn from the publications of the Society of Petroleum Engineers of the American Institute of Mining, Metallurgical, and Petroleum Engineers; the American Gas As- sociation; the Division of Production of the American Petroleum Institutes and the Gas Processors Suppliers Association. Tribute is due to these organi- zations and to the engineers, scientists, and authors who have made so many fine contributions to the field of hydrocarbon phase behavior. 1am indebted to my students at Montana Tech, whose enthusiasm for the subject has made teaching a pleasure. I would like to express my apprecia- tion to all the people who have helped in the preparation of the book bytechnical comment and discussion and by giving permission to reproduce material. Special thanks to my colleagues: Professor Art Story, Dr. Herbert Warren, Dz. Gil Cody, Dr. Gene Collins, and Dr, Dan Bradley, for their en- couragement and for making valuable suggestions for improvement of the book. I would also like to express my appreciation to the editorial staff of Gulf Publishing Company, especially Julia Starr. Thanks to Shanna for her patience and understanding, and believing that one day things would return to normal, Tarek Ahmed 1 Basic Phase Behavior ‘A “phase” is defined as any homogeneous part of a system that is physi- cally distinct and separated from other parts of the system by definite boundaries. For example, ice, liquid water, and water vapor constitute three separate phases of the pure substance HO because each is homogeneous and physically distinct from the others; moreover, each is clearly defined by the boundaries existing between them. Whether a substance exists in a solid, liq- tuid, or gas phase is determined by the temperature and pressure acting on the substance. It is known that ice (solid phase) can be changed to water {liquid phase) by increasing its temperature and, by further increasing tem- perature, water changes to steam (vapor phase). ‘This change in phases is termed Phase Behavior. "Hydrocarbon systems found in petroleum reservoirs are known to display multi-phase behavior over wide ranges of pressures and temperatures. The ‘most important phases which occur in petroleum reservoirs are: *# Liquid phase, e.g., crude oils or condensates © Gas phase, e-g., natural gases ‘The conditions under which these phases exist is a matter of considerable practical importance. The experimental or the mathematical determina tions of these conditions are conveniently expressed in different types of dia sams, commonly called Phase Diagrams. ‘The objective of this chapter is to review the basic principles of hydrocar- bbon phase behavior and illustrate the use of phase diagrams in deseribing and characterizing the volumetric behavior of single-component, two-com- ponent, and multi-component systems. “The simplest type of hydrocarbon system to consider is that containing one component. The word “component” refers to the number of molecular 12 Hydrocarbon Phase Behavior ‘or atomie species present in the substance. A single-component system is composed entirely of one kind of atom or molecule. We often use the word “pure” to deseribe a single-component system. ‘The qualitative understanding of the relationship between temperature T, pressure p, and volume V of pure components can provide an excellent basis for understanding the phase behavior of complex petroleum mixtures. The foregoing relationship is conveniently introduced in terms of experimental ‘measurements conducted on a pure component as the component is sub- jected to changes in pressure and volume at constant temperature. The ef- fects of making these changes on the behavior of pure components are next discussed. Suppose a fixed quantity of a pure component is placed in a cylinder fitted with a frictionless piston at a fixed temperature T, Furthermore, consider the initial pressure exerted on the system to be low enough that the entire system is in the vapor state. This initial condition is represented by point E, oon the pressure-volume phase diagram (p-V diagram) as shown in Figure 1-1. Consider the following sequential experimental steps taking place on the pure component: Step 1. ‘The pressure is increased isothermally by forcing the piston into the cylinder. Consequently, the gas volume decreases until it reaches point F on the diagram, where the liquid begins to con- dense. The corresponding pressure is known as the dew-point pressure pg, and is defined as the pressure at which the first drop- let of li formed. Step 2. The piston is moved further into the eylinder as more liquid con- denses, This condensation process is characterized by a constant pressure and represented by the horizontal line FG. At point G, traces of gas remain and the corresponding pressure is called the bubble-point pressure pp, and defined as the pressure at which the first sign of gas formation is detected. A characteristic of a single-component system is that at a given temperature, the dew-point pressure and the bubble-point pres- sure are equal. Step 3. As the piston is forced slightly into the cylinder, a sharp increase in the pressure (point H) is noted without an appreciable decrease in the liquid volume. That behavior evidently reflects the low compressibility of the liquid phase. By repeating the above steps at progressively increasing temperatures, a family of curves of equal temperatures (isotherms) is construpted as shown in Figure 1-1, The dashed curve connecting the dew points is called the dew-point curve (line FC) and represents the states of the “saturated gas.” ‘The dashed curve connecting the bubble points is called the bubble-point Basic Phase Behavior 9 Pressure Volume ———+ Figure 1-1. Pressure-volume diagram for a single component system. curve (line GC) and similarly represents the “saturated liquid.” These two ‘curves meet at point C which is known as the critical point. The correspond ing pressure and volume are called the critical pressure p. and critical vol- uume Vc, respectively. Notice that as the temperature increases, the length of the straight line portion of the isotherm decreases until it eventually van- ishes, and the isotherm merely has a horizontal tangent and inflection point at the critical point. This isotherm temperature is called the critical temper- ature Tz of the single-component system. This observation can be expressed mathematically by the following relationship; ap : fz). 0 (at the critical point) (ay Pl cal poi - (ea 0 (at the critical point) (2) Referring to Figure 1-1, the area enclosed by the phase envelope AFCGB is called the two-phase region. Within this defined region, vapor and liquid4 Hydrocarbon Phase Behavior can coexist in equilibrium, Outside the phase envelope, only one phase ean exist ‘The critical point (point C) deseribes the critical state of the pure compo- mnt and represents the limiting state for the existence of two phases, ic, liquid and gas. In other words, for a single-component system, the critical point is defined as the highest value of pressure and temperature at which two phases can coexist. A more generalized definition of the critical point which is applicable to a single or multi-component system is: the critical point is the point at which all intensive properties of the gas and liquid phases are equal. {An intensive property is one that has the same value for any part of a homogeneous system as it does for the whole system, i.e., a property which is independent of the quantity of the system. Pressure, temperature, density, composition, and viscosity are examples of intensive properties. ‘Many characteristic properties of pure substances have been measured and compiled over the years. These properties provide vital information for calculating the thermodynamic properties of pure components as well as their mixtures. Those physical properties that are needed for hydrocarbon phase behavior caleulations are presented in Table 1-1 for a number of hy- drocarbon and non-hydrocarbon components. ‘Another means of presenting the results of this experiment is shown, graphically in Figure 1-2 in which the pressure and temperature of the sys- tem are the independent parameters. Figure 1-2 shows a typical pressure- temperature diagram (p-T diagram) of a single-component system. The re- sulting curve, i., line AC, which terminates at the critical point (point C), can be thought of as being the dividing line between the area where liquid ‘and vapor exists. The curve is commonly called the "vapor-pressure curve” Figure 1-2. Pressure-temper ture diagram for a pure compo- rent system. Pressure ‘Temperature ————> Basic Phase Behavior 5 or the “boiling-point curve.” The corresponding pressure at any point on the curve is called the vapor pressure py. Figure 1-2 shows that at the conditions of pressure and temperature speci- fied by the vapor pressure curve, two phases ean coexist in equilibrium. Sys- tems represented by points located below the vapor-pressure curve are com- posed only of the vapor phase. Similarly, points above the curve represent systems that exist in the liquid phase. These remarks can be conveniently summarized by the following expressions: if p < p,~*system is entirely in the vapor phase p > p.-*system is entirely in the liquid phase P = Py7Vapor and liquid coexist in equilibrium where p is the pressure exerted on the pure substance. It should be pointed out that the above expressions are valid only if the system temperature is below the critical temperature 'T, of the substance. ‘A method which is particularly convenient for plotting the vapor pressure as a function of temperature for pure substances is shown in Figure 1-3. The chart is known as the “Cox Charts.” Notice that the vapor pressure seale is, logarithmic, while the temperature scale is entirely arbitrary. Example 1-1. A pure propane is held in a laboratory cell at 80°F and 200 psia. Determine the “existence state” (Le., as a gas or liquid) of the sub- stance. Solution. From the Cox Charts, the vapor pressure p, = 150 psi, and be- ‘cause the propane is under 200 pi (i., p>), this means that the labora- tory cell contains a liquefied propane. "The vapor pressure chart as presented in Figure 1-3 allows a quick estima- tion of the vapor pressure p, of a pure substance at a specific temperature. For computer applications, however, an equation is more convenient. Lee and Kesler (1975) proposed the following generalized vapor pressure equa- tion: Pv = pe EXP (A+ @B) a3) with, A= 5.92714 - 19648 ~ 1,286 In (T,) + 0.16994(T,)® (4) B= 15.2518 - Bes 13.4721 In (T,) + 0.4357(T,)° (sy7 Basic Phase Behavior Hydrocarbon Phase Behavior 6 ui6U3 SIO o4i UI PEYSIIGNE ‘UolleIS0ssy SB\\ddNg si0sse901g SEH Ayp JO ASB}NOD 10 Kousisisu09 on914D8 0; sanyen pareinaye> 0} peppe 16 Sej2euno5e eneY OU Op aIger SIul Ul SJOQUION ‘LON 4P3 uiual, ‘Yoo wie 6 “sanya jeyvowyedxe jo vore|noyeoa: ‘ugaq oney sy/6ip Biix@ S9SE @wWOS UI OOO; Ul Hed | UeUI ‘9st0"0 [iz soc Soez'0 |e osr-les: ze. ri ia ss Zero 0 @ ooze | s0s6:0 3 ‘ata: 0 is| os| c1s0°0 ‘ oa} | Lasoo t ee os] Sois-0 i | | ciso-0 es 3s] tesor0 Ed ss] soro-0 arise ss Fa] tavo-0 Bere les} ce| seco. —— Fe es] teso. — eg 15] tes0 ig os] oss os er] zes0" ¥sor as| vas0:0 ols | ocs0°0 260s oe] cas0-0 ooze Ss] Zes0°0 Sire | $550°0 once Es] o250°0 $568 ey] tes0-0 you is] s6s0°0 08s 955) es ) BAASBRA ARS Raeeas: RRR 88 RR ietee | sez Geil oteed| stousn lee Ba eeakR BSE ETE EE sg: ana: ® SBAROGT AES is 28989 28s! Be os : 35 : zi SEP Rel? : Ualiesiiistis leans ar} ep] E : 7 @ 3 a 3s ed ele; a] § peelec porters S/:S is] Sate ee ale mane won| F £ Siuauoduieg aang 10} samuedosg (eorehid =: Fb arg,8 Hydrocarbon Phase Behavior Basic Phase Behavior 9 RABARRAAAS digits have been wai/s08 HH a v= anlage, \c4yyaos6 21512080) FE Aujmap eanoied ee 2333 | Torsos_| 73.6600 20088 8 Table 1-1 é BRRSRRGE BSISH seasaees E8882 FPITT_TIPPTTTT_FTFET ¥ smyosedee4| 378: | ~0.00300+| 0.1289 | 0:9925 | © sou a1/"108) i is 28 RSRgSER Courtesy of the Gas Processors Suppliers Association. Published in the GPSA Engineering Data Book, Tenth Ect “16/001 2 4609/4900 Beas SoBeEanT 8 3 (fa 0s 215;0t 3 3 e cvntonsieniel eat lad HES EE His EEG | zeaunnf FF RaRAS RRA GNARMRRANS sSTeESTS aaaas AoRAsSwTs| 510 Hydrocarbon Phase Behavior Basic Phase Behavior 11 ‘The term 7, is called the reduced temperature and is defined as the ratio of the absolute system temperature to the critical temperature of the frac- tion, or f. Temperature, °F rocessors where T, = reduced temperature substance temperature, °R ‘T, = critical temperature of the substance, °R P. = critical pressure of the substance, psia ‘& = acentrie factor’ of the substance. Tenth Edition, 1987, ‘The acentric factor w was introduced by Pitzer (1955) as a correlating pa- rameter to characterize the acentricity or non-sphericity of a molecule, and ined by the following expression: w= - Lo |- 1 i) tart for hydrocarbon components. Courtesy of the Gas Pr where p, = vapor pressure of the substance at T = 0.7 Te, psia Po = critical pressure of the substance, psia ls ‘The acentrie factor is frequently used as a third parameter in correspond: ing states and equation-of-state correlations. Values of the acentric factor for pure substances are tabulated in Table 1-1. ‘od in the GPSA Engineering Data Book, Ss Example 1-2. Calculate the vapor pressure of propane at 80°F by using |, 83 the Lee and Kesler correlation. ge 88 Solution BS © Obtain the critical properties and the acentric factor from Table 1-1 28 "7, = 696.01 °R fe Pe = 616.3 psia 22 co = 0.1522 ° B 2 © Calculate the reduced temperature. ‘j94“aunssaud soden 0.81108 + When Equation Ll employed to caleulatep, itis reommended that Eq Chapter 2 be used to compute w. ation 3-13 from12 Hydrocarbon Phase Behavior * Solve for the parameters A and B by applying Equations 1-4 and 1-5, respectively. ~ 1.27359 Be ~ 1147085 ‘Solve for py by applying Equation 1-1 py = 616.3 EXP ( ~ 1.27359 + 0.1572 ( ~ 1.147045)) = 145 psia ‘The densities of the saturated phases of a pure component, i.e., densities of the coexisting liquid and vapor, may be plotted as a function of tempera- ture, as shown in Figure 1-4. It should be noted that for increasing tempera- ture, the density of the saturated liquid is decreasing, while the density of the saturated vapor increases. At the critical point C, the densities of vapor and liquid converge. At this eritical temperature and pressure, all other properties of the phases become identical. crsical Point Average Density qitatee sees eeae Density Tataraved Gas Figure 1-4. Typical density-temperature diagram for a pure component. Figure 1-4 illustrates a useful observation, known as the Law of the Re linear Diameter, which states that the arithmetic average of the densi the liquid and vapor phases is a linear function of the temperature. ‘The straight line of average density versus temperature makes an easily defined intersection with the curved line of densities. Ths intersection then gives the critical temperature and density. Mathematically, this relationship is ex- presed as follows: Basic Phase Behavior 13 Pet Pll aa bT i 7 + a7) where p, = density of the saturated vapor, Ibift® px = density of the saturated liquid, Ibvft? ‘T = temperature, °R a, b = intercept and slope of the straight line, At the ritical point, Equation 1-7 can be expressed in terms ofthe critical density as follows: pow atbT. (18) where pe = critical density of the substance, Ib/ft? Rackett (1970) proposed a simple generalized equation for predicting the saturated liquid density “py,” of pure compounds. Rackett expressed the cor- relation in the following form: (MW) pe PRT ZA + 1-1)" 5 (19) where p;, = saturated liquid density of the pure substance, Ibift? MW = molecular weight of the pure substance Po = critical pressure of the substance, psia ‘T, = critical temperature of the substance, °R Z, = critical gas compressibility factor R = gas constant, 10.73 ft? psia/lb-mole, °R T,= 2, reduoed temperature T = temperature, °R Spencer and Danner (1973) modified Rackett’s correlation by replacing the critical compressibility factor Z. in Equation 1-9 with the parameter Zn, which is a unique constant for each compound. ‘The authors proposed the following modification of the Rackett equation, (MW) Pe RT. Zpall + (= T)*) (2-10) ‘The values of Zn, are given in Table 1-2 for selected components. If a value is not available, Yamada and Gunn (1973) suggested the following correlation to estimate Zan:14 Hydrocarbon Phase Behavior Table 1-2 Values of Zpa for Selected Pure Components Carton dioxide ore ‘-Pontane 0.2684 Nigen 0.2900 nHexane 0.2635 Hydrogen sulfide 0.2885 ‘rHepiane 0.2606 Methane 0.2892 Octane 0.2686 Ethane 0.2808 n-Octane 02871 Propane 0.2766 ‘Nonane 0.2543 Butane 0.2754 nDecane 0.2507 Butane 0.2730 r-Undacane 0.2498 HPentane o27i7 Za = 0.29056 ~ 0.08775 ay where w is the acentric factor of the compound. Example 1-3. Calculate the saturated liquid density of propane at 160°F by using 1. The Rackett correlation b. The modified Rackett equation, Solution. * From Table 1-1 T. = 666.06 °R pe = 616.0 psia MW = 44.097 Ve = 0.0727 Ibitt? # Calculate Z, by applying Equation 3-15 of Chapter 3. peVeMW. RT. __ (616.0) (0.0727) (44.097) 0.2763 (10.73) (666.06) Z 160 + 460 666.06 93085 ‘The Rackett correlation. Solve for the saturated liquid density by apply- ing the Racketp equation, i.e., Equation 1-9 Basic Phase Behavior 15 pL. 0 Ob Or = 25.05 Ibift? b. The modified Rackett equation, From Table 1-2, Za, = 0.2706 © Applying the modified Rackett equation, i.e., Equation 1-10 (44.097)(616) ~ (OT 666. 06)(0-zTERyaaT ~ 25-01 Wie is "TWO-COMPONENT SYSTEM! ‘A distinguishing feature of the single-component system is that, at a fixed ‘temperature, two phases (vapor and liquid) can exist in equilibrium at only ‘one pressure; this isthe vapor pressure. For a binary system, two phases can exist in equilibrium at various pressures at the same temperature, The fol- lowing discussion concerning the description of the phase behavior of a two- component system involves many concepts that apply to the more complex component mixtures of oils and gases. One of the important characteristics of the binary systems is the variation of their thermodynamic and physical properties with the composition, ‘Therefore, it is necessary to specify the composition of the mixture in terms of mole or weight fractions. It is customary to designate one of the compo- nents as the more volatile component and the other the less volatile compo- nent, depending on their relative vapor pressure at a given temperature. Suppose that the experiments previously described for a pure component are repeated, but this time we introduce into the cylinder a binary mixture of a known overall composition. Consider that the initial pressure py exerted on the system, at a fixed temperature of T,, is low enough that the entire system exists in the vapor state. This initial condition of pressure and tem- perature acting on the mixture is represented by point 1 on the p-V diagram of Figure 1-5. As the pressure is increased isothermally, it reaches point 2, at which an infinitesimal amount of liquid is condensed. The pressure at this point is called the dew-point pressure py of the mixture. It should be noted that at the dew-point pressure, the composition of the vapor phase is equal to the overall composition of the binary mixture. As the volume is decreased (by forcing the piston inside the cylinder), a noticeable increase in the pres- sure is observed as more and more liquid is condensed. This condensation process is continued until the pressure reaches point 3, at which traces of gas remain, At point 3, the corresponding pressure is called the bubble-point pressure py. Because at the bubble point the gas phase is only of infinitesimal volume, the composition of the liquid phase is therefore identical with that16 Hydrocarbon Phase Behavior of the whole system. As the piston is forced further into the cylinder, the pressure rises steeply to point 4 with a corresponding decreasing volume. Repeating the above experiments at progressively increasing tempera- tures, a complete set of isotherms is obtained as shown on the p-V diagram of Figure 1-6, The bubble-point curve, as represented by the line AC, repre sents the locus of the points of pressure and volume at which the first bubble of gas is formed. The dew-point curve (line BC) describes the locus of the points of pressure and volume at which the first droplet of liquid is formed, ‘The two curves meet at the critical point (point C). The critical pressure, temperature, and volume are given by ps, Ts, and Ve, respectively. Any point within the phase envelope (line ACB) represents a system consisting of ‘two phases. Outside the phase envelope, only one phase can exist. If the bubble-point pressure and dew-point pressure for the various isotherms on a p-V diagram are plotted as a function of temperature, a p-T diagram similar to that shown in Figure 1-7 is obtained. Figure 1-7 indicates that the pressure-temperature relationships can no longer be represented by a simple vapor pressure curve as in the case of a single-component system, but take on the form illustrated in Figure 1-7 by the phase envelope ACB. ‘The dashed lines within the phase envelope are called the “quality lines”; they describe the pressure and temperature conditions of equal volumes of liquid, Obviously, the bubble-point curve and the dew-point curve repre- sent 100% and 0% liquid, respectively. Figure 1-8 demonstrates the effect of changing the composition of the bi- nary system on the shape and location of the phase envelope. Two of the lines, as shown in Figure 1-8, represent the vapor pressure curves for meth- Figure 1-5. Pressure-volume di- gram for a binary system. Yoese —j-————> Basle Phase Behavior 7 Figure 1-6. Pressure-volume diagram for a two-component system. Pressure Tesperstare Figure 1-7. Typical pressure-temperature diagram for a binary system.} Basic Phase Behavior 19 ‘ane and ethane, which terminate at the critical point. Ten phase boundary curves (phase envelopes) for various mixtures of methane and ethane are also shown. These curves pass continuously from the vapor-pressure curve of the one pure component to that of the other as the composition is varied, ‘The points labeled 1-10 represent the eritical points of the mixtures as de- fined in the legend of Figure 1-8. The dashed curve illustrates the locus of critical points for the binary sys It should be noted by examining Figure 1-8 that when one of the constitu- cents becomes predominant, the binary mixture tends to exhibit a relatively narrow phase envelope and displays critical properties cose to the predomi nant component. The size of the phase envelope enlarges noticeably as the ‘composition of the mixture becomes evenly distributed between the two components. Figure 1-9 shows the critical loci for a number of common binary systems, Obviously, the critical pressure of mixtures is considerably higher than the citical pressure of the components in the mixtures. The greater the differ- cence in the boiling point of the two substances, the higher the critical pres- sure of the mixture will be. No. 17. 3 a =e ‘The Phase Rule It is appropriate at this stage to introduce and define the concept of the “Phase Rule.” Gibbs (1876) derived a simple relationship between the num- ber of phases in equilibrium, the number of components, and the number of independent variables that must be specified to describe the state of the sys- tem completely. Gibbs proposed the following fundamental statement of the phase rule, Teupenarure zi i « a g 2 $ 3 i g 8 : i & 5 é 3 z : F=C-P+2 (1-13) a: iW where F = number of variables required to determine the state of the sys- TELE: 5 tem at equilibrium, or number of degrees of freedom gl sFrscgers sy 2 C = number of independent components te 32 P = number of phases Bh seg gegeees | 2 g ig 6 Sree ease ea . A phase has been defined previously asa homogeneous sytem of uniform as ec physical and chemical composition’In a system containing ice, liquid water, 22 ccccc0e at is and water vapor in equilibrium there are three phases, ie., P= 3. The saenecel number of independent components in the system is one, i.e., C = 1, since ig the system contains only HO. The degrees of freedom F for a system include : * the temperature, the pressure, and the composition (concentration) of e phases, These independent variables must be specified to define the system Buuetelgue Saset: see cseeecsee\- leet eesl® See Sseeued completely i visa aunss3ud20 Hydrocarbon Phase Behavior Basic Phase Behavior 21 i ‘The phase rule as described by Equation 1-12 is useful in several ways. It indicates the maximum possible number of equilibrium phases that can co- exist and the number of components present. It should be pointed out that the phase rule does not determine the nature, the exact composition, or total ‘quantity of the phases, Furthermore, it applies only to a system in stable ‘equilibrium and does not determine the rate at which this equilibrium is at- tained. ‘The importance and the practical application of the phase rule are illus- trated through the following examples: Example 1-4, For a single-component system, determine the number of degrees of freedom required for the system to exist in the single-phase region. Solution. Applying Equation 1-12, gives F = 1-1 +22. There are two degrees of freedom that must be specified for the system to exist in the single phase region. These must be the pressure p and the temperature T. Example 1-5. What are the degrees of freedom allowed for a two-compo- i ‘ nent system in two phases? 3 a3 Solution, Since C = 2.andP = 2, applying Equation 1-12 yields F ~ 2 — 2 e 2 + 2 = 2. The two degrees of freedom could be the system pressure and the g system temperature, or p and the concentration (mole fraction), or some ie other combination of T, p, and composition. Example 1-6. For a three-component system, determine the number of de- agrees of freedom that must be specified for the system to exist in the one: phase region. Convergence Pressures for Hydrocarbons Solution. Using the phase rule expression gives: F = 3 ~ 1 + 2= 4. There are four independent variables that must be specified to fix the system. The variables could be the pressure, the temperature, and the mole fractions of two of the three components MULTI-COMPONENT SYSTEMS ‘The phase behavior of multi-component hydrocarbon systems in the liq- uuid-vapor region is very similar to that of binary systems. However, as the system becomes more complex with a greater number of different compo- Figure 1-9. Critical loci of binary systems. Courtesy of the Gas Processors Suppliers Association, Published in the GPSA Engineering Data Book, Tenth Edition, 1987. 1 HGES a po guaran nents, the pressure and temperature ranges in which two phases exist in- isd "3UNSS3¥é JONZDUIANOD crease significantly.22 Hydrocarbon Phase Behavior scuratod OL Reservoir Lape 12 Gitscat Point ‘Two-Phase Region Figure 1-10. Typical P-T diagram for a multi-component system. Figure 1-10 shows a typical pressure-temperature diagram of a mul component system with a specific overall composition. Although a different hydrocarbon system would have a different phase diagram, the general con- figuration is similar. ‘These multi-component p-T diagrams are essentially used to * Classify reservoirs * Classify the naturally occurring hydrocarbon systems * Describe the phase behavior of the reservoir fluid ‘To fully understand the significance of the p-T diagrams, itis necessary to identify and define the following key points on the p-T diagram: ‘© Cricondentherm (T..)—The ericondentherm is defined as the maxi- mum temperature above which liquid cannot be formed regardless of pressure (point E). The corresponding pressure is termed the criconden- therm pressure Pa. Basic Phase Behavior 23 Cricondenbar (p.,)—The cricondenbar is the maximum pressure above which no gas can be formed regardless of temperature (point D). The corresponding temperature is called the ericondenbar temperature Ty. Critical point—The eritical point for a multi-component mixture is 1e- ferred to as the state of pressure and temperature at which all intensive properties of the gas and liquid phases are equal (point C). At the criti- cal point, the corresponding pressure and temperature are called the critical pressure p, and critical temperature T of the mixture. © Phase envelope (two-phase region)—The region enclosed by the bub- ble-point curve and the dew-point curve (line BCA), wherein gas and liquid coexist in equilibrium, is identified as the phase envelope of the hydrocarbon system. Quality lines—The dashed lines within the phase diagram are called quality lines. They describe the pressure and temperature conditions for equal volumes of liquids. Note that the quality lines converge at the critical point (point ©) * Bubble-point curve—The bubble-point curve (line BC) is defined as the line separating the liquid phase region from the two-phase region. ‘* Dew-point curve—The dew-point curve (line AC) is defined as the line separating the vapor phase region from the two-phase region. ILASSIFICATION OF RESERVOIRS AND RESERVOIR FLUIDS Proper classification of a reservoir requires the knowledge of the thermo dynamic behavior of the phases present in the reservoir and forces responsi- ble for the production mechanism. In general, reservoirs are conveniently classified on the basis of the location of the point representing the initial res: ervoir pressure p; and temperature T with respect to the p-T diagram of the reservoir fluid. Accordingly, reservoirs can be classified into essentially two types. These are: © Oil reservoirs—If the reservoir temperature TT is less than the critical ‘temperature T, of the reservoir fluid, the reservoir is classified as an oil * Gas reservoirs—If the reservoir temperature is greater than the critical temperature of the hydrocarbon fluid, the reservoir is considered a gas Oil Reservoirs Depending upon initial reservoir pressure p,, oil reservoirs can be subclas- sified into the following categories:24 Hydrocarbon Phase Behavior 1. Undersaturated Oil Reservoir. Ifthe initial reservoir pressure p, (as repre- sented by point 1 on Figure 1-10), is greater than the bubble-point pressure po of the reservoir fluid, the reservoir is labeled an undersaturated oil reser- 2, Saturated Oil Reservoir. When the initial reservoir pressure is equal to the bubble-point pressure of the reservoir fluid, as shown on Figure 1-10 by point 2, the reservoir is called a saturated oil reservoir, 3. Gas-cap Reservoir. If the initial reservoir pressure is below the bubble- point pressure of the reservoir fluid, as indicated by point 3 on Figure 1-10, the reservoir is termed a gas-cap or two-phase reservoir, in which the gas or ‘vapor phase is underlain by an oil phase. The ratio of the gas-cap volume to reservoir oil volume is given by the appropriate quality line Crude oils cover a wide range in physical properties and chemical compo- sitions, and itis often important to be able to group them into broad catego- ries of related oils. In general, crude oils are commonly classified into the following types: Ordinary black oil * Low-shrinkage crude oil © High-shrinkage (volatile) crude oil © Near-eritical crude oil The above classification is essentially based upon the properties exhibited by the crude oil, including: * Physical properties * Composition oil ratio ‘ Appearance ‘ Pressure-temperature phase diagram Note that the reservoir temperature also plays a role in the classification of the crude oil. 1. Ordinary Black Oil. A typical p-T phase diagram for an ordinary black oil is shown in Figure 1-11. The phase diagram is characterized by quality lines that are approximately equally spaced. Following the pressure reduc- tion path as indicated by the vertical line EF on Figure 1-11, the liquid shrinkage curve, as shown in Figure 1-12, is prepared by plotting the liquid volume percent as a function of pressure. The liquid shrinkagé curve ap- proximates a straight line except at very low pressures. When produced, or- dinary black oils usually yield gas-oil ratios betwoen 200-700 scf/STB and Basic Phase Behavior 95 Liguig Gptescad Point toot Teaperacure —————> Figure 1-11. A typical P-T diagram for an ordinary black oil Pet tvrano Residval OLL paae Ligatd Volune 2 Figure 1-12. Liquid shrinkage curve for black ol.26 Hydrocarbon Phase Behavior oil gravities of 15 to 40°API. The stock-tank oil is usually brown to dark green in color. 2, Low-shrinkage Oil. A typical p-TT phase diagram for a low shrinkage ofl {s shown in Figure 1-13. The diagram is characterized by quality lines that are closely spaced near the dew-point curve. The liquid shrinkage curve, as given in Figure 1-14, shows the shrinkage characteristics of this category of crude oils. The other associated properties of this type of crude oil are: Figure 1-13. A typical phase diagram for a low shrinkage oll Figure 1-14. A typical liq- uid shrinkage curve for a low shrinkage oil Ligasd Voluse £ Basic Phase Behavior 27 * Gas-oil ratio less than 200 scf/STB © Oil gravity less than 15°APT Black or deeply colored ‘¢ Substantial liquid recovery at separator conditions as indicated by point G on the 85% quality line of Figure 1-13, 3. Volatile Crude Oil. The phase diagram for a volatile (high-shrinkage) crude oil is given in Figure 1-15. Note that the quality lines are close to- gether near the bubble point and at lower pressures they are more widely spaced. This type of crude oil is commonly characterized by a high liquid shrinkage immediately below the bubble point as shown in Figure 1-16, The other characteristic properties of this oil include: *# Gasol ratios between 2,000-3,500 scf/STB © Oil gravities between 45-55°API # Lower liquid recovery of separator conditions as indicated by point G on Figure 1-15 * Greenish to orange in color 4. Near-critical Crude Oil. If the reservoir temperature T is near the critical temperature’T, of the hydrocarbon system, as shown in Figure 1-17, the hy- drocarbon mixture is identified as a near-critical crude oil. Because all the Liguta cpsetcat Point Figure 1-15. A typical P-T diagram for a volatile crude oil28 Hydrocarbon Phase Behavior ‘quality lines converge at the critical point, an isothermal pressure drop (as shown by the vertical line EF in Figure 1-17) may shrink the rude oil from 100% of the hydrocarbon pore volume at the bubble point to 55% or les at 1 pressure 10 to 50 pi below the bubble point. The shrinkage characteristic behavior of the near-crtical crude oil is shown in Figure 1-18. Ligeid Volume Figure 1-16. A typical liquid shrinkage curve for a volatile crude oil Figure 1-17. A schematic phase diagram for the near-crtical crude oil. Basic Phase Behavior 29 100 50 Liquie Voluse Pressure Figure 1-18. A typical liquid shrinkage curve for the near-critical crude ol. Gas Reservoirs In general, if the reservoir temperature is above the critical temperature of the hydrocarbon system, the reservoir is classified as a natural gas reser- voir. Natural gases can be categorized on the basis of their phase diagram ‘and the prevailing reservoir condition into four categories: ‘ Retrograde gas-condensate ‘* Near-critcal gas-condensate # Wet gas © Dry gas Retrograde Gas-condensate Reservoir. Ifthe reservoir temperature T lies be- ‘tween the critical temperature T. and cricondentherm T.; of the reservoir fluid, the reservoir is classified as a retrograde gas-condensate reservoir. This category of gas reservoir is a unique type of hydrocarbon accumulation in that the special thermodynamic behavior of the reservoir fluid is the control- ling factor in the development and the depletion process of the reservoit. Consider that the initial condition of a retrograde gas reservoir is repre sented by point 1 on the pressure-temperature phase diagram of Figure 1-19, Because the reservoir pressure is above the upper dew-point pressure, the hydrocarbon system exists as a single phase (ic., vapor phase) in the reser- voir, As the reservoir pressure declines isothermally during production from the initial pressure (point 1) to the upper dew-point pressure (point 2), liquid begins to condense. As the pressure is further decreased, instead of expand. ing (if a gas) or vaporizing (if a liquid) as might be expected, the hydrocar-30 Hydrocarbon Phase Behavior See egerim cae Figure 1-19. A typical phase diagram of a retrograde system. 1auid drop-out T cle Ligute vot ° T Figure 1-20. A typical liquid drop-out curve. bon mixture tends to condense. This retrograde condensation process contin- ues with decreasing pressure until the liquid drop-out reaches its maximum at point 3. However, at point 4, the dew-point curve must be crossed again. ‘This means that all the liquid which formed mast vaporize because the sy- tem is essentially all vapor at the lower dew-point. “The lguldsifukage vlumo curv, eommorly called the Kiquid drop-out curve, for a condensate system is shown in Figure 1-20. In most gas-conden- Basie Phase Behavior 31 sate reservoirs, the condensed liquid volume seldom exceeds more than 10% of the pore volume. This liquid saturation is not large enough to allow any liquid flow. It should be recognized, however, that around the wellbore where the pressure drop is high, enough liquid drop-out might accumulate to give two-phase flow of gas and retrograde liquid, The associated physical characteristics of this category are: * Gas-oil ratios between 8,000 to 70,000 scfiSTB. Generally, the gas-oil ratio for a condensate system increases with time due to the liquid drop- ‘out and the loss of heavy components in the liquid. # Condensate gravity above 50°API # Stock-tank liquid is usually water-white or slightly colored. Near-critical Gas-condensate Reservoir. Ifthe reservoir temperature is near the critical temperature, as shown in Figure 1-21, the hydrocarbon mixture is classified as a near-eritical gas-condensate. The volumetric behavior of this category of natural gas is described through the isothermal pressure de- lines as shown by the vertical line 1-3 in Figure 1-21 and also by the corre- sponding liquid drop-out curve of Figure 1-22. Because all the quality converge at the critical point, a rapid liquid build-up immediately below the dew-point will result (Figure 1-22) as the pressure is reduced to point 2. critical poine Pressure Figure 1-21. A typical phase diagram for a near crtical-crtical gas condensate reservoir32 Hydrocarbon Phase Behavior a Figure 1-22. Liquid shrinkage curve for a near-critical gas-condensate system. Ligutd votunes ‘This behavior can be justified by the fact that several quality lines are crossed very rapidly by the isothermal reduction in pressure. At the point ‘where the liquid ceases to build up and begins to shrink again, the reservoir goes from the retrograde region to a normal vaporization region. Wet Gas Reservoir. A typical phase diagram of a wet gas is shown in Figure 1.23, where reservoir temperature is above the cricondentherm of the hy- drocarbon mixture. Because the reservoir temperature exceeds the ericon- dentherm of the hydrocarbon system, the reservoir fluid will always remain in the vapor phase region as the reservoir is depleted isothermally, along the vertical line A-B. However, as the produced gas flows to the surface, the pressure and temperature of the gas will decline. If the gas enters the two- phase region, a liquid phase will condense out of the gas and be produced from the surface separators. ‘Wet gas reservoirs are characterized by the following properties: ‘© Gas-oil ratios between 60,000 to 100,000 sef/STB © Stock-tank oil gravity above 60°APL ‘© Liquid is water-white in color © Separator conditions, i.e., separator pressure and temperature, lie within the two-phase region Dry Gas Reservoir. The hydrocarbon mixture exists as a gas both in the res- ervoir and the surface facilities. The only liquid associated with the gas from a dry gas reservoir is water. A phase diagram of a dry gas reservoir i given in Figure 1-24. Usually a system having a gas-oil ratio greater than 100,000 scf/STB is considered to be a dry gas. Basic Phase Behavior 33 eritical point INITIAL RESERVOTR tiger Temperature > Figure 1-23. Pressure-temperature diagram for a wet gas reservoit Pressure ——» / Toneronure Figure 1-24. A typical pressure-temperature diagram for dry gas reservoir.u Hydrocarbon Phase Behavior ‘PROBLEMS 1. A pure component has the following vapor pressure: TF 104 40 176 a2 Pos Bi 46.09 195.04 345.19 713.75 a. Plot the above data so as to obtain a nearly straight line b. Determine the boiling point at 200 psi c. Vapor pressure at 250°F 2. ‘The critical temperature of a pure component is 260°F, The densities of the liquid and vapor phase at different temperatures are: oF 86. Le 158 212 pu. loin | 40.28 38.16 35.79 30.89 Lp, Wit? 0.886 1g | 2.402 5.054 | Determine the eritical density of the substance. 3. Using the Lee and Kesler vapor correlation, calculate the vapor pres- sure of i-butane at 10°F. Compare the calculated vapor pressure with that obtained from the Cox charts. 4, Calculate the saturated liquid density of n-butane at 200°F by using: a, The Rackett correlation. D. The modified Rackett correlation. 5. What is the maximum number of phases that can be in equilibrium at constant temperature and pressure in one-, two-, and three-compo- nent systems? 6, For a sever-component system, determine the number of degrees of freedom that must be specified for the system to exist in the following regions: a. One-phase region b. Two-phase region ‘7. Figure 1-8 shows the phase diagrams of eight mixtures of methane and ethane along with the vapor pressure curves of the two components. Determine: a. Vapor pressure of methane at ~ 160°F . Vapor pressure of ethane at 60°F . Critical pressure and temperature of mixture 7 d. Cricondenbar and cricondentherm of mixture 7 Basic Phase Behavior 35 €. Upper and lower dew-point pressure of mixture 6 at 20°F £. The bubble-point and dew-point pressures of mixture 8 at 60°F 8, Using Figure 1-8, prepare and identify the different phase regions of the pressure-composition diagram (commonly called the F-X diagram) for the following temperatures: a. — 120°F b, 20°F 9. Using Figure 1-8, prepare the temperature-composition diagram (commonly called the FX diagram) for the following pressures: a, 300 psia b, 700 psi . 800 psia __ REFERENCES Clark, N., “It Pays to Know Your Petroleum,” World Oil, March 1953, Vol. 136, pp. 165-172, Gibbs, J. W., The Collected Works of J. Willard Gibbs, Trans. Conn. Acad. Arts Sci, Vol. 1, Yale University Press, New Haven, reprinted 1948; original text published 1876. Lee, B. I. and Kesler, M. G., “A Generalized Thermodynamics Correla- tion Based on Three-parameter Corresponding States,” AIChE Journal, Vol. 21, No. 3, May 1975, pp. 510-527. |. Pitzer, K. $., “The Volumetric and Thermodynamics Properties of Flu- ids,” J. Amer. Chem. Soc., Vol. 77, No. 13, July 1955, pp. 3427-3433, Rackett, H. G., “Equation of State for Saturated Liquids,” J. Chem. Eng. Data, Vol. 15, No. 4, 1970, pp. 514-517. Spencer, F. F. and Danner, R. P, “Prediction of Bubble-point Density of Mixtures,” J. Chem, Eng. Data, Vol. 18, No. 2, 1973, pp. 230-234. Yamada, T. and Gunn, R., “Saturated Liquid Molar Volumes: The Rack- ‘ett Equation,” J. Chem. Eng, Data, Vol. 18, No. 2, 1973, pp. 234-936.2 Pure Component Physical Properties and Characterizing Undefined Petroleum Fractions Many of the physical properties of pure components have been measured and compiled over the years. These properties provide essential information for studying the volumetric behavior and determining the thermodynamic properties of pure components and their mixtures. The most important of these properties are: © Critical pressure, pe ‘Critical temperature, T. © Critical volume, Ve ‘Critical compressibility factor, Z, * Acentrie factor, o # Molecular weight, MW Petroleum engineers are usually interested in the behavior of hydrocarbon mixtures rather than pure components. However, the above characteristic constants of the pure component can be used with the independent state variables such as pressure, temperature, and composition to characterize and define the physical properties and the phase behavior of mixtures. This chapter's primary objective is review. Several of the well-established physical property correlations are presented to illustrate how they can be lused if no experimental data are available on the petroleum fraction. ‘GENERALIZED CORRELATIONS FOR ESTIMATING __ PHYSICAL PROPERTIES OF HYDROCARBON FRACTIO! ‘There are numerous correlations for estimating the physical properties of petroleum fractions, Most of these correlations use the specifi gravity y and the boiling point T, as correlation parameters. Selecting proper values for 36 Pure Component Properties/Characterizing Undefined Fractions 37 the above parameters is very important because slight changes in these pa- rameters can cause significant variations in the predicted results. Several of these correlations are presented below. A ized Correlations // iazi-Daubert Gener Riazi and Daubert (1980) developed a simple two-parameter equation for predicting the physical properties of pure compounds and undefined hydro- carbon mixtures. The proposed generalized empirical equation is based on the use of the normal boiling point and the specific gravity as correlating parameters. The basic equation is: On aThy @) where any physical property normal boiling point, °R specific gravity correlation constants are given in Table 2-1 for each prop- erty Table 2-1 Correlation Constants for Equation 2-1 Deviation % e b c ‘Average Maximum “4.5679 » 10°* aie 1016s 26 118 Jin 242787 Ossses = 03596 1.3 108 papsia 312281109 29125 2s21 at 93 Veto 75214 x 10"? 0206-07685 23 8a ‘The average error for each property is given in Table 2-1. ‘The prediction accuracy is reasonable over the boiling point range of 100- 850°F, Riazi and Daubert (1987), in their development of new correlations for improving the prediction of physical properties of petroleum fractions, con- sidered various factors. These factors were accuracy, simplicity, generality, availability of input parameters, extrapolatability, and finally, comparabil- ity with similar correlations developed in recent years. ‘The authors proposed the following modification of Equation 2-1, which ‘maintains the simplicity of the previous correlation while significantly im- proving its accuraey:38 Hydrocarbon Phase Behavior @ = 2 0} OL EXP (dO; + € © + FO; Oy] where = any physical property e-f = constants for each property Riazi and Daubert stated that @; and ©, can be any two parameters ca- pable of characterizing molecular forces and molecular size of a compound, ‘They identified (T,, 1) and (MW, 7) as appropriate pairs of input parame- ters in the above equation. The authors finally proposed the following two forms of the generalized correlation: Form 1. In this form, the boiling point T, and the specific gravity of the petroleum fraction are used as correlating parameters. © = a Ty EXP [A Ty +07 + FT 7] ) ‘The constants a-f for each property @ are given in Table 2-2. Table 2-2 Correlation Constants for Equation 2-2 ° 5 © aw 581.96 97476 e5i2ra Toth 10.8463 0.81067 0.53691 Be. psia 6.162 x 108 ~ 0.4946 4.0046 Ve, tf 6.238 x 10-* 0.7506 ~ 1.2028 e e 1 643076 x 10-* =o5sse4 1.11056 x 10-° = 5.1747 x 10-* To5eaas 315996 x 10"* = 4.725 x 10-2 = 4p014 3.1998 x 10-9 = 1.4879 x 10-9 = 0.26008 41.095 x 10"* Form 2. In this form, molecular weight MW and specific gravity -y of the component are used as correlating parameters. © = a (MW) 7 EXP [d (MW) + ey + £ (MW) 7] 23) where the correlation constants are given in Table 2-3. In developing and obtaining the coefficients of the above two correla- tions, Riazi and Daubert used data on the properties of 38 pure hydrocar- bons in the carbon number range 1-20, including paraffins, olefins, Pure Component Properties/Characterizing Undefined Fractions 39 Table 2.3, Correlation Constants for Equation 2-3 b e 0.2988 1.0585 es, psia 4.5203 x 10" 018063 1.6015 Ve 18M 1.206 > 10-7 0.20378 ~ 113096 TOR 67887 o.aor673 = 1158262 i a e t 13478 x 10" ~osieat 00 - = 18078 x 10° = 0.3084 00 = 21857 x 10-2 0.5207 2.6012 x 10-2 8.7409 x 10°> 2.984036 = 425288 x 10-2 the naphthenes, and aromatics in the molecular weight range 70-300 a boiling point range 80-650°F. Lin-Chao Generalized Correlation Lin and Chao (1984) correlated the physical properties of hydrocarbon components with the molecular weight, specific gravity, and normal boiling point. The proposed correlation was developed by using perturbation the- ‘ory; it contains 33 numerical constants for each physical property. The phys- ical properties of C, to Cy n-alkanes (n-paraffins) were correlated with the molecular weight. Properties of other hydrocarbons and derivatives were expressed as perturbations from those of the n-paraffins with the boiling point and the specific gravity as the correlating parameters Lin and Chao expressed the physical properties of C, to Coy n-alkanes by the following generalized equation @q = Cy + Cx(MW) + CMW)? + CMW)? + Cy(MW) (2-4) where O, represents either T., In(pJ, Ve, (# *T,), of Ty of a n-alkane. The coefficients C; to Cs are reported in ‘Table 2-4, ‘The correlation produced an average absolute deviation of 0.15% for To, 1.0% for p, excluding methane), 1.2% for w, 0.11% for Ty, and 0.07% for +7, when compared to the physical properties value, as listed in the American Petroleum Institute project 44 table values. Properties of the general hydro- carbons and derivatives were correlated as perturbations of those of n-al kanes according to the following equation:40 Hydrocarbon Phase Behavior “Table 2-4 Costticients for Ox in Equation 2-4 & SEENICs 7. 0A woe 7056062 iio. 6759446 = darore ot ~ 26.21598 2200516 ro 0.65405 {4st00 x 10-2 wen 240.976 Ssowaee Comnnaai & & = aneii6708 Berea «0; ~a100202 2551406 x 10-4 -a7s776 10"* 350737 rracaee x 10> = 9685056 x 10-* = 128:35094 = S702 x 10-* e2i4i4 x 10°? weaseie = .012761604 19,8405 x 10-4 = 2.029.158 ee : = Gy +A, Ay + Az ATy + Ay (Ay)? + Ag (Ay) (ATA) + As (ATL)? + Ag (Ay)? + Ay (Ay)? (ATs) + As (Ay) (ATL)? + Aa (ATL)? (25) with Ay=7-% ATy = Ty ~ (Tie 4 where +y = specific gravity of the substance of interest 4, Ty = boiling point of the substance of interest, °R_“'* ‘1m (Ti)s = specific gravity and boiling point of a hypothetical n-al- kane with a molecular weight (MW) of the substance of interest (given by Equation 2-4), ‘The coefficients A,~As in Equation 2-5 are given by the following expres- (2-6) where values of the coefficients a, and b, are listed in Table 2-5. ‘The proposed correlation can be best explained through the following ex- ample: Example 2-1. Estimate the critical temperature of a petroleum fraction with a boiling point of 731°R, specific gravity of 0.7515 and molecular ‘weight of 127 by using the Lin and Chao method. Solution. : Step 1. Using Equation 2-6, calculate the critical temperature (T.), spe- cific gravity 7,, and boiling point (T,), of a hypothetical n-alkane Pure Component Properties/Characterizing Undefined Fractions 41 Table 2-5 Coefficients tor Equation 2-6 a 8S onis7e 2.008702 x 10° a = 5.68509 ~ 1.844466667 x 10-* 3.48210 a = 219a62 x 10" © — 86.0975 5.000706 x 10* a 75.0863 o.soseatiti1 = 2.05257 x 10 a ~5.3668056 x 10-* ~ 2.777868860 x 10-* 0.2532090009 a 8.908016 x 10* 1.85927 x10? 7.19722 x 10" a = 1.87999 x 108 ~ 018396277778 5.08888 x 10° os 0.20029 1.99582716 x 10-? ~ 0.3390405556 a = 0.851117204 x 10° 0.6541941015 x 10-% 0.5207160494 x 10-2 be = 2131776 = 75087 x 10-8 3.418698 be 5.77384 x 10-2 4.759989993 x 10°? 2.61662 x 10-7 bs 1.992546 x 10? o.saze54 = 4.014316 x 108 be ~ 0.858450 = 2.p97022222 x 10°? 2.06071 be 4.346186667 x 10-+ 2.430015492 x 10-* ~ 2900589333 x 10-? be ~ 367.841 ~ 1.85490 “7.66070 x 10° b 1.32064 o.75seaa8080 x 10-* 5.75141 be = 126440556 x 10-2 ~ 0,9997808642 x 10°F 4.814816867 x 10°? be 21598461358 x 10-7 0.5753412200 x 10-* 05407067001 x 10-* with a molecular weight of 127. These applications produce the following results (1), = 1,067.8°R = 0.1977 (i), = 759.19°R Step 2. Calculate the coefficients A, by using Equation 2-6. A, = 137.09 Ag = L647 Ay = 8,406,714 Ay= 8.5579 As ~ 0.001508 Ay = ~ 7,610.25 A= 9.72928 Ay = 0.03971 ‘Ay = ~ 000005084 Step 3. Solve for . by applying Equation 25. Ay = 0.7515 - 0.7977 = ~ 0.0462 AT, = 731 ~ 759.19 = ~ 28.19 Te = 1,067.8 + 137.09( ~ 0.0462) + 1.6477( ~ 28.19) + 3,406.714( — 0.0462)? — 8.5579( — 0.0462)( ~ 28.19) + 0.001508 — 29.19)? ~ 7,610.25( ~ 0.0462) + 9.72228 ( ~ 0.0462)? ( ~ 28.19) + 0.03971 ( ~ 0.0462)( - 28.19) ~ 0,00005084{ - 28.19}? = 1,012.2°R42 Hydrocarbon Phase Behavior ‘OTHER METHODS OF ESTIMATING PHYSICAL PROPERTIES OF PETROLEUM FRACTIONS Pure Component Properties/Cheracterizing Undefined Fractions 43 5 1 caveres Correlations _// Cavett (1962) proposed correlations for estimating the critical pressure and temperature of hydrocarbon fractions. The correlations have received a ‘wide acceptance in the petroleum industry due to their reliability in extra- polating at conditions beyond those of the data used in developing the corre- lations. The proposed correlations were expressed analytically as functions of the normal boiling point Ty and API gravity. Cavett proposed the follow- ing expressions for estimating the critical temperature and pressure of petro- Jeu fractions: Critical Temperature Ty = ay + ay Ty + ay TH + ay (APD(TS) + aT)? + as(API)(T)* + as (APL)? (Th)? (27) Critical Pressure Log (p.) = by + by (To) + by (Ta)? + by (API) (Ta) + by (To)? + bs (API) (T.)® + be (API)? (Ix) + br (API? (TL)? (2-8) where T, = critical temperature, °R po = critical pressure, psia ‘Ty = normal boiling point, °F API = API gravity of the fraction ‘The coefficients of Equations 2-7 and 2-8 are tabulated in Table 2-6. Cavett presented these correlations without reference to the type and source(s) of data used for their development. y ns U/ Kesler-Lee Cori Kesler and Lee (1976) proposed a set of equations to estimate the critical temperature, critical pressure, acentric factor, and molecular weight of pe- troleum fractions. The equations, as expressed below, use specific gravity and boiling point in °R as input parameters. Table 2-6 Coetticients of Equations 2-7 and 2-8 1 a b ° 768.07121 2aps0406 1 1.7183693, (094120109 x 10" 2 = 0.0010834003 = 090474749 x 10-* 3 = 0.0089212579 = 020876110 x 10-* 4 0.99890588 x 10-* 0.16184108 x 10" 5 (053094920 x 10-* (0.11047899 x 10-? 6 0.32711600 x 10-7 = 0148271598 x 10-7 7 = (019949619 x 10°" Caitical Pressure aaa (tes) In (p) = 8.3634 — 0.0566/y ~ (0.24944 + 2.9898/+y + 0.11857/4*)10-° Ty, + (1.4685 + 3.648/y + 0.47297/2)10-7 T,? - (0.42019 + 1.6977/y")10-"° TY 9 Critical Temperature Ty = 41.7 + SILL y + (0.444 + 0.1174) Th + (0.4669 - 3.26238) 10°/T,, (2-10), Molecular Weight MW = ~ 12,272.6 + 9,486.4 + (4.6525 ~ 3.32877) Ty + (1 = 0.77084y ~ 0.020584)(1.3437 ~ 720.79/T,)10"7Ts ++ (1 = 0.80882y + 0.022264)(1.8828 ~ 181.98/T,)104/T? (eu) The above equation was obtained by regression analysis using the avail- able data on molecular weights ranging from 60 to 650. ‘Acentrie Factor. Defining the Watson characterization factor K and the re- duced boiling point © by the following relationships x- Y44 Hydrocarbon Phase Behavior where Ty = boiling point, °R Kesler and Lee proposed the following two expressions for calculating the acentric factor For @>0.8: = ~ 7.904 + 0.1352K ~ 0.007465K? + 8.359 8 + (1.408 ~ 0.01063K)/9 (2-12) For 0<0.8: —In(p./14.696) — 5.92714 + 6.09648/0 + 1.28862 In(@) ~ 0.169347 08 15.251 15.6875/0 ~ 13.4721 In(O) + 0. (213) where pe = critical pressure, psia T, = critical temperature, °R Ty = boiling point, °R @ = acentric factor MW = molecular weight +7 = specific gravity Kesler and Lee stated that Equations 2-9 and 2-10 give values for p, and ‘T, that are nearly identical with those from the API Data Book up to a boil- {ng point of 1,200°F. Modifications were introduced to extend the correla tions beyond the boiling point limit of 1,200°F. These extensions (extrapola- tions) were achieved by ensuring that the critical pressure approaches the atmospheric pressure as the boiling point approaches critical temperature. Hf Wixm-Siva-Daubert Correlations _// Sim and Daubert (1980) concluded that the Winn (1957) nomograph is the mast accurate method for characterizing petroleum fractions. For this reason, Sim and Daubert represented the critical pressure, critical tempera- ture, and molecular weight of the Winn nomograph analytically by the fol- lowing equations: 48242 x 10? Ty 25177 44865 Ty = EXP [3,9094718 122" yoo — MW se) 15) “4d50476 x 10-9 TEI"! YS (@16> Pure Component Properties/Characterizing Undefined Fractions 45 where p. = critical pressure, psia ‘T, = critical temperature, °R T,, = boiling point, °R ‘Watansiri-Owens-Starling Correlations Watansiri, et. al. (1985) developed a set of correlations to estimate the critical properties and acentric factor of coal compounds and other hydro- carbons and their derivatives. The proposed correlations express the charac- terization parameters as functions of the normal boiling point, specific grav- ity, and molecular weight. These relationships have the following forms: Critical Temperature In(T,) = ~ 0.0650504 ~ 0.005217 7, + 0.03095 In(MW) + 1.11067 In(Ty) + MW [0.078154 ‘ = 0.061061 +! ~ 0.016943 4} (217) where T, = critical temperature, °R Critical Volume In(V,) = 76.313887 - 129.8038 y + 63.1750 4 ~ 13.175 + 1.10108 In(MW) + 42.1958 In(q) (218) where V, = critical volume, ft?lb-mole Critical Pressure In(p.) = 6.6418853 + 0.01617283 (JV) ~ 8.712(MWIT) ~ 0.08843889(T,/MW) (2-19) critical pressure, psia where pe Acentric Factor wo = [5.12916667 x 10-* Ty, + 0.281826067(TYMW) + 382.904/MW + 0.074691 x 10-%(Ty/y)? ~ 0.12087778 x 10-4(T)(MW) + 0.001261(y)(MW) + 0.1265x10~4 (MW)? + 0.2016x10-# ()(MW)! — 66.29959(T,)!"/MW = 0.00255452 1.29/41 TH(9 MW) (2-20) ‘The proposed correlations produce an average absolute relative deviation of 1.2% for Te, 3.8% for Ve, 5.2% for pe, and 11.8% for a.46 Hydrocarbon Phase Behavior . YL eamisters Corration Edmister (1958) proposed a correlation for estimating the acentric factor of pure fluids and petroleum fractions. The equation, widely used in the petroleum industry, requires boiling point, critical temperature, and eritical pressure. The proposed expression is given by the following relationship: 3[Log (p/14.70) _ ~ oe eat (2-21) where w = acentric factor pe critical pressure, psia Ty = critical temperature, °R ‘Ty = normal boiling point, °R If the acentrie factor is available from another correlation, the Edmister equation can be rearranged to solve for any of the three other properties (providing the other two are known). (CRITICAL COMPRESSIBILITY FACTORS ‘The critical compressibility factor is defined as the component compress- ibility factor calculated at its critical point, This property can be conve- niently computed by the real gas equation-of-state at the critical point, or pe Ve he (2-20 RT. aeeet where R = universal gas constant, 10.73 psia.ft'/Ib-mole.°R Ve = critical volume, ft'lb-mole If the critical volume Ve is given in ft/lb, Equation 2-22 is written as _VeMW ccnawT where MW = molecular weight V.. = critical volume, ft/lb ‘The accuracy of Equation 2-22 depends on the accuracy of the valies of p., TT, and V,. Table 2-7 presents a summary of the critical compressibility est- mation methods. ‘Pure Component Properties/Characterizing Undefined Fractions 47 ‘Table 2-7 Critical Compressibility Estimation Methods Method z Equation No. Haugen 169m 286 + Bat) 223 FRoid-Prausnitz- ‘Sherwood 1977 Z=0.291 0.080 224 Salome ota 1985 Z = 0201 - 0.800 0.018 uF 225 Nath 1985 = 02918 - 0.0928 w 226 ‘Ware oi he aoeniia factor Example 2-3. Estimate the critical properties, molecular weight, and centric factor of a petroleum fraction with a boiling point of 198°F and specific gravity of 0.7365, by using the following methods: Riazi-Daubert (Equation 2-1) Riazi-Daubert (Equation 2-2) Cavett's Kesler-Lee Winn-Sim-Daubert Watansiri-Owens-Starling pusepr Solution. 1, Riazi-Daubert: Equation 2-1 © MW = 4.5673 x 10-* (858)? 2 (0.7365) "101 = 96.4 ©, = 24.2787 (658)°5 (0.7365) = 990.67°R fp. = 3.12281 x 10° (658)-*525 (0.7365) = 466.9 psia 2 V. = 7.5214 x 10-9 (658)°% (0.7365) 97% = 0.06227 ft/lb # Solve for Z_ by applying the above calculated properties in Equation 06227)(96.4) (0.73) (o90.67) —~ 26355 © Solve for w by applying Equation 2-21: = Sillog (466.9714.7)] 7 [(@00.677658) —1) 17° a 2, Riazi-Daubert: Equation 2-2 Applying Equation 2-2 and using the appropriate constants yields:48 Hydrocarbon Phase Behavior * MW = 96.911 eT, = 986.7 °R ep, = 465.83 psia ©V. = 0.06257 feb « Solve for the acentrie factor and the critical compressibility factor by applying Equations 2-21 and 2-22, respectively: ¢u = 0.2877 © Z, = 0.2668 3, Cavett’s Correlation: « Solve for T. by applying Equation 2-7: T, = 978.1 °R © Caleulate p. with Equation 2-8: Pe = 466.1 psia © Solve for the acentric factor by applying the Edmister correlation, Equation 2-21: =1=0.3147 © Compute the critical compressibility by using Equation 2-25; Z, = 0.291 ~ (0.08)(0.3147) ~ 0.016 (0.8147)? = 0.2642 ‘* Estimate V, from Equation 2-22: Z_R Tz _, (0.2642)(10.731)(980) = 5.9495 f/lb-mole Pe 466.1 Assume MW = 96 y, = 5:95 _ 9.06197 feb 4. Kesler-Lee * Calculate p, from Equation 20 pe = 470 psta * Solve for T. by using Equation 2-10: 1. = 990 °R : 5 * Calculate the molecular weight MW by using Equation 2-11 MW = 98.7 Pure Component Properties/Characterizing Undefined Fractions 49 ' * Compute the Watson characterization factor K and the parameter 0: (658)! | ~ ocraes “118 658 0 = 88 ap 70-67 © Solve for acentrie factor by applying Equation 2-13: 0 = 0.306 ‘ Estimate for the critical gas compressibility Z, by using Equation 2-26: Z, = 0.9918 — (0,0928)(0.306) = 0.2634 © Solve for V. by applying Equation 2-22: Ze RT, (0.2634)(10.73)(980) peMW — (470)(08.7) = 0.0597 Ibift? 5. Winn-Sim-Daubert: ‘* Estimate pe from Equation 2-16: Po = 478.6 psi * Solve for T. by applying Equation 2-15: T. = 979.2°R © Calculate MW from Equation 2-16: MW = 95.93 © Solve for the acentric factor from Equation 2-21: @ = 0.3280 * Solve for Z, by applying Equation 2-24: Z, = 0.291 ~ (0.08)(0.3980) = 0.2648 © Calculate the critical volume V. from Equation 2-22: __ (0.2848)(10.731)(979.2) oR EER 7 00080 feb 6, Watansiri-Owens-Star © Because Equations 2-17 through 2-19 require the molecular weight, as- sume MW = 9650 Hydrocarbon Phase Behavior ‘© Calculate T, from Equation 2-17: T, = 980.0 °R ‘¢ Determine the critical volume from Equation 2-18 to give ‘V, = 0.06548 fe°/Ib, «@ Solve for the critical pressure of the fraction by applying Equation 2-19 to produce P, = 426.5 psia ‘© Calculate the acentrie factor from Equation 2-20 to give = 0.2282 ‘© Compute the critical compressibility factor by applying Equation 2-26 Z, = 0.27112 ‘Table 2-8 summarizes the results of Example 2-3, Table 2-8 ‘Summary of the Calculated Results of Example 2-3 v % 6b. Method oA ia__mole SMW z FiaziDaubert No.1 99067 4659 0.06227 964 0.2731 0.26065 RiaziOaubert No.2 986.7 465.83 0.06257 96.911 02877 0.668 Cavett g7e1 466.1 0.06197 ——O3147 0.2642 KeslorLee 980 © 479.«=0.0597 987 0.3060 0.2834 Winn 979.2 478.8 0.06059 96.99 (0.9280 0.2648 Watansi 900° 4265 006548 = — aaa? zTII2 (CHARACTERIZING HYDROCARBON HEAVY FRACTIONS ‘Nearly all naturally occurring hydrocarbon systems contain a quantity of heavy fractions that are not well defined and are not mixtures of discretely {identified components. These heavy fractions are often lumped together and identified as the plus fraction, e.g., Cr. fraction. ‘A proper description of the physical properties of the plus fractions and other undefined petroleum fractions in hydrocarbon mixtures is essential in performing reliable phase behavior calculations and compositional model- ing studies. Frequently a distillation analysis or a chromatographic analysis {s available for this undefined fraction, Other physical properties such as Pure Component Properties/Characterizing Undefined Fractions 51 molecular weight and specific gravity may also be measured for the entire fraction or various cuts of it. ‘To use any of the thermodynamic property-prediction models, e.g, equa- tion of state, to predict the phase and volumetric behavior of complex hy- drocarbon mixtures, one must be able to provide the acentric factor, critical temperature, and critical pressure for both the defined and undefined (heavy) fractions in the mixture. The problem of how to adequately charac- terize these undefined plus fractions in terms of their critical properties and acentric factors has been long recognized in the petroleum industry. Whit- son (1984) presented an excellent documentation on the influence of various heptanes-plus (C;) characterization schemes on predicting the volumetric behavior of hydrocarbon mixtures by equations-of-state Numerous characterization procedures have been proposed over the years. Some of the most widely accepted and used procedures are reviewed below. METHODS BASED. THE “PNA” DETERMINATION ‘The vast number of hydrocarbon compounds making up naturally occur- ring crude oil have been grouped chemically into several series of com- pounds. Each series consists of those compounds similar in their molecular make-up and characteristics. Within a given series, there exist compounds ranging from extremely light, or chemically simple, to heavy, or chemically complex. In general, it is assumed that the heavy (undefined) hydrocarbon fractions are composed of three hydrocarbon groups, namely: «© Paraffins (P) © Naphthenes (N) Aromatics (A) ‘The PNA content of the plus fraction of the undefined hydrocarbon frac- tion can be estimated experimentally from a distillation analysis and/or a chromatographie analysis. Both types of analysis provide information valu- able for use in characterizing the plus fractions. In the distillation process, the hydrocarbon plus fraction is subjected to standardized analytical distillation, first at atmospheric pressure, and then ina vacuum at a pressure of 40 mm Hg. Usually the temperature is taken when the first droplet distills over. Ten fractions (cuts) are then distilled off, the first one at 50°C and each successive one with a boiling range of 25°C. For each distillation cut, the volume, specific gravity, and molecular weight, among other measurements, are determined. Cuts obtained in this manner are identified by the boiling-point ranges in which they were collected,52 Hydrocarbon Phase Behavior Generally, there are five different methods of defining the normal boiling point for petroleum fractions. These are: 1, Volume Average Boiling Foint (VABP), which is defined mathemati- cally by the following expression: VABP = )) vi Tux (2-27) T where T= boiling point of the distillation cut i, °R vi = volume fraction of the distillation cut i 2. Weight Average Boiling Point (WABP), defined by the following ex- pression: WABP = JO w, Tw (2-28) where w, = weight fraction of the distillation cut i 3. Molar Average Bolling Point (MABP), given by the following relation- ship: MABP = J) x; Ty (2-29) 7 where x; = mole fraction of the distillation cut i 4, Cubie Average Boiling Point (CABP) which is defined as Pp CABP =|) x: nerf (2-0) 5. Mean Average Boiling Point (MeABP): MeABP = Mapp ons? (231) As indicated by Edmister and Lee (1984), these five expressions for caleu- lating normal boiling points result in values that do not differ significantly from one another for narrow boiling petroleum fractions. Figure 2-1 shows a typical graphical presentation of the molecular weight, specific gravity, and the true boiling point TBP as a function of the volume fraction of liquid vaporized. It should be pointed out that when a single boiling point is given for a plus fraction, itis given as its Volume Aver- age Boiling Point. ‘Bergman et al. (1977) outlined the chromatographic analysis’ procedure by which distillation cuts are characterized by the density and molecular ‘weight as well as Weight Average Boiling Point, Pure Component Properties/Characterizing Undefined Fractions 53 Figure 2-1. Properties of a crude oil fraction. All three parameters (i.e, molecular weight, specific gravity, and VABP/ WABP) are employed, as discussed below, to estimate the PNA content of the heavy hydrocarbon fraction which in turn is used to predict the critical properties and acentric factor of the fraction. Hopke and Lin (1974), Erbar (1977), Bergman et al. (1977), and Robinson and Peng (1978) have used the PNA concept to characterize the undefined hydrocarbon fractions. As a rep- resentative of this characterization approach, the Robinson-Peng method and the Bergman method are discussed below. Robinson-Peng Method Robinson and Peng (1978) proposed a detailed procedure for characteriz- iiig heavy hydrocarbon fractions. The procedure is summarized in the fol- lowing steps: Step 1. Calculate the PNA content (Xp, Xyy X4) of the undefined fraction by solving the following three rigorously defined equations: D Mel (2-32)54 Hydrocarbon Phase Behavior (MW, Te Xi = (MW)(WABF) (2-33) Ra Dp mw. x)-Mw 34) iA where Xp = mole fraction of the paraffinic group in the undefined frac- tion Xw = mole fraction of the naphthenic group in the undefined fraction Xq = mole fraction of the aromatic group in the undefined frac- tion WABP = weight average boiling point of the undefined fraction, °R MW = molecular weight of the undefined fraction (MW) = average molecular weight of each eut, ie, PNA, (fj); = boiling point of each cut, °R Equations 2-32 through 2-34 can be written in a matrix form as follows: 1 1 1 Xe] a [MW = TyJe (MW + Tyly [MW Tula] |X) = |MW + WABP ) (2-35) (MW [MWk (MW, [Xa] MW Robinson and Peng pointed out that itis possible to obtain negative values for the PNA contents. To prevent these negative values, the authors imposed the following constraints: 0=Xps0.90 Xyz0 X20 ‘To solve Equation 2-35 for the PNA content requires the weight average boiling point and molecular weight for the cut of the undefined hydrocar- bbon fraction, If the experimental values of these cuts are not available, the following correlations proposed by Robinson and Peng can be used: Determination of (Ti (Toss and (Toa. Paraffinie group Ln(Ty) = Ln(1.8) + Y) [a(n - 6)'-!] (2-36) ‘© Naphthenic group Ln(T}) = La(l.8) + J) {a(n - 7)'-4] (237) Pure Component Properties/Characterizing Undefined Fractions 55 6 © Aromatic group Ln(Ts) = Ln(1.8) + Y) [a(a - 7) (2-38) where n= number of carbon atoms in the undefined hydrocarbon fraction 1a; = coefficients of the equations and are given in Table 2-9 Table 2-9 Coefficients a, in Equations 2-36 through 2-38, Parattin ‘Naphthene ~~ Aromatic Cootficlent Pp N a‘ 5.89451690 5.8579802 5.86747600, (0,84909035 x 10°? 0,79805995 x 10-' _0,80496947 x 10 a = 0152695420 x 10-7 - 0.49096101 x 10-2 — 0.47196506 x 10-* a (0.21252008 x 10-2 _0.14783123 x 10"? 0.18299965 x 10°? a = 0444999963 x 10-* — 0.27095216 x 10° — 0.98927290 x 10-* % 0137285965 x 10-7 __0.19907794 x 10. 0132550876 x 10-7 Determination of (MW) (MW)y, and (MW). «© Paraffinie group (MW)p = 14.026 n + 2.016 (2-39) ‘© Naphthenic group (MW)y = 14.026 n ~ 14.026 (2-40) ‘* Aromatic group (MW), = 14.026 n~ 20.074 (2-41) Step 2. Having obtained the PNA content of the undefined hydrocarbon fraction, as outlines in Step 1, calculate the critical pressure of the fraction by applying the following expression: Pe = Xe(Pode + Xn(Pedn + XaPoda (2-42) where P, = critical pressure of the heavy hydrocarbon fraction, psia ‘The critical pressure for each cut of the heavy fraction is calculated ac- cording to the following equations: _ 206.126006n 136 © Paraffinic group (P,)p = aeeeErsEareetttt (2-43) :206,126096n ~ 206.126096 (@.28in- 0.137)" ‘© Naphthenie group (P.)y = (2-44)36 Hydrocarbon Phase Behavior 206, 126096n ~ 295.007504 «Aromatic group (Pa = Sone — 5 aa (45) step 3. Calculate the acentri factor of each cut ofthe undefined fraction by using the following expressions: ¢ Paraffinic group (u)p = 0.0432n + 0.0457 (2-46) ‘© Naphthenie group (a)y = 0.0432n ~ 0.0880 (47) ‘© Aromatic group (1), = 0.0445n ~ 0.0995 (2-48) Step 4, Calculate the critical temperature of the fraction under eonsider- ation by using the following relationship: Te Xp (Top + Xn (Ton + Xa (Toda (2-49) where T, = critical temperature of the fraction, °R ‘The critical temperatures of the various cuts of the undefined fractions are calculated from the following expressions: (P,)p] — 3.501952 5 «Pate pou (Te [1M BE] ey .)~ 3.01850 « phe op =f + RAP 818 SLog{ (P.)4] ~ 3.501952 ‘Aromatic group (Te)a = Si(To)a bh eal | (2-52) where the correction factors $ and S; are defined by the following expres- § = 0.996704 + 0.000431550 8, = 0.99627245 + 0.00043155n Step 5. Calculate the acentric factor of the heavy hydrocarbon fraction by using the Edmister correlation (Equation 2-21) to give 3 tLog Pe14.7)) _ 59 7avT =H Pure Component Properties/Characterizing Undefined Fractions 37 where @ = aventric factor of the heavy fraction P, = critical pressure of the heavy fraction, psia TT, = critical temperature of the heavy fraction, °R Ty = average-weight boiling point, °R Example 2-4. Calculate the critical pressure, the critical temperature, and acentric factor of an undefined hydrocarbon fraction with a measured mo- lecular weight of 94 and a weight average boiling point of 655°R. The num- ber of carbon atoms of the component is 7 Solution. Step 1. Calculate the boiling point of each cut by applying Equations 2- 36 through 238 to give (To)p = 666.58°R, (Ty)x = 630.0°R, (Ty), = 635.85°R Step 2. Compute the molecular weight of various cuts by using Equa- tions 2-39 through 2-41 to yield (MW)p = 100.198, (MW)x = 84.156, (MW), = 78.18 Step 3. Solve Equation 2-35 for Xp, Xy, and Xa, to give Xp = 0.6313, Xy = 0.3262, Xq = 0.0495 Step 4. Calculate the critical pressure of each cut in the undefined frac- tion by applying Equations 2-43 and 2-45. (Pp = 395.7 psia, (Pv = 586.61 psia, (P.)q = 718.46 psia Step 5. Calculate the eritical pressure of the heavy fraction from Equa- tion 2-42 to give P, = 471.7 psia Step 6. Compute the acentric factor for each cut in the fraction by using Equations 2-46 through 2-48 to yield (o)p = 0.3481, (a) = 0.2144, (0) Step 7. Solve for (T.)p, (Tx, and (T.)q by using Equations 2-50 through 9-52 to give (Tp = 969.4°R, (T)y = 947.3°R, (Tea = 1014.9°R Step 8. Solve for (T) of the undefined fraction from Equation 2-49. T. = 964.1°R o.21258 Hydrocarbon Phase Behavior stop 9. Calculate the acentric factor from Equation 259, to give wo = 0.3680 Bergman's Method. Bergman et al. (1977) proposed a detailed procedure for characterizing the undefined hydrocarbon fractions based on calculating the PNA content Sf ithe fraction under consideration. The proposed procedure was originated from analyzing extensive experimental data on lean gases and condensate systems. The authors, in developing the correlation, assured that the paraf- finie, naphthenic, and aromatic groups have the same boiling point. The ‘computational procedure is summarized in the following steps: Step 1. Estimate the weight fraction of the aromatic content in the unde- fined fraction by applying the following expression: owe 847 Ky Fe 04 (rA~ ke) (254) where wa = weight fraction of aromatics K.. = Watson characterization factor, defined mathematically by the following expression: Ku = (Th)y (2-55) where _y = specific gravity of the undefined fraction T, = weight average boiling point, °R Bergman etal. imposed the following constraint on the aromatic content: 0.08. w, 0.35 Step 2. With the estimate of the aromatic content, the weight fractions of the paraffinic and naphthenie euts are calculated by sotving the following system of linear equations: wy te a (256) vey we es) © 7 where W> = weight fraction of the paraffin cut eight fraction of the naphthene cut Pure Component Properties/Characterizing Undefined Fractions 50 -y = specific gravity of the undefined fraction “resvwcia = specific gravity of the three groups at the weight aver- age boiling point of the undefined fraction. These sgravities are calculated from the following relatfon- ships: ‘yp = 0.582486 + 0.00069481 (Ty ~ 460) = 0.7572818(10-9\(T, ~ 460) + 0.3207736(10-8)(T, - 460)? (2-58) ‘yw = 0.694208 + 0.0004909267(T, ~ 460) ~ 0.659746(10-*)(T, ~ 460)* + 0.390966(10-*)(T, ~ 460)* (2-59) ‘yn = 0.916103 ~ 0.000250418(T ~ 460) + 0.357967(10"8)(Tr, - 460)? = 0.166318(10-*)(T,, - 460)? (2-60) ‘A minimum paraifin content of 0.20 was set by Bergman et al. Tb insure that this minimum value is met, the estimated aromatic content that results in negative values of wp is increased in increments of 0.03 up to a maximum of 15 times until the paraffin content exceeds 0.20. They pointed out that this procedure gives reasonable results for fractions up to Cis. Step 3. Calculate the critical temperature, the critical pressure, and acentric factor of each cut from the following expressions: © Paraffins: (op = 275.23 + 1.2061(T, ~ 460) ~ 0,00032984(T, ~ 400)? (2-61) (Pp = 573.011 ~ 1.13707(7, ~ 460) + 0.00131625(T, ~ 460) = 0,85103(10-9)(Ty, ~ 460)* (2-62) (o)p = 0.14 + 0.0009(T, ~ 460) + 0.283(10-9)(T, ~ 460)? (2-63) © Naphthenes: (Tox = 156.8906 + 2.6077(Ty ~ 460) ~ 0.003801(7, ~ 460)? + 0.2544(10-5)(Ty = 460)° (2-64) (P)y = 726.414 ~ 1.9275(T, ~ 460) + 0.9846(10-8)(T,, ~ 460)? = 0.45169(10-9)(T,, ~ 460)? (2-65) (on = (ae ~ 0.075 (2-66)60 Hydrocarbon Phase Behavior Bergman et al. assigned the following special values of the acentric factor to the Cs, Co, and Cp naphthenes. (wy = 0.26 (oy = 0.27 Gyo: (wy = 0.35 © Aromatics: (T)q = 289.535 + 1.7017(T, ~ 460) ~ 0.0015843(T, - 460)? + 0.82358(10"9(T, — 460)? (2-67) (Bq = 1.184.514 - 9.44681(T, ~ 460) + 0.0045512¢7, ~ 460)? = 0.23416(10-5)(T, — 460) (2-68) a= Wp 0.1 (2-69) Step 4. Calculate the critical pressure, the critical temperature, and the ‘centric factor of the undefined fraction from the following relationships: P. = Xe(P.)p + Xw(Paln + XalPeda (2-70) Te = Xpl(Tee + Xn(Tw + XaTea (2-71) = Xp(u)p + Xnle)y + X (2-72) ‘Whitson (1984) suggested that the Peng-Robinson and the Bergman PNA ‘methods are not recommended for characterizing reservoir fluids containing fractions heavier than Crp. ‘OTHER METHODS OF CHARACTERIZING ‘THE HYDROCARBON HEAVY FRACTIONS Rowe's Characterization Method Rowe (1978) proposed a set of correlations for estimating the normal boil- ing point, the critical temperature, and the critical pressure of the heptanes- pplus fraction, i.e., C;,. The prediction of the C;, properties is based on the assumption that the “lumped” fraction behaves as a normal pargifin hydro- carbon, Rowe used the number of carbon atoms n as the only correlating parameter. He proposed the following set of formulas for characterizing the Coy fracti Pure Component Properties/Characterizing Undefined Fractions 61 ‘ Caleulation of the eritical temperature: (Toor, = 1.8 [961 — 10") (273) where (Tor, = critical temperature of C;., °R 4 = coefficient of the equation and is given by the follow- ing expression a = 2.95597 ~ 0.090597n2° where 1 is the number of carbon atoms and is calculated from the mo- lecular weight of the C;, fraction by the following relationship: ni» (MWe, ~ 20)14 (en where MWo,, is the molecular weight of the heptanes-plus fraction, * Calculation of the critical pressure: Pde;. = 10° /(T Joy, (2-75) with Y = ~ 0.0137726826 n + 0.6801481651 where (Poy, is the critical pressure of Cr. in psi. © Calculation ofthe cstioal temperature: x!" Vic ~ (Trop, = 0.0004347(T yo, , + 265 (2-76) where (Ty)o;, is the normal boiling point in °R. Mathews, Roland, and Katz (1942) presented graphical correlations for determining the critical temperature and pressure of the heptanes-plus frac- tion. Standing (1977) expressed these graphical correlations more conve- niently in mathematical forms as follows: (Ter, = 608 + 364 Log [(MW)c, + [2,450 Log (MW)c;, -7112] 8,800] Log (aor. em Poder. 1,188 ~ 431 Log [(MW)o, ~ 61.1] + [2,319 ~ 852 Log [(MW)c;, = 53.7]} ((r)cr, - 0-8) (2-78) where (MW, and (no, ate the moleular weight and specific gravity of the Cr, 562 Hydrocarbon Phase Behavior ‘Example 2-5. If the molecular weight and specifie gravity ofthe heptanes- plus fraction are 216 and 0.8605, respectively, calculate the critical tempera- ture and pressure by using 1. Rowe's Correlations 2. Standing’s Correlations Solution. 1. Solution by using Rowe's Correlation Step 1. Calculate the number of carbon atoms of Cr, from Equation 274 to give n= 15.29 Step 2. Solve for the critical temperature from Equation 2-75 to yield (Te, = 1,279.8°R Step 3. Solve for the eritical pressure from Equation 2-75 to give (Poor, = 280-4 psia 2, Solution by using Standing’s Correlations Step 1. Solve for the critical temperature by using Equation 2-77 to give (Tey, = 1,269.3°R Step 2. Calculate the eritical pressure from Equation 2-78 to yield Poy, = 270 psia Katz-Firoozabadi Method Katz and Firoozabadi (1978) presented a generalized set of physical prop- erties for the petroleum fractions Cy through Cys. The tabulated properties inelude the average boiling point, specific gravity, and molecular weight. ‘The authors’ proposed tabulated properties are based on the analysis of the physical properties of 26 condensates and naturally occurring liquid hydro- carbons. Whitson (1983) found inconsistency in the Katz and Firoozabadi tabu- lated molecular weight data after analyzing and comparing these data with sources from which they were developed. Whitson pointed out that this in- consistency was found in the hydrocarbon fractions Caz through Cys. Pure Component Properties/Characterizing Undefined Fractions 63 Whitson modified the original tabulated physical properties to make their use more consistent, ‘The modification was accomplished by employing the Riazi and Daubert correlation form (Equation 2-1) to extrapolate the molec- ular weight data from Czz to Cis. The coefficients a, b, and ¢ of Equation 21 were recalculated by using a nonlinear regression model to fit the molec- ular weight data of Ce through Cac. The equation was then used to calculate molecular weights of Cas through C,s. The author also calculated the crti- cal properties and acentrie factors of Cy through Cg in terms of their boiling point, specific gravity, and the modified values of the molecular weight. ‘These generalized properties are given in Table 2-10, ‘Ahmed (1985) correlated Katz-Firoozabadi-Whitson tabulated physical properties with the number of carbon atoms of the fraction by using a re- gression model. The generalized equation has the following form: © =a + ayn tag rt + ayn? + (ayn) (279) where © = any physical property ‘n= number of earbon atoms, ie., 6,7, . . 45 a,~as = coefficients of the equations and are given in Table 2-11. Riazi-Daubert Method Riazi and Daubert (1980 and 1987) suggested that their proposed correla- tions for calculating the physical properties of pure petroleum fractions (Equations 2-1 through 2-3) can be used to predict the physical properties of the undefined pertroleum fractions. The authors proposed that the follow- boiling points be used for estimating the physical properties. ing “averag Physical Property ° Average Boiling Point rs Molal Average Boiling Point (MABP) Pe, MW, 7, Ve___Mean Average Boiling Point (MeABP) Cavett’s Method With the appropriate boiling point, Cavett's correlations, as given by Equations 2-7 and 2-8, can be used to predict the critical temperature and the critical pressure of the heavy hydrocarbon fraction, Cavett proposed that the molal average boiling point (MABP) is used in Equation 2-7 to cal- culate T, and the mean average boiling point (MeABP) is used in Equation 2-8 for calculating P,.8 vogmnag ebereny YEH = GY FO 6600 e-O1XeseLiOy _.-01 x vORuNSL x eeieouez «Ox esveees aM *A 2 wo coo 01 x aoeerar'2 x goverir'e 67612980 + § (ee art ‘0% 0586999" 1120008 +0129908'0 ~ 3 0 auto Ot x 1890820'L £9212060 ~ exzszi'05 e086 re E es we 996820 eozzzs2t — suzes S12 FO Seh0 oh xeussz0et ~ ‘65009520 - ascizriy wes si8 3 set avo Susze ear 720610%6'0 ~ suche et — 3 4% 7 . 7 3 soa sawn ym € 61:2 vonenb Jo squ2I>1H809 5 Lee age 8 3 3 waht “any 0 neuig wneanag jo ho0g a fa yma 0 HEL — 8 creoo es oreo #0 So eese00 es ee60 "9 = 89 ese00 12s oreo £9 = 70 ezse00 zs ve60 ®) 2 0 aesao0 203 exe0 "0 2 > is800 ser 1680 °9 & 2 lissoo ver 660 #9 eer) 903000 sur 2260 * Eg 2 — sersco v9 5260 “9 => esra0.0 or 260 %9 = 0680.0 ovr oso 9 9 6ara00 oy uso "9 = oae00 ser siso %9 *) sure suv zis0 = tsa0 ent cos “9 60 es $050 * si60 rs 2050 #5 vea0 sat ero = e980 63 960 rd yao eu 2690 = 6.0 ua sero = exo za $290 "0 e920 eat e009 &% ec es euwo "= aco 002 us0 = ose0 1 9980 "9 zo90 we 180 290 zzz ose0 e190 ore 890 zo Wve oreo oss0 ssz 9ea0 5 sso oz sao 3 vero 992 sig0 2 vs¥0 zoe voro & siro see exo 2 sec ise zaxo 2 ereo cae e270 = zco or ero g ovo esr a0 g osz0 say ___ 0680 8 ° ‘exse) * = i] 6 soniedosd 1eotsfyg paziiesou[ on-z organ,66 Hydrocarbon Phase Behavior Willman-Teja Method Willman and Teja (1987) proposed correlations for determining the eriti- cal pressure and critical temperature ofthe n-alkane homologous series. The suthors used the normal boiling point and the number of carbon atoms of the n-alkane as a correlating parameter. The applicability of the Willman and Teja proposed correlations can be extended to predict the eritical tem- perature and pressure of the undefined petroleum fraction by recalculating the exponeats of the original expressions. These exponents were recalculated by using # nonlinear regression model to best match the critical properties data of Berman et al. (1977) and Whitson (1980). The empirical formulas are given by Te = Ty [1 + (1.25127 + 0.197242n)-08800] (2-80) P, = [399.0416805 + 1,184.157759n][0.873159 “+ 0.54985) mt 281) where n= number of carbon atoms ‘Ty, = average boiling point of the undefined fraction, °R Itshould be noted that the Edmister acentrie factor correlation (Equation 291) and the Kesler and Lee correlations (Equations 2-9 through 2-13) can also be used to characterize the undefined hydrocarbon fraction from their average boiling point and specific gravity. Example 2-6. Calculate the eritical properties and the acentrie factor of C), with a measured molecular weight of 198.71 and specifie gravity of 0.8527. Employ the following methods: 1. Rowe's correlation 2. Standing's correlation 3. Riazi-Daubert correlation Solution. 1. Solution by using Rowe's Correlation. Step 1. Calculate the number of carbon atoms of the fraction n= 14,0507 Step 2. Determine T. from Equation Te = 1,247.06°R 113 to give ‘Pure Component Properties/Characteriaing Undefined Fractions 67 Step 3. Compute P, from Equation 2-75 to yield P, = 245.89 psia Step 4. Determine T, by applying Equation 2-76 to give ‘T, = 941.03°R Step 5. Solve for the acentric factor by applying Equation 2-21 to give w = 0.6123 2. Solution by using Standing’s Correlation. Step 1. Solve for the critical temperature of Gr, by using Equation 2-77 to give (Ter, Step 2. Determine the critical pressure from Equation 2-78 to give oer, = 291.41 psia 1,247.73°R 3. Solution by using Riazi-Daubert Correlation. Step 1. Solve Equation 2-3 for T, to give Te = 1,294.1°R Step 2. Caleulate P, from Equation 2-3 to give P. = 263.67 Step 3. Determine Ty by applying Equation 2-3 Ty = 958.5°R Step 4, Solve for the acentrie factor from Equation 2-21 to give = 0.5346 —_ DETERMINATION OF THE PHYSICAL PROPERTIES OF THE. HEAVY PETROLEUM FRACTION FROM GRAPHICAL CORRELATIONS Several mathematical correlations for determining the physical and eriti- cal properties of petroleum fractions have been presented. These correla- tions are readily adapted to computer applications. However, it s important to present the properties in graphical forms for a better understanding of the behaviors and interrelationships of the properties.68 Hydrocarbon Phase Behavior Boiling Points ‘Numerous graphical correlations have been proposed over the years for determining the physical and critical properties of petroleum fractions. Most of these correlations use the normal boiling point as one of the correla- tion parameters. As stated previously, there are five different methods of de- fining the normal boiling point: ‘a. Volume Average Boiling Point (VABP) . Weight Average Boiling Point (WABP) ¢. Molal Average Boiling Point (MABP) 4d. Cubie Average Boiling Point (CABP) fe. Mean Average Boiling Point (MeABP) Figure 2-2 shows the conversions between the VABP and other boiling points. The following steps summarize the use of Figure 2-2. Step 1. On the basis of ASTM D-86 distillation data, calculate the volumet- ric average boiling point from the following expressions: VABP = (ho + too + too + to + i)/5 (2-82) where t is the temperature in °F and the subseripts 10, 30, 50, 70, and 90 refer to the volume percent recovered during the distillation sgnameentn treet gy ¥ Figure 2-2. Correction to volumetric average boiling points. Courtesy of the Gas. Processors Suppliers Association. Published in the GPSA Engineering Data Book, Tenth Edition, 1987. Pure Component Properties/Characterizing Undefined Fractions 6 5 Step 2. Calculate the 10% to 90% “slope” of the ASTM distillation curv: from the following expression: ? slope = (too ~ t)/80 83 Stop 3. Enter the value of the slope in the graph and travel vertically to the appropriate set for the type of boiling point desired. Step 4. Read from the ordinate a correction factor for the VABP and apply the relationsh Desired Boiling Poin VABP + Correction Factor (284 ‘The use of the graph can best be illustrated by the following examples: Example 2-7. The following ASTM distillation data for a 55°API gravity petroleum fraction is given: Distillation cut % Over jan SRG Reem eee Sree eee eee ee oee 7 co 2 10 3 20 4 20 5 40 6 60 7 6 e 70 9 8% 10 90 Residue eps * initial boiling point *+* Bnd poiat Caloulate: 1. WABP 2, MABP, 3. CABP 4, MeABP Solution, Step 1. Calculate VABP from Equation 2-82: VABP = (178 + 200 + 253 + 318 + 410)/5 = 273°F10 Hydrocarbon Phase Behavior Step 2. Calculate the distillation curve slope from Equation 2-83: slope = (410 - 178)/80 = 2.9 Step 3. Enter the slope value of 2.9 in Figure 2-2 and move down to the appropriate set of boiling point curves. Read the corresponding correction factors from the ordinate to give: ‘© Correction factor for WABP = 6°F ‘© Correction factor for CABP = ~ 7°F ‘© Correction factor for MeABP =~ 18°F © Correction factor for MABP = ~ 33°F Step 4. Calculate the desired boiling point by applying Equ: © WABP = 273 + 6 = 279°F © CABP = 273 ~ 7 = 266°F © MeABP = 273 ~ 18 = 255°F © MABP = 273 ~ 93 = 240°F Molecular Weight Figure 2-3 shows a convenient graphical correlation for determining the molecular weight of petroleum fractions from their mean average boiling points (MeABP) and API gravities. ‘The following example illustrates the practical application of the graphical method. Example 2-8. Calculate the molecular weight of the petroleum fraction with an API gravity and MeABP as given in Example 2-7, Solution. From Example 2-7: API = 55° MeABP = 255°F Enter the above values in Figure 2 to give MW = 118. Critical Temperature ‘The critical temperature of a petroleum fraction can be determined by using the graphical correlation shown in Figure 2-4. ‘The required correla- tion parameters are the API gravity and the molal average boiling point (MABP) of the undefined fraction, Molecular weight Pure Component Properties/Characterizing Undefined Fractions. 71 MW, Boling Points, Graves, Petoleum Fractions Tm ETT RAN aN ERASE ty ARITA HH TE i AO eet He Ht i ae HEEL Es at AL a TEE nal AG PE a En MT ‘Mean average boiling point, Figure 2-3. Relationship between molecular weight, API gravity, and mean aver- ‘age boiling points. Courtesy of the Gas Processors Suppliers Association, Pub- lished in the GPSA Engineering Data Book, Tenth Edition, 1987. Example 2-9. Calculate the critical temperature of the petroleum fraction with physical properties as given in Example 2-7. Solution, From Example 2-7: MABP = 240°F API = 55° Enter the above values in Figure 2-4 to give: T. = 600°F72 Hydrocarbon Phase Behavior Pando Pressures ot hyarcarbont Penud te press, ple Mean average bang pale Figure 2-4. Relationship between critical pressure, API gravity, and mean aver- ‘age boiling points. Courtesy of the Gas Processors Suppliers Association. Pub- lished in the GPSA Engineering Data Book, Tenth Edition, 1987, Critical Pressure Figure 2-5 is a graphical correlation of the critical pressure of the unde- fined petroleum fractions as a function of the mean average boiling point (MeABP) and the API gravity. The following example shows the practical tse of the graphical correlation, Example 2-10, Caleulate the critical pressure of the petroleum fraction from Example 2-7 Pure Component Properties/Charactertzing Undefined Fractions 73. aS ‘Normal bolting point, *F Figure 2-5. Critical temperature as a function of API gravity and boiling points. Courtesy of the Gas Processors Suppliers Association. Published in the GPSA Engineering Data Book, Tenth Edition, 1987. Critical temperature, °F14 Hydrocarbon Phase Behavior Solution. From Example 2-7: APL = 55° MeABP = 240°F Determine the critical pressure of the fraction from Figure 2-5 to give: P, = 460 psia — PROBLEMS: 1, Ifa petroleum fraction has a measured molecular weight of 190 and a specific gravity of 0.8762, characterize this fraction by calculating the boiling point, critical temperature, eritical pressure, and critical vol- ‘ume of the fraction. Use the Riazi and Daubert correlation, 2. Caleulate the acentrie factor and critical compressibility factor of the component in the above problem. 3. Using the Lin and Chao generalized correlation, caleulate the physical and critical properties of a component with a MW, Q, and T of 200, 0.8251, and 500°% respectively 4. A petroleum fraction has the following physical properties: API = 50°, T, = 400°F, MW = 165, Calculate p., Te, Ves , and Z; by using the following correlations: a. Cavett b. Kesler and Lee ec. Winn-Sim-Daubert 4. Watansiri-Owens-Starling 55. An undefined petroleum fraction with ten carbon atoms has a mea sured average boiling point of 791°R and a molecular weight of 134. If the specific gravity of the fraction is 0.78, determine the critical pres- sure, the critical temperature, and acentric factor of the fraction by using: . Robinson-Peng PNA Method . Bergman PNA Method Riazi-Daubert Method |. Cavett’s Correlation : Kesler-Lee Correlation Willman-Teja repege Pure Component Properties/Characterizing Undefined Fractions 15 6. A heptanes-plus fraction is characterized by a molecular weight of 200 and specific gravity of 0.810. Calculate P,, T., Ty, and acentric factor of the plus fraction by using: a. Riazi-Daubert Method b. Rowe's Correlation ¢. Standings Correlation 7, Using the data given in Problem 6, and the boiling point as calculated by the Riazi and Daubert correlation, determine the eritical properties and acentric factor by employing ‘a, Cavett’s Correlation b. Kesler-Lee Correlation ¢, Compare the results with those obtained in Problem 6. EFERENGES 1. Ahmed, T, “Composition Modeling of Tyler and Mission Canyon For- ‘mation Oils with CO, and Lean Gases,” final report submitted to Mon- tanans on a New Track for Science (MONTS) (Montana National Sei- ence Foundation Grant Program), 1985. 2, Bergman, D. F,, Tek, M. R., and Katz, D. L., “Retrograde Condensa- tion in Natural Gas Pipelines,” Project PR 2-29 of Pipelines Research Committee, AGA, Jan. 1977. 3. Cavett, R. H., “Physical Data for Distillation Caleulations—Vapor- Liquid Equilibrium,” Proc. 27th Meeting, API, San Francisco, 1962, pp. 351-366. 4, Edmister, W. C., “Applied Hydrocarbon Thermodynamics, Part 4: Compressbility Factors and Equations of State,” Petroleum Refiner, April 1958, Vol. 37, pp. 173-179. 5, Edmister, W. C. and Lee, B. I., Applied Hydrocarbon Thermodynam- ics, Vol. 1, Gulf Publishing Company: Houston, 1986. 6. Erbar, J. H., “Prediction of Absorber Oil K-Values and Enthalpies, search Report 13, GPA, Tulsa, Oklahoma, 1977. 7. Haugen, O. A., Watson, K. M., and Ragatz, R. A., Chemical Process Principles, 2nd ed., New York: Wiley, 1959, p. 57. 8, Hopke, $. W. and Lin, C. J., “Application of BWRS Equation to Ab- sorber Oil Systems,” proceedings 53rd Annual Convention GPA, Den- vver, Colorado, March 1974, pp. 63-71. 9. Katz, D. L. and Firoozabadi A., “Predicting Phase Behavior of Con- densate/Crude-Oil Systems Using Methane Interaction Coefficients, JPT, Nov. 1978, pp. 1649-1655. Re.16 Hydrocarbon Phase Behavior 410. Kesler, M. G. and Lee, B. I, “Improve Prediction of Enthalpy of Frac- tions,” Hydrocarbon Processing, March 1976, pp. 153-158. (i) Lin, H. M. and Chao, K. C., “Correlation of Critical Properties and ? Acentric Factor of Hydrocarbons and Derivatives,” AIChE Journal, Vol. 20, No. 6, Nov. 1984, pp. 981-983. 12. Nath, J, “Acentric Factor and the Critical Volumes for Normal Fluids,” Ind. Eng. Chem, Fundam, Vol. 21, No. 8, 1985, pp. 325-326, 13. Reid, R,, Prausitz, J. M., and Sherwood, '., The Properties of Gases and Liquids, 3rd ed., McGraw-Hill, 1977, p. 21. 1. Riazi, M. R. and Daubert, T. E., “Simplify Property Predictions,” Hy- drocarbon Processing, March 1980, pp. 115-116. 15. Riazi, M. R. and Daubert, T. E., “Characterization Parameters for Pe- troleum Fractions,” Ind. Eng. Chem. Res., Vol. 28, No. 24, 1987, pp. 155-159. 16, Robinson, D. B. and Peng, D. ¥., “The Characterization of the Hep- tanes and Heavier Fractions,” Research Report 28, GPA, Tulsa (1978). 17. Rowe, A. M., “Internally Consistent Correlations for Predicting Phase Compositions for use in Reservoir Compositional Simulators,” paper SPE 7475 presented at the 53rd Annual Fall Technical Conference and Exhibition. 18, Salerno, S., et al., “Prediction of Vapor Pressures and Saturated Vol- umes,” Fluid Phase Equilibria, Vol. 27, June 10, 1986, pp. 15-34. 19, Sim, W. J. and Daubert, T. E., “Prediction of Vapor-Liguid Equilibria of Undefined Mixtures,” Ind. Eng. Chem. Process Des. Dev., Vol. 19, No. 3, 1980, pp. 380-393. 20, Standing, M. B., Volumetric and Phase Behavior of Oil Field Hydrocar- bon Systems, Society of Petroleam Engineers, Dallas, 1977, p. 124. 21, Watansiri, 5., Owens, V. H., and Starling, K. E., “Correlations for Esti- mating Critical Constants, Acentric Factor, and Dipole Moment for Un- defined Coal-Fluid Fractions,” Ind. Eng. Chem. Process Des. Dev., 1985, Vol. 24, pp. 294-296. 2, Whitson, C. H., “Effect of Physical Properties Estimation on Equation- of-State Predictions,” SPEJ, Dec. 1984, pp, 685-696 23, Willman, B. and Teja, A., “Prediction of Dew Points of Semicontinuous Natural Gas and Petroleum Mixtures,” Ind. Eng. Chem, Res., 1987, Vol. 226, No. 5, pp. 948-952. 24, Winn, F W,, “Simplified Nomographic Presentation, Characterization of Petroleum Fractions,” Petroleum Refiner, Vol. 38, No. 2, 1957, p. 157. 3 Properties of Natural Gases Laws which describe the behavior of gases in terms of pressure p, volume \V, and temperature T have been known for many years, These laws are rela~ tively simple for a hypothetical fluid known as a perfect (ideal) gas. This chapter reviews the perfect gas laws and how they can be modified to de- scribe the behavior of real gases which may deviate significantly from these Jaws under certain conditions of pressure and temperature. ‘A gas is defined as a homogeneous fluid of low density and viscosity, which has no definite volume but expands to completely fill the vessel in which itis placed. Knowledge of pressure-volume-temperature (PVT) rela- tionships and other physical and chemical properties of gases is essential for solving problems in natural gas reservoir engineering. ‘The physical proper- ties of a natural gas may be obtained directly either by laboratory measure- ‘ments or by prediction from the known chemical composition of the gas. In the latter case, the calculations are based on the physical properties of indi- ‘vidual components of the gas and upon physical laws, often referred to as mixing rules, relating the properties of the components to those of the gas mixture. BEHAVIOR OF IDEAL GASES ‘The kinetic theory of gases postulates that the gas is composed of a very large number of particles called molecules. For an ideal gas, the volume of these molecules is insignificant compared with the total volume occupied by the gas. It is also assumed that these molecules have no attractive or repul- sive forces between them, and it is assumed that all collisions of molecules are perfectly elastic. Pure Gases Based on the above kinetic theory of gases, a mathematical equation called Equation-of-State can be derived to express the relationship existing 118 Hydrocarbon Phase Behavior between pressure, volume, and temperature for a given quantity of gas. This relationship for perfect gases is called the Ideal Gas Law, and is ex- pressed mathematically by the following equation: pV = oRT @1 where n is the quantity of gas in moles and is defined by the expression m = “ Mw (3-2) or-|g}m = in which, for the conventional field units used in the Petroleum industry, p= absolute pressure, psia V = volume, ft? T = absolute temperature, °R umber of moles of gas, Ib-mole m = weight of gas, 1b MW = molecular weight, IbyIb-mole R = the universal gas constant which, for the above units, has the value 10.790 psia f?/Ib-mole °R Because the density is defined as the mass per unit volume of the sub- stance, Equation 3-3 ean be solved for the density to yield (3-4) where py = density of the gas, Ib/f, and tb refers to Ibs mass in any subse- uent discussions of density in this text. In dealing with gases at a very low pressure, the ideal gas relationship is a convenient and generally satisfactory tool. For the calculation of the physi- cal properties of natural gases at elevated pressure, the use of the ideal gas equation-of-state may lead to errors as great as 500% , as compared to errors of 2-3% at atmospheric pressure. Example 3-1. Assuming an ideal gas behavior, calculate the density of pro- pane with a constant temperature of 100°F and 20 psi Properties of Natural Gases 79 Solution. Applying Equation 3-4 yields (20) (44.097) Pe" To.ay 100 + 460) ~ O48 DE IDEAL GAS MIXTURES Petroleum engineers are usually interested in the behavior of mixtures and rarely deal with pure component gases. Because natural gas is a mixture of hydrocarbon components, the overall physical and chemical properties can be determined from the physical properties of the individual components in the mixture by using appropriate mixing rules. Conventionally, natural gas compositions are expressed in terms of mole fraction, weight fraction, and volume percent. These are derived as follows: Mole Fraction: The mole fraction of a particular component, component i, {s defined as the number of moles of that component divided by the total number of moles of all the components in the mixture. my 65) where yj = mole fraction of component i in the mixture 1, = number of moles of component { n= total number of moles in the mixture Weight Fraction: The weight fraction of any component is defined as the ‘weight of that component divided by the total weight. wee (36) weight fraction of component i ‘eight of component i in the gas phase jotal weight of the gas mixture Volume Fraction: The volume fraction of a specific component in a mixture is defined as the volume of that compound divided by the total volume of the mixture. MMi yu T (37)80 Hydrocarbon Phase Behavior where vj = volume fraction of component i in the gas phase V; = volume occupied by component i YV = total volume of the mixture It is convenient in many engineering calculations to convert from mole fraction to weight fraction and vice versa. The procedure of converting the composition of the gas phase from mole fraction to weight fraction is sum- marized in the following steps. Step 1. Assume that the total number of moles of the gas phase is one, ie,n= 1. Step 2. From Equation 3-5, it is apparent that a= ys Step 3. Because the number of moles of a component is equal to the ‘weight of the component divided by the molecular weight of the component, as expressed mathematically by Equation 3-2, the ‘weight of the component can be expressed as m= ysMW; and m rm Dn Step 4. By recalling the definition of weight fraction then yi MW, (38) yMW, ced Similarly, one can convert from weight fraction to mole fraction by applying the following relationship: (w/MW)) 09 (wiMW)) oo ‘The above procedure is conveniently illustrated through the following ex- amples. Example 3-2. Determine the composition in weight fraction of the follow- ing gas: Properties of Notural Gases 81 Mole Fraction ‘Component tL G 0.65 Ce 0.10 G 0.10 G 0.10 7 0.05 Solution. Component Mw, s GQ 16.04 10.4260 0.3824 G 0.10 30.07 3.0070 0.1103 G 0.10 44.10 4.4100 0.1618 GQ 0.10 58.12 5.8120 0.2132 cs 0.05 72.15 3.6075 0.1393 m = 27.2625 Example 3-3, Determine the composition in mole fraction of the following gas: Weight Fraction Component ws G 0.40 G 0.10 & 0.20 Gq 0.20 Cs 0.10 Solution. Component = _wi_ MW, wiMW, y= min G 0.40 16.04 0.02494 0.6626 Cs 0.10 30.07 0.00333 0.0885 G 0.20 © 44.10 0.00454 0.1206 G 0.20 58.12 0.00344 0.0914 ro 0.10 72.15 0.00139, 0.0369 n= 0.03764 ‘PROPERTIES OF IDEAL GAS MIXTURES. Usually the petroleum engineer is interested in studying the volumetzic behavior and evaluating the basic properties of natural gas mixtures. It is82 Hydrocarbon Phase Behavior ‘appropriate first to introduce and define the physical properties of ideal gas mixtures. “The basic properties of ideal gases are commonly expressed in terms of the apparent molecular weight, standard volume, density, specifie volume, and specific gravity. These properties are defined as follows: Apparent Molecular Weight ‘One of the properties that is frequently of interest to engineers is the ap- parent molecular weight. Ify zepresents the mole fraction of the ith compo- nent in a gas mixture, the apparent molecular weight is defined mathemati- cally by the following equation Mw. De MW, 10) where MW, = apparent molecular weight of the gas mixture MW, = molecular weight of the ith component in the mixture Standard Volume In many natural gas engineering caleulations, it is convenient to measure the volume occupied by 1 Ib/mole of gas at a reference pressure and temper- ature, These reference conditions are usually 14.7 psia and 60°F, and com- monly referred to as standard conditions. The standard volume is then de- fined as the volume occupied by 1 Ib/mole of an ideal gas at standard conditions. Applying the above conditions to Equation 3-1 and solving for the standard volume yields vpn RTs Pe Substituting for pressure and temperature, produces Va. = 879.4 sefilb-mole @u) where V,. = standard volume, sefilb-mole sef = standard cubie feet . ‘Ty, = standard temperature, °R Pe = standard pressure, psia Properties of Natural Gases 83 Density ‘As defined previously by Equation 3-4, the density of an ideal gas mixture is calculated by applying Equation 3-6 and replacing the molecular weight with the apparent molecular weight of the gas mixture to yield: Mw, a 12) where pg = density of the gas mixture, F/lb ‘MW, = apparent molecular weight Specific Volume “The specific volume is defined as the volume occupied by a unit mass of the gas. For an ideal gas, this property can be calculated by applying Equa tion 3-3: iu 8-13) where y = specific volume, f0¥/Ib py = gas density, Ib/f Specific Gravity ‘The specific gravity is defined as the ratio of the gas density to that of the air, Both densities must be taken at the same temperature and pressure, or: noe G14) Par Assuming the behavior of both the gas mixture and the air is described by the ideal gas equation, the specific gravity can be expressed by the following relationship: (3-15)84 Hydrocarbon Phase Behavior where 7g = gas specific gravity par © density of the air MWy, = apparent molecular weight of the air = 28.96 Example 3-4. A gas has the following composition: Component GQ 0.75 Cy 0.07 Cs 0.05 Gy 0.04 Cs 0.04 Ce 0.03 Cc: 0.02 “Assuming an ideal gas behavior, calculate the following gas properties at 1,000 psia and 100°F: a. Apparent molecular weight b. Specific gravity c. Gas density 4. Specific volume Solution. Component ae Mw. yc MW G 0.75 16.04 12.030 CG 0.07 30.07 2.105 G 0.05 44.10 2,205 Cy 0.04 38.12 2.395 Cs 0.04 72.15 2.886 Cs 0,03 86.18 2.585 Gr 0.02 100.21 2.004 26.14 a. Applying Equation 3-10 yields MW, = 26.14 bb, From Equation 3-15 26.14 _ 0.903, : 96 ” ©. Compute the gas density by using Equation 3-12 Properties of Natural Gases 85 __(1,000)(26.14) Pe*"(10.73)(660) 7 1 d. From Equation 2-13, specific volume = == = 0.93 ft*/Ib Equation 2-13, specific volume = —-3¢ = 0.23 4.35 Ioift ——— BEHAVIOR OF REAL GA! Basically the magnitude of deviations of real gases from the conditions of the ideal gas law increases with increasing pressure and temperature and varies widely with the composition of the gas. Real gases behave differently than ideal gases. The reason for this is that the perfect gas law was derived under the assumption that the volume of molecules is insignificant and no ‘molecular attraction or repulsion exists between them. This is not the ease for real gases. ‘Numerous equations-of-state have been developed in the attempt to cor- relate the pressure-volume-temperature variables for real gases with experi- ‘mental data. More recent equations-of-state are presented and discussed in detail in Chapter 6. In order to express @ more exact relationship between the variables p, V, and TT, a correction factor called the gas compressibility factor, gas deviation factor, or simply the Z-factor, must be introduced into Equation 3-1 to account for the departure of gases from ideality. This is: pV = ZnRT (16) where the compressibility factor Z is a dimensionless quantity and is defined as the ratio of the actual volume of n-moles of gas at T and p to the ideal volume of the same number of moles at the same T and p. aos uy G17) where V, = actual gas volume V, = ideal gas volume For a perfect gas, the gas compressibility factor is equal to one. For a real ‘gas, the Z-factor is greater or less than one depending on the pressure, tem- perature, and the composition of the gas. “The value of Z at any given pressure and temperature can be determined ‘experimentally by measuring the actual volume of some quantity of gas at the specified p and ‘T and solving Equation 3-16 for the compressibility fac- tor Z. A typical curve of the Z-factor for a natural gas is shown in Figure 3:1, where the Z-factor is plotted as a function of pressure for a given con-