Constantes de Equilibrio

Tech ncal Publcation
TP-22
Convergence Pressure and Vapor-Liquid Equilibrium Ratios
Published by the Gas Processors Association
June, 1999
6526 East 60th Street * Tulsa, Oklahoma 74145

Copyright Gas Processors Association Provided by IHS under license with GPA No reproduction or networking permitted without license from IHS
~~
Phone: 918/493-3872 Fax:

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GPA Disclaimer
GPA publications necessarily address problems of a general nature and may be used by anyon' desiring to do so. Every effort has been made by GPA to assure accuracy and reliability of the informatioi contained in its publications. With respect to particular circumstances, local, state, and federal laws ani regulations should be reviewed. It is not the intent of GPA to assume the duties of employers manufacturers, or suppliers to warn and properly train employees, or others exposed, concerning healtl and safety risks or precautions. GPA makes no representation, warranty, or guarantee in connection with this publication and hereb expressly disclaims any liability or responsibility for loss or damage resulting from its use or for thl violation of any federal, state, or municipal regulation with which this publication may conflict, or for an infringement of letters of patent regarding apparatus, equipment, or method so covered.
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"Copyright O 1999 by Gas Processors Association. All rights reserved. No part of this report may be reproduced without the written consent of the Gas Processors Association."
Not for Resale
Convergence Pressure and Vapor-Liquid Equilibrium Ratios
GPA Technical Publication TP-22
Prepared by
Gas Processors Suppliers Association Editorial Review Board
6526 E. 60th Street Tulsa, OK 74145
June, 1999
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Not for Resale
Introduction
This Technical Publication, TP-22, serves to archive the GPSA Convergence Pressure Vapor Liquid1 Equilibrium Ratios (K-data) along with other K-data charts. The convergence pressure approach to handling1 composition dependency of K-values was omitted when the eleventh edition of the GPSA Engineering Data, Book was published in 1998. The Editorial Review Board explained this change in the data book with the^ following statement: Previous editions of this data book presented extensive sets of K-data based on the GPSA Convergence Pressure Pk method. A component's K-data is a strong function of temperature and pressure and a weaker function of composition. The convergence pressure method recognized composition effects in predicting Kdata. The convergence pressure technique can be used in hand-calculations, and it is still available as computer correlations for K-data prediction. There is now general availability of computers. This availability coupled with the more refined K-value1 correlations in modern process simulators, has rendered the previous GPA convergence pressure charts outdated. The convergence pressure method is presented in dual metric (SI) and English (FPS)units. This TP contains the full explanatory text on convergence pressure from section 25 of the tenth Edition of the GPSA Engineering Data Book (the blue books) supplemented with the SI information from the corresponding material from section 18 in the 1980 SI Engineering Data Book (the green book). All of the standard charts are from the 1980 SI Engineering Data Book (the green book). In addition, other charts from the 1957 edition relating to acid gas components in ethane and propane have been included. For quick trouble-shooting and evaluation work a set of K-charts can be very helpful. They present an illustration of the effect of temperature and pressure on K-values for light hydrocarbons. A composite set has been retained in the eleventh edition of the data book for both the SI and FPS units. The charts represent decades of careful comprehensive research directed by GPA and GPSA. Accordingly, the Associations decided that they are to be retained as a resource available to the industry and academia. Also included in this TP are K-data for High-Boiling Hydrocarbons (Poettman charts), some hydrogen sulfide binanes and hydrogen binaries, The Equilibrium or K-value curves were first published in chart form by the NGAA and NGSMA (predecessors to the present day GPA and GPSA) in the early 1950's. Much of the basic data was compiled in tabular form under the direction of Dr. G. G. Brown, Dean of Engineering,University of Michigan. The data were taken from numerous published articles and unpublished experimental data. From these tabular data the first charts to be used by the industry were prepared by the Fluor Corporation Engineering Department under the guidance of Blaine Kuist, C. W. Leggett and C.K. Walker. Most of the painstaking draftsmanship was done by Orville McAdams, also of Fluor. Stuart Hadden developed the concept of convergence pressure, thereby making the charts useful for predicting K-values in a mixture containing any number of components. The charts were first published by the NGAA in 1955.
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In anticipation of needing additional information to expand the data and improve the accuracy. NGAA appointed the first Equilibrium Committee chaired by Elliott Organik, United Gas Corporation. Members of the committee were C. L. DePreister, California Research Corporation; Karl Hackmuth, Phillips Petroleum Company; James Kilmer, Stanolind Oil and Gas Company; H. H. Rackford, Humble Oil and Refining Company; Bryon Woertz, The Pure Oil Company; and Charles Webber, Sun Oil Company.
In 1957 the charts were completely redrawn to provide data at lower temperatures and to increase the internai consistency of the K-values. Karl Hackmuth guided the chart revision. By then Byron Woertz had assumed chairmanship of the Equilibrium Committee. E.A. Gromatzky, The Texas Company; R. H. Jacoby, Pan American Petroleum Company; Herbert L. Stone, Humble Oil and Refining Company; and C. J. Walters. California Research Corporation had become members of the committee.
This committee continued to act as a clearing house for new equilibria data and correlation methods. In 1958 these charts were published as Tables of Coefficients for use with early computers. Robert Norman and Brymier Williams presented a paper at the 57th Annual NGAA convention in Dallas April, 1958 that was the basis for the initial work that developed these machine computations.
A set of equations was developed to represent each page in the Data Book. The NGAA prepared a reproduction of the data from these charts in two forms - point cards and coefficient cards. The point cards were IBM cards containing approximately 70,000 data points (pressure, temperature, composition and convergence pressure) punches on 17,000 cards. The coefficient cards were IBM cards that contained the coefficients for the equations used to empirically correlate the point data. This required only 432 cards because each card contained seven coefficients. This drastically reduced the number of cards which in turn reduced the computer storage space required.
Through the years the convergence curves have been modified and improved. They are still published in the GPSA Engineering Data Book and represent decades of careful and comprehensive research directed by GPA and GPSA.
Not for Resale
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STDnGPA TP-ZZ-ENGL
1997
382qb97 00201178 1173
TP-22
EQUILIBRIUM RATIO (K) DATA
The equilibrium ratio (Ki) of a component i in a multicomponent mixture of liquid and vapor phases is defined as the ratio of the mole fraction of that component in the vapor phase to that in the liquid phase. Note that the critical data from these binary mixtures were NOT used to adjust the critical loci of Figure 5 . Such an adjustment would necessitate complete cross-plotting and redetermination of all of the convergence pressure charts.
Use of Binary Charts - At temperatures below - 0 ' 10F
K , = - Yi
xi
[-73T], light hydrocarbon system is most easily approximated a as a pseudobinary. Determine the average molecular weight on
a methane-free basis; then interpolate the K-values between the two binaries whose heavy component lies on either side of this pseudocomponent. This calculation becomes poor for systems with N2 content greater than 3 to 5 mole percent. The ternary methane-ethane-propane system is well defined.5 At temperatures below -75F [-60C], (except for the highest pressures 700-800 psia [4800-5500 kPa(abs)] at -75F [-60"Cl and -100F [-73"C]. if f=XE(Mp) /xECMi ratio of = ethane mole fraction in the liquid phase of the ternary system to the ethane mole fraction in the liquid phase of the methaneethane system, then the ternary K-values can be calculated from:
log KM = log KM(P)
For an ideal system (ideal gas and ideal solution), this equilibrium ratio is reduced to the ratio of the vapor pressure of component i to the total pressure of the system. pi* Ki = P This TP presents an outline procedure to calculate the liquid and vapor compositions of a two-phase mixture in equilibrium using the concept of a pseudobinary system and the convergence pressure equilibrium charts. Discussion of CO;! separation. alternate methods to obtain K values, and equations of state follow. Finally, three sets of equilibrium rat:, charts are presented: K-values for specific binary systems K-values of various components based on different convergence pressures of hydrocarbon systems K-values of pseudocomponents based on normal boiling point and characterization factor
[KM(P)IKM(E)1
Eq 3
log KP = log KP(M)
log [KP(M)/KgME)l
E 5 q
Note that xE(MP) I xE(M), and KAo, denotes K-value of A in the A-B binary system. These are found from pages 102 and 103. The infinite dilution KE(MP) and G,,,, given on page are
104.
BINARY SYSTEMS DATA CHARTS

The 1972 edition of the GPSA Engineering Data Book included for the first time several charts representing binary combinations of N2,Cl. C , C3, n-C4. These data resulted , and from GPA-sponsored research at Rice University. Binary data with heavier components and acid gases have been added as revisions as they have become available. These charts are useful for low temperature (below - 100"F,
[-73"C]) calculations. Below the critical temperature of

methane (-1 16F [-82"C]), the convergence pressure of a system no longer has a real significance, since the K-values for heavy components do not reach a value of 1.O.
These generalizations can be made about the ternary Kvalues: Addition of propane increases the methane K-value and decreases the ethane K-value. Addition of ethane decreases the methane K-value and increases the propane K-value. The propane K-value is highest when at infinite dilution in the ternary (.e., a methane-ethane binary). The ethane K-value is highest when no propane is present (.e., a methane-ethane binary). These generalizations can be extended to other ternary (or
Figure 1 Nomentclature
K = qulibrium ratio, y/x L = ratio of moles of liquid to moles of total mixture N = mole fraction in the total mixture or system O = acentric factor = log Pv, - 1.o0 where. Pvr = reduced vapor pressure at Tr = 0.7 P = absolute pressure, psia [kPa(abs)] Pk = convergence pressure. psia [kPa(abls)] P* = vapor pressure, psia [kPa(abs)]
y = mole fraction in the vapor phase Superscripts ' = pseudobinary o0 = at infinite dilution
R = universal gas constant, (psia
CU
ft)Ab mole "R)[(kPa m3 ) /(kmole K)]
T = temperature, O R or OF [K or OC] V = ratio of moles of vapor to moles of total mixture x = mole fraction in the liquid phase
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Subscripts I = component c = critical M = methane E = ethane P = propane

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1
Not for Resale
STD-GPA TP-ZZ-ENGL
1799
3824b99 0020479 30"
higher) systems: the heaviest component (propane in this case) is analogous to a "lean oil" in an absorber system. The methaneethane is acting in this case as a "natural gas" with the heaviest component (ethane) being preferentially absorbed into the "lean oil" (propane), with the resulting effects on the K-values. The liquid mole fraction of the middle (volatility) component is a useful parameter. The user should be aware that the composition effect on K-values is very pronounced in the regions covered by the binary and ternary data systems. Accurate values can be obtained only by cross-plots of K-value versus composition. Limiting conditions should be considered in the analysis and use of K-data. For example, the limits on a binary system are defined by the vapor pressure of the pure components, as shown of by the Locus K G and Locus KS page 102. The limits of a ternary system are the binary systems. The GPA/GPSA sponsors investigations iL systems of interest to gas processors. Detailed results are given in the annual proceedings and in various research reports and technical publications, which are listed in Section 1 of the Engineering Data Book.
0.674 v
+ 0.0674 (100 - v ) = 60
v = 87.8
The mixture consists of 87.8 moles of vapor and 13.2 moles of liquid.
K-VALUES CORRELATION BY CONVERGENCE PRESSURE

The convergence pressure chart representation of K-values. used since 1957 by the GPA, provides a useful and rapid graphical approach for engineers. Within limits the values are sufficiently accurate to satisfy many calculations required by the practicing engineer. Moreover. these charts are widely used in industry and are generally preferred over most nomographs. The charts included in this TP are a mixture of past and present, as shown in Figure 2. The Pk charts for methane, ethane, and propane are based on extensive cross plots of available experimental data. Properly used, they should represent both absorber oil and condensate systems adequately. Charts for components heavier than propane are selected from previous editions, based on general experience as to whether the 1957 or 1966 edition of the Engineering Data Book gave the best results. The present convergence pressure charts do not have as many low temperature isotherms as in past editions. This is because no experimental data existed in these regions when the charts were prepared. Calculations of systems at very low temperatures and at high convergence pressures do not have much significance in hydrocarbon systems, and therefore should not be shown. As an example, refer to Figure 5. Assuming methane as the light componet and methylcyclohexane as the heavy, the critical locus line indicates that the lowest possible temperature for a 3000 Pk is -50F [-46OC]. This is about the practical limit in real systems; therefore, isotherms significantly below this would be imaginary. This deletion of low-temperature isotherms is intended to warn the user not to apply these charts beyond the range of good practice. The accuracy of the P, charts depends in part on how carefully the convergence pressure has been determined. At moderate to high values of operating pressurekonvergence pressure (ratio > 0.4), both accurate convergence pressure determination and interpolation between P, charts can be made. K-values from an equation of state are likely to be more reliable. In the case of methane, interpolation between P, charts is a must to obtain accurate K-values. This is true to a lesser degree for heavier components. The revised charts were back-calculated from data and cross-plotted using Figure 5 as the basis of critical locus; therefore, ali determinations of convergence pressure must be made from Figure 5.
Example 1 - Binary System Calculation

To illustrate the use of binary systerm K-value charts, assume a mixture of 60 moles of methane and 40 moles of ethane at -125OF [-87"C] and 50 psia [345 kPa(abs)]. From the chart on page 102, the K-values for methane and ethane are 10 and 0.35 respectively. This method is valid for either Ibmols or kmols. Solution Steps From the definition of K-value, Eq 1 :
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Y G2= z = 0.35
x c2
Rewriting
' -- yci - 0.35
'-
xc1
Solving
xcl = 0.0674
ycl = 0.674 Hence
xc2
= 0.9326 = 0.326
yo
To find the amount of vapor in the mixture, let v denote moles of vapor. Summing the moles of methane in each phase gives:
2
Not for Resale
If any other source of critical locus is substituted, the revised charts will be less accurate in predicting the system of K-values. Recent binary data for the Cl-nC6, C1-nC,. C,nC6, Cz-nCIo, C3-nC6, and C3-nC7 systems allowed the addition of their respective critical loci.
Component
Binary Data
Convergence pressure, kPa (abc) [psia]
5500
w1 I o
Nitrogen
Methane Ethylene
I
6900 [l@JJI
10300 [I5001
13800 20700 [2000] j [3000]
34500
[SOOO]
69000 (iO,OOO]
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* * * *
I
i
I
Ethane Propylene Propane

iso-B utane n-Butane isoPentane
O V O V
O
O V O
V
O
V
V
X
V
0
V
O O O
V O V O V
X X
V V
1
I
V
X X
V
X X X
X X
X X X X I
*t
I
O O
X X
X
X
I Octane
Nonane Decane Hydrogen sulfide
O Q
x
X X
x
X X X
x
X
~~
x
X
,
1
O
X
,
I
I
I
Carbon dioxide
Binary data from Price & Kobayashi; Wichterle & Kobayashi; Stryjek. Chappelear. & Kobayashi; and Chen & Kobayashi Drawn for Data Book, 1972 Edition based on available data 0 Reused from Data Book, 1966 Edition Note: The charts shown in bold outline are published in the 1 1th X Reused from Data Book, 1957 Edition edition of the data book. All charts shown in this Figure t Prepared for Data Book. Second Revisions 1972Edition or revised are published in this Technical Publication (TP-22),as well as the 10th Edition of the data book. * * Limited to Cop concentrationof 1O mole percent of feed or less
Method of Calculating Convergence Pressure The vapor-liquid equilibrium K-value of each component in a system is a function of the system temperature, system pressure, and the composition of the vapor and liquid phase. For natural gas processes, the convergence pressure can usually be used as the parameter that represents the compasiton of the vapor and liquid phase in equilibrium. The c.onvergence pressure is, in general, the critical pressure of a system at a given temperature. At a given temperature, as the system pressure increases, the K-values of ail components of the system converge to unity when the system pressure reaches the convergence pressure. In other words, it is the pressure for a system at a given temperature when vapor-liquid separation is no longer possible. Naturally, it is equally impossible to have a vapor-liquid separation at a given temperture i n which the system pressure is greater than the convergence pressure. Although the convergence pressure charts include values for methane, ...n-butane ai - 120F [-84"C] and lower, the use of the
binary K-data is recommended below the critical of methane

11 6 ' F
[-82OC].
(-
The convergence pressure of systems as encountered generally in natural gas processes is a function of the temperature and the composition of the liquid phase. This presumes that the liquid composition is known from a flash calculation using a first approximate guess for convergence pressure. Therefore, the method of calculating convergence pressure is an iterative procedure. This calculation procedure is suggested. Step 1: Assume the liquid phase composition or make an approximation. (If there is no guide, use the total feed composi ton.) Step 2: Identify the lightest hydrocarbon component which is present at least 0.1 mole 480 in the liquid phase. Step 3: Calculate the weight average critical temperature and critical pressure for the remaining heavier components to form a pseudobinary system. (A shortcut approach good for most hydrocaron systems is to calculate the weight average T, only.)
3
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S T D I G P A TP-22-ENGL
1999
3 8 2 q b 5 002OLi81 Tb
Step 4: Trace the critical locus of the binary consisting of the light component and pseudoheavy component. When the averaged pseudoheavy component is between two real hydrocarbons. an interpolation of the two critical loci must be made. Step 5: Read the convergence pressure (ordinate) at the temperature (abscissa) corresponding to that of the desired flash conditions, from Figure 5. Step 6: Using the convergence pressure determined at Step 5 , together with the system temperature and systrm pressure, obtain K-values for the components from the appropriate convergence-pressure K-charts. Step 7: Make a flash calculation with the feed composition and the K-values from Step 6, as shown in Figure 3.
When the convergence pressure so determined is beweein the values for which charts are provided, interpolation between charts may be necessary depending on how close the operating pressure is to the convergence pressure.
If K-values do not change rapidly with P, ( P p > P ) then the set of charts nearest to the calculated PI; m a y he used. Otherwise, a cross-plot of K values versus P,. all at constant temperature and pressure, must be constructed for interpolation.
Step 8: Repeat Steps 2 through 7 until the assumed and calculated convergence pressures check within an acceptable tolerance, or until the two successive calculations give the same light and pseudoheavy components check within an acceptable tolerance. Figure 3 SI Example Flash Calculation at 4000 kPa (abs) and -30C
Aromaticity Corrections - These K-chrirrs for which Pk = 800, 1000, and 2000 were based entirely on binary parafin hydrocarbon systems, while those for P, = 4000 and 10.000 were derived from early data on mixtures containing some naphthenes (cycloparaffins) and aromatics. It is believed that small amounts of cyclic components added to mixtures of paraffins do not seriously affect the K-values obtained from these charts. However, as the concentration of cyclics increases the K-values are affected in a manner that is not fully accounted for by the convergence pressure variable.
'
2
KI tor
Pk = 2000
Feed Gas :omponent I Composition

Ni
1 4 1 5 Trial values of L L = 0.02 L = 0.04 L = 0.06

Ni
Column 1 7 1 8 Final L = 0.030 Liquid 1 Vapor
Merhane-free basis
MW
113800 kPaabs)
0.90 I O 0.0106 0.0499 0.0187

0.0065 0.0055
3.2
1.14 0.41
0.0017 0.0019 0.0029 0.0023
0.097 0.038 0.024 0.0088 0.0062 0.0019 O.ooo66
L+VKi 0.28549 0.00932 0.11830 0.16252 0.11356 0.10340 0.05939 0.07286 O. 13265 0.1 I140
Ni -
Ni
L+V&
.+VK,
kg liquid 7x9
m s s trac
liquid
T. K ' P,. kPa (absi ,
0.29368 0.00937 O. 1 1203 0.12369 0.06791

0.05451
C.28952 c.00934 O. 1 1508
o. 14047
0.02490 0.02886
0.04694
0.08499 0.01138 0.03509 0.04135 0.06934

0.05661
0.03794 0.79983
3.1I . 13580 0.42770 O. 12409 0.06686 0.05328 0.03854 0.03641 0.03184 0.03064
0.28749 0.00933 0.1 1667 O. I5070 0.09722 0.08446

0.04411
0.91997
0.01064
0.05276 0.09107 0.07506
0.01183 0.01462 0.00369 0.00203 0.00039 0.00033

O.WO17 0.ms
44.01 30.07
44.10
58.12 58.12 72.15 72.15 86.18 107.0
0.4106 3.5083 6.6459 5.6504 4.9088 3.1825 3.8066
0.0093 0.079X
0.1511
305.2
o. 1284
0.1 I I6 0.0723 0.0865
0.1784
7.8484
8.0314
2=
'Avaagc of nC,
1.16889
0.91317
I .O0887
0.99972
43.9929
+ nC, properties
End of flash calculation
-!
Calculation to confirm PI.
Figure 3 FPS Example Flash Calculation at 600 psia and -20F

Column
Ib liquid
30S.J 369.8 408.1 425.2 460.4 469.6 507.4

554.5
7382 4880
424s
O. 1826
1 .oooo
36111 3797 3381 3369 3012 261 I 3542
-273.2
175.4OC
448.6li
:omponeni
Composition
ITCI CO2 C Z
-q-T
L+VKi L+VK,
0.00945
~~
1 4 Trial values of L=O.O2 I L=0.06
8 Methane-free basis
ral L = 0.0210
L = 0.04
Ni
__
- .._ ._ Tc. "U

~
0.9010
0.0106
c 3
iC1 nC4 ic, nC3
cb
0.0499 0.0187
0.0065
T,+
0.0045 0.00 I7 0.0019 0.0029 0.0023
3.2m 1.13000 0.4oooO O. 10500 0.01500 0.03300 0.01300 0.01000 0.00290 O.WO55
Taala
A v m g e of nC,
i nCKproperties
i
0.28549 o.oO940 0.12112 0.15216 0.29368
0.10140
L+VK,
L+VK,
MW
mass frac.
la9 0.28689
0.00941
liquid
Pc. psia
0.08598 0.05192 0.06376 0.12696 0.1 I198

1.11017
0.11445 0.11783 0.06354 0.04944 0.02354 0.02738 0.04623 0.03801 0.78354
0.28952 0.00942 0.11769 O. I3281 0.078 I3 0.06278 0.03239 0.03831 0.06778 0.05675 0.88559
3.14060 1.12649 0.4 I620 o. I29 17 0.07079 0.0591 I 0.03965 0.03673 0.02982 0.02754
O. I 1989 0.14478 0.09183 0.07613 0.04288 0.02173 0.09724 0.08353 1.00431
0.91 804 0.01063 0.04796 0.01520 0.00413 0.00251 0.00056 0.00052 0.00028 0.00005 0.99988
44.01 30.07 44.10 58.12 58.12 72. I5 72.15 86.18 107.00
End of flash calculation
-I
Calculation IO confirm Pk
44.3096
0.4141 3.6052 6.3846 5.3370 4.4247 3.0935 3.7322 8.3805 8.9377
0.0093 0.08 I4 0.1441 o. I204

0.0999
0.0698 0.0842 0.1891 0.2017

I .oooo
557.6 -549.6 665.8 734.2 765.3 828.8 845.5 913.3 998. I 813.11"R
1071.0
706.5
616.0 527.9 550.6 490.4 48.6 436.9 378.7 SOY.?
3M.I"F
-459.7
4
Not for Resale
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The GPA has sponsored research to study these effects in absorber systems, and the experimental results of this work are published.' In general. the data show that the presence of aromatics in paraffin mixtures serves to increase the K-values of the paraffins.
HIGH BOILING OIL FRACTIONS

At the end of the convergence pressure series of charts is appended a small set of K-charts developed by Poettman and Mayland2 for high boiling petroleum fractions. They are useful for low pressure, high temperature flash calculations on heavy oils, such as in the reboiler of an absorber oil stripper or an atmospheric crude distillation tower, provided information on ASTM or IBP of the oil is available. At pressures below 100 psia [690 kPa (abs)] K s from these charts are fairly compatible with those from the convergence pressure series, if a plot of K vs. component boiling point is made. The reader is referred to White and Brown3 and Grayson and Streed4 for additional data.
A situation of reproducible sieady state condition> in ;1 piecc of equipment does not necessarily imply that c l a s s i ~ i ~ l thermodynamic equilibrium exists. If the steady composition differs from that for equilibrium, the reason can be the result of time-limited mass transfer and diffusion rates. This wming is made because i t is not at all unusual for flow rates through equipment to be so high that equilibrium is not attained or even closely approached. In such cases. equilihrium flash calculations as described here fail to predict conditions in the system accurately, and the K-values are suspected for this failure-when in fact they are not at fault.
Yi Ki = Xi
Eq. 6 Eq. 7
L + V = 1.0
By writing a material balance for each component in the liquid, vapor, and total mixture, one may derive the flash equation in various forms. A common one is.
xxi = N. zI = 1.0 L + VK, Eq. 8
DATA FOR NONHYDROCARBONS

Hydrogen Sulfide Since the hydrocarbon charts for Pk = 4000 were also eliminated, the Pk = 4000 chart for H2S was reduced to Pk = 3000 by simply adjusting the isotherms at pressures near 3000 psi. The H2S chart for Pk = 1000 was reused from the 1957 edition of the Engineering Data Book. Nitrogen The convergence pressure charts for N2 which are based largely on binary and ternary data from the University of Texas were retained from the 1966 editon of the Engineering Data Book, as illustrated in Figure 2. Data for N2-CH4 and N2-C2H6 are given on pages 109- 1 1O. These data, and data on the ternary, show that the K-values in this system show strong compositional dependence. In this system, the component order is N2-CH4-C2H6,and the K-values are functions of the amount of methane in the liquid phase. For example, at -190F [-123"C] and 300 psia [2070 kPa(abs), the K-values vary from:
N2
Other useful versions may be written as Eq. 9 KiNi
Eq. 10 L + VK, At the phase boundary conditions of bubble point (L = 1 .OO) and dew point (V = 1.00). these equations reduce to
xyyi=
~
I;Ki Ni = 1.0 (bubble point) and
Eq. 11 Eq. 12
--`````-`-`,,`,,`,`,,`---
mi/Ki = i .O (dew point)
These are often helpful for preliminary calculations where the phase condition of a system at a given pressure and temperature is in doubt. If CK, Ni and LNi/K, are both greater than I .O, the system is in the two phase region. If XK,Ni is less than 1.O, the system is all liquid. I f If ZKi Ni is less than 1 .O, the system is ail vapor. Example 2-FF'S - A typical high pressure separator gas is used for feed to a natural gas liquefaction plant, and a preliminary step in the process involves cooling to -20Fat 600 psia to liquefy heavier hydrocarbons prior to cooling to lower temperatures where these components would freeze out as solids. Estimate the convergence pressure Pk. Solution Steps - The feed gas composition, shown in Figure 3-FPS,column 1, is similar to that used in the enthalpy and entropy problems in Section 24 of the Engineering Data Book. Pk is first estimated to be 2000 psia and K's are determined as in column 2. Then the flash equation 8 is solved for three estimated values of L as shown in columns 3, 4, and 5. By plotting estimated L versus calculated Exi, the correct value fo L where Zxi = 1.00 is L=0.027, whose solution is shown in columns 6 and 7. The gas composition is then calculated using
5
Not for Resale
CH4
0.824*
C2H6
10.2 3.05
0.635
0 0 18 .1 0.035*
where * indicates the limiting infinite dilution K-value. See TP-45for the data on this ternary.
FLASH CALCULATION PROBLEM

To illustrate the calculation of multicomponent vapor-liquid equilibrium using the flash equations and the K-charts, a problem is worked out in detail below.
The variables are defined in Figure I. Note that the K-value is implied to be at thermodynamic equilibrium.
--`````-`-`,,`,,`,`,,`---
yi = K,xi in column 8. This "correct" value is used for purposes of illustration. It is not a completely converged solution, for xi = 1.00431 and yi = 0.99988, columns 7 and 8 of Figure 3-FPS. This error will be too large for many applications. To check the convergence pressure assumption. the components heavier than methane in the liquid are converted to a weight fraction basis as shown in columns 10 and 11 using the molecular weights in column 9. Using this composition (column 1 1 ) of the pseudoheavy component, calculate the weight average critical temperature and pressure using the Tci and PCi in columns 12 and 13; the results are shown at the bottom of those columns. By referring to Figure 5 , the calculated T c of 354F is seen to fall between n-butane and n-pentane, and the calculated P c falls in line with the other paraffin hydrocarbons. By interpolation, as follows, the critical pressure for the pseudobinary, or the convergence pressure, may be calculated at -20F without actually sketching in a new locus:
13) of the pseudo heavy component. calculate the mash averapt. critical temperature and pressure using the T,, Irnd Pi,I I I columns 10 and 11; the results are shown at the bottom of those columns. By referring to Figure 3-SI. the calculated T,' o t 175.4"C is seen to fail between n-butane and n-pentane. and the calculated P,' falls in line with the other paraffin hydrocarbons. By interpolation, as follows. the critical pressure for the pseudo binary, or the convergence pressure. may be calculated at -30C without actually sketching in a new locus:
All the Pks are read from the loci at -30C and the prime quantitites, Tcx' and Pkx'. refer to the pseudo binary. Thus.
(448'6 - 425.2) (1 3800 - i 1700)+ 1700 (469.6 - 425.2)
Eq. 13
23.4 (2100) + 11700 = 12800 kPa

44.4 12800 6.895
All the Pks are read from the loci at -20F and the prime quantitites, TCx P'kx, refer to the pseudobinary. Thus and (813.8 765.6) P'k = (845.3 - 765.6)
= 1856 psia
(2000 - 1700) + 1700
48.2 PIk= -(300) + 1700 = 1881 psia 79.7 This confirms the assumed Pk = 2000 closely enough for this illustration. The more closely the operating pressure approaches the convergence pressure the more accurately the calculated Pk must check the assumed Pk because in this region, the K-values are most sensitive to the Pk value used. Example 2-SI- A typical high pressure separator gas is used for feed to a natural gas liquefaction plant, and a preliminary step in the process involves cooling to -30C at 4000 kPa (abs) to knock out heavier hydrocarbons prior to cooling to lower temperatures where these components would freeze out as solids. Estimate the convergence pressure Pk. Solution Steps - The feed gas composition. shown in Figure 3 SI, column I , is similar to that used in the enthalpy and entropy problems in Section 24 of the Engineering Data Book. Pk is first estimated to be 2000 psia (1 3800 kPa) and K's are read off as in column 2. Then the flash equation 8 is solved for three estimated values of L as shown in columns 3, 4 and 5 . By plotting estimated L versus calculated L xi, the correct value of L where C xi = 1.00 is L = 0.030, whose solution is shown in columns 6 and 7. The gas composition is then calculated using yi = Kixi as in column 8. This "correct" value is used for purposes of illustration. It is not a completely converged solution. for xi = 1.0089 and yi = 0.99972, columns 7 and 8 of Figure 3-SI. This error will b too large for many applications. To check the convergence pressure assumption. the components heavier than methane in the liquid are converted to a mass fraction basis as shown in columns 12 and i 3 using the molecular masses in column 9. Using this composition (column 6
Not for Resale
This confirms the assumed Pk = 2000 closely enough for this illustration. The more closely the operating pressure approaches convergence pressure the more accurately the calculated Pk must check the assumed Pk because in this region, the K-values are most sensitive to the Pk value used. Example 3-FPS- Dew Point Calculation
As gas stream at 100F and 800 psia is being cooled in a heat exchanger. Find the temperature at which the gas starts i o condense.
Solution Steps - The approach to find the dew point of the gas stream is similar to the last example. Assume a convergence pressure of 1000 psia. The equation for dew point condition (CNi/Ki=l.O) is solved for two estimated dew point temperatures as shown in Figure 4-FPS. By interpolation. the temperature at which LNi/Ki = 1.0 is estimated at -44F. To check the convergence pressure, assume the corresponding saturated liquid consists largely of the heaviest componet, propane. This agrees with the fact that the First condensed liquid droplet from any gas stream is the heaviest component in that stream. From Figure 5 , the convergence pressure at -44F for the pseudoheavy component, propane, is 1240 psia. This is close to the assumed convergence pressure of 1O00 psia.
Example 3-SI -Dew
Point Calculation
A gas stream at 40C and 5500 kPa (abs) is being cooled in a heat exchanger. Find the temperature at which the gas starts to condense.
Solution Steps -The approach to find the dew point of the gas stream is similar to the previous example. The equation for dew point condition (ZNi/Ki = 1.0) is solved for two estimated dew point temperatures as shown in Figure 4-SI. By interpolation, the temperature at which cNi/Ki = i .O is estimated at -4 1.4"C.
Figure 4 FPS Dew Point Calculation at 800 psia

1
Column
1 Feed
Component CH4 CO2
C2H6 C3H8
2 P, = loOO. T = -50F
3 P, = 1000, T = -40F
Ni
Ki
i .420
Ni
Ki
Ki
Ni
Ki 0.589
0.854 00 1 .5 0.063 0.032

1.o00
0.790 0.440
0.145
0.601 0.065 0.143 0.221

1.O30
1.450 0.834 0.480 0.158
0.06 1 0.131 0.203

0.984
E=
k o 2calculated as 4K,-, G2
Linear interpolation: Tdew = -50 + 1-50 (-4011 Alternatively iterate until Z N i 6 = 1.O
Figure 4 SI
Dew Point Calculation at 5500 kPa (abs)
Column Feed Component CH4 CO2
C2H6
C3H8
Estimated T = -45C Ki
Estimated T = -40C
Ni
Ni
K;
Ki
Ni
K:
L
0.854 0.051 0.063 0.032

1.o00
2.73 0.866
0.275 0.070
0.313 0.059 0.229 0.457

1 .O58
27 .5
0.9 1O 0.300
03 1 .1
0.056
0.080
0.21 o 0.400
0.977
2=
&o2 calculated as 4 QI
G2
Linear interpolation: Tdew = -40 i 4 - (-4511 -0 Alternatively iterate until Z NiKi = 1 .O
~ =-41.4"C ~
Note that the heaviest component is quite important in dew point calculations, since it essentially determines the convergence pressure. For more complex mixtures, the characterization of the heavy fraction as a pseudocomponent such as hexane or octane will have a significant effect on dew point calculations.
Carbon Dioxide Early conflicting data on CO, systems was used to prepare convergence pressure (Pi, = 4000)charts for the 1966 Edition.
Later, experience showed that at low concentrations of CO2, the rule of thumb
could be used with a plus or minus 10% accuracy. Developments in the use of CO2 for reservoir drive have led to extensive investigations in CO, processing. See the more recent GPA research reports (listed in Section 1 of the Engineering Data Book) and the Proceedings of GPA conventions. The reverse volatility at high concentration of propane and/or butane
7
Not for Resale
--`````-`-`,,`,,`,`,,`---
2 -
3 -
has been used effectively in extractive distillation to effect CO2 separation from methane and ethane.z2 In general, CO, lies between methane and ethane in relative volatility. Separation of CO2and Methane See Section 16, Hydrocarbon Recovery, of the 11th Edition of the GPSA Engineering Data Book. C02-Ethane Separation See Section 16, Hydrocarbon Recovery of the 11th Edition of the Engineering Data Book. Separation of CO2 and H2S See Section 16, Hydrocarbon Recovery of the 1lth Edition of the Engineering Data Book.
hydrocarbon components are necessary in the Redlich-Kwong equation to predict the K-values accurately when high concentrations of non-hydrocarbon components are present. They are especially important in CO, fractionation processes. and i n conventional fractionation plants to predict sulfur compound distribution. The Chao-Seader correlation' uses the Redlich-Kwong equation for the vapor phase, the regular solution model for liquid-mixture non-ideality, and a pure-liquid property correlation for effects of component identity. pressure. and temperature in the liquid phase. The correlation has been applied to a broad spectrum of compositions at temperatures from -0F 5' [-46"C] to 300F [150C] and pressures to 2000 psia [13.8 MPa(abs)]. The original (P,T) limitations have been reviewed.]? Prausnitz and Chueh have developed16 a procedure for highpressure systems employing a modified Redlich-Kwong equation for the vapor phase and for liquid-phase compressibility together with a modified Wohl-equation model for liquid phase activity coefficients. Complete computer program listings are given in their book. Parameters are given for most natural gas components. Adler et al. also use the Redlich-Kwong equation for the vapor and the Wohl equation form for the liquid phase.6 The corresponding states principlelo is used in all the procedures discussed above in that the behavior of all substances is assumed to follow the same equation forms and equation parameters are correlated versus critical properties and acentric factor. An alternate corresponding states approach is to refer the behavior of all substances to the properties of a reference substance, these properties being given by tabular data or a highly accurate state equation developed specifically for the reference substance. The deviations of other substances from the simple criticalparameter-ratio correspondence to the reference substance are then correlated. Mixture rules and combination rules, as usual, extend the procedure to mixture calculations. Leland and coworkers have developed9 this approach extensively for hydrocarbon mixtures. "Shape factors" are used to account for departure from simple corresponding states relationships, with the usual reference substance being methane. The shape factors are developed from PVT and fugacity data for pure components. The procedure has been tested over a reduced temperature range of 0.4 to 3.3 and for pressures to 4000 psia r27.6 MPa(abs)]. Sixty-two components have been correlated including olefinic, naphthenic, and aromatic hydrocarbons. The Soave Redlich-Kwong (SRK)I3 is a modified version of the Redlich-Kwong equation. One of the parameters in the original Redlich-Kwong equation, a, is modified to a more temperature dependent term. It is expressed as function of the acentric factor. The SRK correlation has improved accuracy in predicting the saturation conditions of both pure substances and mixtures. It can also predict phase behavior in the critical region, although at times the calculations become unstable around the critical point. Less accuracy has been obtained when applying the correlation to hydrogen-containing mixtures.
OTHER K-VALUE PROCEDURES

Numerous procedures have been devised to predict Kvalues. These include state equations, combinations of state equations with liquid theory or with tabular data, and corresponding states correlations. This section describes several of the more popular procedures currently available. It does not purport to be all-inclusive or comparative. State equations have appeal for predicting thermodynamic properties because they provide internally consistent values for all properties in convenient analytical form. Two popular state equations for K-value predictions are the Benedict-Webb-Rubin (BWR) equation and the Redlich-Kwong equation. The original BWR equation17 uses eight parameters for each component in a mixture plus a tabular temperature dependence for one of the parameters to improve the fit of vapor-pressure data. This original equation is reasonably accurate for light paraffin mixtures at reduced temperatures of 0.6 and above.* The equation has difficulty with low temperatures, nonhydrocarbons, non-paraffins, and heavy paraffins. Improvements to the BWR include additional terms for temperature dependence, parameters for additional compounds, and generalized forms of the parameters. Starling20 has included explicit parameter temperature dependence in a modified B W R equation which is capable of predicting light paraffin K-values a cryogenic temperatures. t The Redlich-Kwong equation has the advantage of a simple analytical form which permits direct solution for density at specified pressure and temperature. The equation uses two parameters for each mixture component, which in principle permits parameter values to be determined from critical properties. However, as with the BWR equation, the Redlich-Kwong equation has been made useful for K-value predictions by empirical variation of the parameters with temperature and with acentric factor l9 and by modification of the parametercombination rules. l 5 ~l 9 Considering the simplicity of the Redlich-Kwong equation form, the various modified versions predict K-values remarkably well. Interaction parameters for non-hydrocarbons with
--`````-`-`,,`,,`,`,,`---
8
Not for Resale
STDmGPA TP-ZZ-ENGL
1799
3824b97 002048b 547'
Peng and Robinson14 similarly developed a two-constant Redlich-Kwong equation of state in 1976. In this correlation, the attractive pressure term of the semi-empirical van der Waals equation has been modified. It accurately predicts the vapor pressures of pure substances and equilibrium ratios of mixtures. In addition to offering the same simplicity as the SRK equation, the Peng-Robinson equation is more accurate in predicting the liquid density. In applying any of the above correlations, the original critical/physical properties used in the derivation must be inserted into the appropriate equations. One may obtain slightly different solutions from different computer programs, even for the same correlation. This can be attributed to different iteration techniques, convergence criteria, initial estimation values, etc. Determination and selection of interaction parameters and selection of a particular equation of state must be done carefully, considering the system components, the operating conditons, etc.
a=a,a a, = 0.42747
() q
m = 0.48 + 1.574 o - 0.176 02

b = 0.08664 Peng Robinson27
23-
(7)
(1
- B) Z2+ (A - 3B* - 2B) Z - (AB - B* - B3) = O
EQUATIONS OF STATE
Refer to original papers for mixing rules for multicomponent mixtures. van der Waals"
23
- (1 + B) 2 2 + AZ - A B= O
A=
m = 0.37464 + 1.54226 o - 0.26992 a 2 b=0.0778
R2T2
aP
>: (
bP B= RT
a=
Benedict-Webb-Rubin-Starling(BWRS)20-25
P=V
27 R*T2, 64 Pc
C D E B,RT-A,-o+o-o T2 T3 T'l
--`````-`-`,,`,,`,`,,`---
RTC b= pc Redlich-Kwong" Z3 - Z2 + ( A - B - B2) Z - AB = O
(bRT-a--$-)$+CX
(a+$)
1
V6
- YN2
v 3
aP A= bP B= RT a = 0.42747
~2~2.5
REFERENCES AND BIBLIOGRAPHY

1.
() +
R2T 2.5 2.
Wilson, G. M., Barton, S.T., NGPA Report RR-2: "KValues in Highly Aromatic and Highly Naphthenic Real Oil Absorber Systems," (197 I). Poettman. F. H., and Mayland, B. J.. "Equilibrium Constants for High-Boiling Hydrocarbon Fractions of Varying Characterization Factors," Petroleum Refiner 28. 101-102, July. 1949. White, R.R., and Brown, G. G., "Phase Equilibria of Complex Hydrocarbon Systems at Elevated Temperatures and Pressures," Ind. Eng. Chem. 37, 1162 (1942). Grayson, H.G.,and Streed, C. W., "Vapor-Liquid Equilibria for High Temperature. High Pressure HydrogenHydrocarbon Systems," Proc. 6th World Petroleum Cong., Frankfurt Main, III, Paper 20-DP7, p. 223 (1963).
Soave Rediich-Kwong (SRK)13
Z3- Z2 + (A - B - B2 ) Z - AB = O
A=
3.
aP R ~ T ~
4.
bP B= RT
Not for Resale
5.
Chappelear, Patsy, GPA Technical Publication TP-4, "Low Temperature Data from Rice University for Vapor-Liquid and P-V-T Behavior," April (1 974). Adler, S. B., Ozkardesh, H., Schreiner, W. C., Hydrocarbon Proc., 47 (4) 145 (1968). Chao, K. C., Seader, J. D., AIChEJ, 7,598 (1961). Bamer, H. E., Schreiner, W. C., Hydrocarbon Proc., 45 (6) 161 (1966). Leach, J. W., Chappelear, P. S..and Leland, T.W., "Use of Molecular Shape Factors in Vapor-Liquid Equilibrium Calculations with the Corresponding States Principle," AIChEJ. 14,568-576 (1968).
Hydrocarbons and Their Mixtures,'' Chem. Eng. Prog. 47. 419-422 (1951); J. Chem. Phys. 8.334 (1940). 26. van der Waals, J., "Die Continuitat des Gasformigen und nussigen Zustandes," Barth, Leipzig ( 1899). 27. Peng, D.Y., Robinson, D. B.. "A New Two-Constant Equation of State," Ind. Eng. Chem. Fundamentals 15. 5964 (1976).
6.
7.
8. 9.
ADDITIONAL REFERENCES
See listing in Section I of the Engineering Data Book for GPA Technical Publications (TP) and Research Reports (RR). Note that RR-64, RR-77, and RR-84provide extensive evaluated references for binary, ternary. and multicomponent systems. Also as a part of GPNGPSA Project 806. a computer data bank is available through the GPA Tulsa office. Another extensive tabulation of references only is available from Elsevier Publishers of Amsterdam for the work of E. Hala and I. Wichterle of the Institute of Chemical Process Fundamentais, Czechoslovak Academy of Sciences, PragueSuchdol. Czechoslovakia. Also, Hiza, M. J., Kidnay, A. J., and Miller. R . C., Equilibrium Properties of Fluid Mixtures Volumes I and II. IFyPienum, New York, 1975. See Fluid Phase Equilibria for various symposia.
10. Leland, T. W., Jr., and Chappelear, P. S.,"The Corresponding States Principie-A Review of Current Theory and Practice," Ind. Eng. Chem. 60, 15-43 (July 1968); K.C.Chao (Chairman), "Applied Thermodynamics," ACS Publications, Washington, D.C., 1968, p. 83. I l . Bamer, H. E., Pigford, R. L., Schreiner, W. C.. Proc. Am. Pet. Inst. (Div. Ref.) 46 244 (1966). 12. Lenor, J. M., Koppany, C. R.. Hydrocarbon Proc. 46,249 (1967). 13. Soave, Giorgio, "Equilibrium Constants from a Modified Redlich-Kwong Equation of State," Chem. Eng. Sci. 27, 1 197-1203 (1972). 14. Peng, D.Y., Robinson, D. B., Ind. Eng. Chem. Fundamentals 15 ( 1976). 15. Spear, R. R., Robinson, R. L.. Chao, K. C., IEC Fund., 8 (1) 2 (1969). 16. Prausnitz, J. M., Cheuh, P. L., Computer Calciilations for High-pressure Vapor-Liquid Equilibrium, Preiitice-Hall (1968). 17. Benedict, Webb, and Rubin, Chem. Eng. Prog. 47,419 ( 195 1 ). 18. Wilson, G. M., Adv. Cryro. Eng., Vol. II, 392 (1966). 19. Zudkevitch. D., Joffe. J.. AIChEJ., 16 ( I ) 112 (1970). 20. Starling, K. E., Powers, J. E., IEC Fund., 9 (4) 531 (1970). 21. Hwang, S . C., Lin. H.M.. Chappelear. P. S., and Kobayashi, R., "Dew Point Values for the Methane Carbon Dioxide System," GPA Research Report RR-21 (1976). 22. Price, B. C., "Looking at COz Recovery", Oil & Gas J., p. 48-53 (Dec. 24, 1984). 23. Nagahana, K., Kobishi, H., Hoshino, D., Hirata, M., and "Binary Vapor-Liquid Equilibria of Carbon Dioxide-Light Hydrocarbons at Low Temperature," J. Chem. Eng. Japan 7, No. 5, p. 323 (1974). 24. Redlich, O.. Kwong, J. N. S., Chem. Rev. 44,233 (1 949).
CHARTS FOLLOW AS LISTED BELOW

Convergence Pressure Charts: 80W to 10000# pages I l through 101 Binaries: Pages 102 - 1 1 1 Methane-Ethane Methane-Propane Methane-Ethane & Methane-Propane Infinite Dilution Methane-n-Butane Methane-n-Pentane Methane-n-Hexane Methane-n-Heptane Nitrogen-Methane Nitrogen-Ethane Methane-Carbon Dioxide Poettmann Charts: Pages 112 through 117 1957 Engineering Data Book Hydrogen Sulfide-Ethane Hydrogen Sulfide-Propane Hy drogen-Ethane Hydrogen-Propane Hydrogen-Isobutane Hydrogen-n-Bu tane Hydrogen-Octane through Dodecane Hydrogen-Benzene Hydrogen-Toluene
--`````-`-`,,`,,`,`,,`---
25. Benedict. M.. Webb, G. B., Rubin, L. C., "An Empirical Equation for Thermodynamic Properties of Light
118 119 120 121 122 123 124 125 126
10
Not for Resale
VlSd
'
3YflSS3d
39N393AN03
S T D - G P A TP-22-ENGL
1999
Not for Resale
3829b97 002Oi188 312
I'
--`````-`-`,,`,,`,`,,`---
r R E S S U H t . PSIA
--`````-`-`,,`,,`,`,,`---
K=
Not for Resale
STDmGPA TP-22-ENGL
1999
3 8 2 4 b 7 0172U470 T70 E l
PRESSURE. PSIA
1
PRESSURE, kPa (abs)

--`````-`-`,,`,,`,`,,`---
13
Not for Resale
METHANE
CONV. PRESS. 800 PSIA
--`````-`-`,,`,,`,`,,`---
14
Not for Resale
--`````-`-`,,`,,`,`,,`---
Not for Resale
I
I 4
F
PRESSURE. PSIA
m a3-
I3 ni
O O
[ r
r
J I
I
ni
a l
II
ci-
aaF l
I W
I
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I -
n
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K Y
16
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--`````-`-`,,`,,`,`,,`---
I l u l u
S T D - G P A TP-ZZ-ENGL
1 7 7 7 ssl 3 8 2 4 b l 9 0020494 bLb
m-.
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S T D * G P A TP-ZZ-ENGL 1779 3 8 2 9 b 7 7 0020475 552 PRESSURE, PSIA
K = Y/,
'X
O.
.o
--`````-`-`,,`,,`,`,,`---
PRESSURE, kPa (abs)
18
i-BUTANE
Not for Resale
CONV. PRESS. 800 PSlA
= ytx
PRESSURE, kPa (abs)
Not for Resale
19
n-BUTANE
--`````-`-`,,`,,`,`,,`---
--`````-`-`,,`,,`,`,,`---
Not for Resale
PRESSURE, PSIA
K=Y/
PRESSURE, kPa (abs)

21Not for Resale
n-PENTANE
--`````-`-`,,`,,`,`,,`---
--`````-`-`,,`,,`,`,,`---
~ ~~
PRESSURE, kPa (abs)
HEXANE'
22Not for Resale

~
K = Y/,
.E
.o0
--`````-`-`,,`,,`,`,,`---
PRESSURE, kPa (abs)

Not23 for Resale
OCTANE
I
n
4l
d
PRESSURE. PSIA
a
O
ir)
O
l u
O O
ur n
U
uuui l
z
w
I I 111
ru
c a
I Y
Y I'X
~. . .
PRESSURE, kPa (abs)

DECANE
24
Not for Resale
--`````-`-`,,`,,`,`,,`---
~~
S T D O G P A TP-22-ENGL 3999 SB 3824b99 Il020502 512 PRESSURE, PSIA

,000
O0
,000
100
1 0
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ia
1.
1.o
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--`````-`-`,,`,,`,`,,`---
Not for Resale
1777 H 3824h77 0020503 457
Pgs
K :Y
--`````-`-`,,`,,`,`,,`---
PRESSURE, kPa (abs)

26
Not for Resale
METHANE
~-
S T D = G P A TP-22-ENGL
1797 W 3824b99 00205U4 395 PRESSURE. PSIA
--`````-`-`,,`,,`,`,,`---
Not for Resale
STDOGPA TP-22-ENGL
1979
3824b99 0020505 2 2 1 W
PRESSURE. PSIA
K=
PRESSURE, kPa (abs)

28
--`````-`-`,,`,,`,`,,`---
ETHANE
Not for Resale
~~
~~
STD-GPA TP-22-ENGL
1999 1118 3824b99 O2050b Lb I

. .
PRESSURE, PSIA
PRESSURE, kPa (abs)

29
Not for Resale
PROPANE
--`````-`-`,,`,,`,`,,`---
~~
I
3 -
PRESSURE. PSIA
tO
O
u l
111
O
CI
n-
a-
d
3 -
111
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I
b
ai l
.I Q I
n-
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I
a
k-
a
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r.4
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--`````-`-`,,`,,`,`,,`---
W I N N
1999 I 3829679 0020508 T30 I I PRESSURE, PSIA

2
3.000
910.000
.I
.u1
9
8 7 6 3
4
.u1
9
8
1
6
5
4
.O01
.O01
PRESSURE, kPa (abs)
Not 31 for Resale
CONV. PRESS. loo0 PSIA
i-BUTANE
--`````-`-`,,`,,`,`,,`---
.~
-~
L999 I 3824b99 0020509 977 I I PRESSURE. PSIA
K Y
Not for Resale
--`````-`-`,,`,,`,`,,`---
STD-GPA TP-22-ENGL 1999
S 3824b99 RDi?051R 699 M
PRESSURE. PSIA
4 84100
I I !
--`````-`-`,,`,,`,`,,`---
300
' 5Oo6
I
I I I I ' I
"9L333
I 2
3,333
I 4
I I I I !
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PRESSURE, kPa (abs)
33for Resale Not
i-PENTANE
-~
S T D = G P A TP-22-ENGL 1999 Is 382'ib97 00205Ll 525 111 PRESSURE. PSIA
I :Y
--`````-`-`,,`,,`,`,,`---
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i
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I
Il
FI
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W I N
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I
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t-
a
R
W
t -
vl
.c
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--`````-`-`,,`,,`,`,,`---
PRESSURE, kPa (abs)

35 Not for Resale
HEXANE
K : Y/X
I
36
Not for Resale
--`````-`-`,,`,,`,`,,`---
K=
--`````-`-`,,`,,`,`,,`---
PRESSURE, kPa (abs)

Not for Resale
DECANE
37
U
-I
i l
u l
i l
u l
O
N
nnd
f
N
dl
rn
I Q
ca a
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PRESSURE, kPa (abs)
38
Not for Resale
HYDROGEN SULFIDE
--`````-`-`,,`,,`,`,,`---
PRESSURE, PSIA.
PRESSURE, kPa (abs)

39
Not for Resale
METHANE
--`````-`-`,,`,,`,`,,`---
1777
382Lib99 O020537 T 9 3
PRESSURE, PSIA
K J
PRESSURE, kPa (abs)

--`````-`-`,,`,,`,`,,`---
40
Not for Resale
ETHANE
STDOGPA TP-22-ENGL 1777 BI 3824b77 0020538 98T IIP
--`````-`-`,,`,,`,`,,`---
PRESSURE, kPa (abs)

41
Not for Resale
PROPANE
PRESSURE. PSIA
Not for Resale
--`````-`-`,,`,,`,`,,`---
O
N
VI
I
w
I
N lu
Yx
--`````-`-`,,`,,`,`,,`---
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PRESSURE, PSIA
~ ~
--`````-`-`,,`,,`,`,,`---
PRESSURE, kPa (abs)

~
44
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i - PENTANE
~~
S T D * G P A TP-22-ENGL
1999 W 382ib99 0020522 300 IBI PRESSURE, PSIA
IK fI
--`````-`-`,,`,,`,`,,`---
Not for Resale
1
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PRESSURE, PSIA
m m
N
vl
a-
111
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3-
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D-
o-
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n
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K :Ir/X
--`````-`-`,,`,,`,`,,`---
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N
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51
Not for Resale
NITROGEN
--`````-`-`,,`,,`,`,,`---
S T D * G P A TP-ZZ-ENGL
1 9 9 9 W 382'4b94 0020527 7b5
PRESSURE. PSIA
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1.1
--`````-`-`,,`,,`,`,,`---
Not for Resale
T D = G P A TP-22-ENGL
1997 M 382Yb97 013205313 487 W
PRESSURE. PSIA
PRESSURE, kPa (abs)
53
Not for Resale
ETHYLENE
--`````-`-`,,`,,`,`,,`---
S T D - G P A TP-ZZ-ENGL 1777 61 382qb97 0020531 3 2 3 E
K YI
PRESSURE, kPa (abs)

54
Not for Resale
ETHANE
--`````-`-`,,`,,`,`,,`---
1977 H 3824b97 0020532 25T PRESSURE. PSIA
K Y
PRESSURE, kPa (abs)
-PROPYLENE
Not for Resale
55
--`````-`-`,,`,,`,`,,`---
K :Y
Not for Resale
--`````-`-`,,`,,`,`,,`---
~ ~
~~
~~
B
m o
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=r
m w
m o
O
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--`````-`-`,,`,,`,`,,`---
PRESSURE, kPa (abs)
57
Not for Resale
i - BUTANE
I
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PRESSURE, PSIA
IV)
m w
ru
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r r
d
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ru
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--`````-`-`,,`,,`,`,,`---
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PRESSURE, kPa (abs)
58 for Resale Not
P
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PRESSURE. PSIA
I-
rn
Ln
D N D O
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--`````-`-`,,`,,`,`,,`---
PRESSURE, kPa (abs)
Not for Resale
59
CONV PRESS. 3000 PSIA
i - PENTANE
PRESSURE, PSIA
N O O
z
w
K Y
/X
PRESSURE, kPa (abs)
60
Not for Resale
~tPENTANE CONV. PRESS. 2000 PSIA
--`````-`-`,,`,,`,`,,`---
B
a
I C I C
PRESSURE, PSIA
a
VI
m n
O
--`````-`-`,,`,,`,`,,`---
PRESSURE, kPa (abs)
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61
HEXANE
B
aO J I
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PRESSURE. PSIA
rn
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--`````-`-`,,`,,`,`,,`---
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rn
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--`````-`-`,,`,,`,`,,`---
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111
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111
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PRESSURE. PSIA
--`````-`-`,,`,,`,`,,`---
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PRESSURE, kPa (abc)
Not for Resale
65
DECANE
S T D - G P A TP-22-ENGL 1797 88 3829b97 0020543 035
I I
A
66
Not for Resale
--`````-`-`,,`,,`,`,,`---
1999
382qb99 0 0 2 0 5 ~ 4T7L
PRESSURE, kPa (abs)

67
Not for Resale
ETHANE
--`````-`-`,,`,,`,`,,`---
S T D - G P A TP-22-ENGL 1999 W 3824b79 0020545 908

PRESSURE, PSIA
K Y
--`````-`-`,,`,,`,`,,`---
PRESSURE, kPa (abs)

68
Not for Resale
PROPANE
--`````-`-`,,`,,`,`,,`---
Not for Resale
PRESSURE. PSIA
--`````-`-`,,`,,`,`,,`---
Not for Resale
1181
I
aIT IT
F I
I W
w I m
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W
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71
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--`````-`-`,,`,,`,`,,`---
S T D * G P A TP-22-ENGL 1 9 9 9 3824b77 0 0 2 0 5 ~ 7553 P PRESSURE. PSIA

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K Y
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--`````-`-`,,`,,`,`,,`---
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PRESSURE, kPa (abs)

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73
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O
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74
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PRESSURE, kPa (abs)
75
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OCTANE
--`````-`-`,,`,,`,`,,`---
PRESSURE, PSIA
O Tu O O
z
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I
I lu lu
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--`````-`-`,,`,,`,`,,`---
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NONANE
Yi'X
PRESSURE, kPa (abs)
Not for Resale
77
--`````-`-`,,`,,`,`,,`---
1999
382Lib79 0020555 857
PRESSURE. PSIA
=
.o00
K=
--`````-`-`,,`,,`,`,,`---
Not for Resale
S
PRESSURE. PSIA
--`````-`-`,,`,,`,`,,`---
K Y
Not for Resale
79
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IK
--`````-`-`,,`,,`,`,,`---
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80for Resale Not
TOM\I
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--`````-`-`,,`,,`,`,,`---
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--`````-`-`,,`,,`,`,,`---
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--`````-`-`,,`,,`,`,,`---
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83 Not for Resale
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PRESSURE, PSIA
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~~
S T D O G P A TP-22-ENGL
1 9 9 9 11111 382qb77 0020563 050 R PRESSURE, PSIA
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--`````-`-`,,`,,`,`,,`---
PRESSURE, PSIA
O
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Not for Resale
O N O O
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-0
a-
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I
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--`````-`-`,,`,,`,`,,`---
Not for Resale
PRESSURE. PSIA
--`````-`-`,,`,,`,`,,`---
nun4 I W
w I rn
I
l u
n
t-
a
0-
a
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PRESSURE, kPa (abs)
Not for Resale
88
PRESSURE. PSIA
z
w
I I l l N I
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I -
a
o ,
W
I -
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K=
--`````-`-`,,`,,`,`,,`---
PRESSURE, kPa (abs)

Not for Resale
89
PRESSURE. PSIA
oooi l
I
I -
a
W
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Fi
c
VI
PRESSURE, kPa (abs)

90 Not for Resale
~
DECANE
~
--`````-`-`,,`,,`,`,,`---
1999 H 362qb77 00205b8 405 lai
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--`````-`-`,,`,,`,`,,`---
F I f
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O
I
uI-I W
I
LI
N
lu
I
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92
Not for Resale
CONV. PRESS. 10,000 PSIA
PROPANE
--`````-`-`,,`,,`,`,,`---
--`````-`-`,,`,,`,`,,`---
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I I
111
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--`````-`-`,,`,,`,`,,`---
PRESSURE, PSIA
ZRESSURE, kPa (abs)
Not for Resale
95
C ~ + P \ , ..in---
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--`````-`-`,,`,,`,`,,`---
--`````-`-`,,`,,`,`,,`---
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0 111
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d
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111 111
I Q
I -
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A
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I VI
IK =
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--`````-`-`,,`,,`,`,,`---
PRESSURE, kPa (abs)
97
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HEXANE
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PRESSURE. PSIA
--`````-`-`,,`,,`,`,,`---
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PRESSURE, kPa (abs)
98 for Resale Not

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PSIA
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PRESSURE. PSIA
o
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PRESSURE, kPa (abs)
33 Not for Resale
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OCTANE
PRESSURE. PSIA
PRESSURE, kPa (abs)
1O0
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NONANE
--`````-`-`,,`,,`,`,,`---
PRESSURE. PSIA
--`````-`-`,,`,,`,`,,`---
Not for Resale
101
CONV. PRESS. 10.000 PSIA

~~ ~ ~~ ~
PRESSURE. PSIA
'ature lents
O C
- 18 - 32
46 59 - 73 - 87 -101 -1 15 -129 -143
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--`````-`-`,,`,,`,`,,`---
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--`````-`-`,,`,,`,`,,`---
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"F
50 O - 50 - 75 -100 -125 -150 -175 -200 -225
"C
10 18 46 59 73 - 87 -101 -115 -1 29 -143
PRESSURE, kPa (abs)

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103
BISA RI'
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--`````-`-`,,`,,`,`,,`---
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105 Not for Resale
METHAN E - 11BUTAN E BIhARY
S T D a G P A TP-22-ENGL
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K = Y/X
K = y&
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10
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100
300 500 1,000
3.000
10,000 1O0
IT IT
11
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PRESSURE, kPa (abs)

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107
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--`````-`-`,,`,,`,`,,`---
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PRESSURE, kPa (abs)
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METHANE-nHEPTANE BINARY
PRESSURE. PSIA
Tempe!rature Equivid e n t s
OF
"C
-1 30
90
-150 -1 70 -1 90 -210 -230 -250 -270
-101 -112
-123
-134 -146 -157 -168
PRESSURE, kPa (abs)

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NITROGEN - METHANE
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- 79
- 90 -101 -112 -123 -134
PRESSURE, kPa (abs)

--`````-`-`,,`,,`,`,,`---
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.Not for Resale
NITROGEN- ETHANE
isothermal K values for methane-carbon dioxide system

I
60 70 80 90100
200
Pressure, psia 300 400
500 600
800 1.000
!
1
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700
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0.:
2000
3000
5000
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Mraw, Hwang, and Kobayashi, Rice University
11 1
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PRESSURE,
PSIA
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PRESSURE, PSIA
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HYDROGEN IN PROPANE
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124
PSIA
HYDROGEN IN OCTANE THROUGH DODECANE-
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125
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126
Not for Resale

Constantes de Equilibrio

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Constantes de Equilibrio

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Tech ncal Publcation

Published by the Gas Processors Association

6526 East 60th Street * Tulsa, Oklahoma 74145

Phone: 918/493-3872 Fax:

Not for Resale

Not for Resale

Convergence Pressure and Vapor-Liquid Equilibrium Ratios

GPA Technical Publication TP-22

6526 E. 60th Street Tulsa, OK 74145

Not for Resale

Not for Resale

Not for Resale

382qb97 00201178 1173

Use of Binary Charts - At temperatures below - 0 ' 10F

log KP = log KP(M)

BINARY SYSTEMS DATA CHARTS

[-73"C]) calculations. Below the critical temperature of

R = universal gas constant, (psia

ft)Ab mole "R)[(kPa m3 ) /(kmole K)]

Subscripts I = component c = critical M = methane E = ethane P = propane

3824b99 0020479 30"

K-VALUES CORRELATION BY CONVERGENCE PRESSURE

Example 1 - Binary System Calculation

Convergence pressure, kPa (abc) [psia]

13800 20700 [2000] j [3000]

Ethane Propylene Propane

binary K-data is recommended below the critical of methane

Feed Gas :omponent I Composition

1 4 1 5 Trial values of L L = 0.02 L = 0.04 L = 0.06

Column 1 7 1 8 Final L = 0.030 Liquid 1 Vapor

0.90 I O 0.0106 0.0499 0.0187

0.0017 0.0019 0.0029 0.0023

0.097 0.038 0.024 0.0088 0.0062 0.0019 O.ooo66

T. K ' P,. kPa (absi ,

0.29368 0.00937 O. 1 1203 0.12369 0.06791

C.28952 c.00934 O. 1 1508

0.08499 0.01138 0.03509 0.04135 0.06934

0.28749 0.00933 0.1 1667 O. I5070 0.09722 0.08446

0.05276 0.09107 0.07506

0.01183 0.01462 0.00369 0.00203 0.00039 0.00033

58.12 58.12 72.15 72.15 86.18 107.0

0.4106 3.5083 6.6459 5.6504 4.9088 3.1825 3.8066

End of flash calculation

Calculation to confirm PI.

Figure 3 FPS Example Flash Calculation at 600 psia and -20F

30S.J 369.8 408.1 425.2 460.4 469.6 507.4

36111 3797 3381 3369 3012 261 I 3542

1 4 Trial values of L=O.O2 I L=0.06

- .._ ._ Tc. "U

0.0045 0.00 I7 0.0019 0.0029 0.0023

0.08598 0.05192 0.06376 0.12696 0.1 I198

0.11445 0.11783 0.06354 0.04944 0.02354 0.02738 0.04623 0.03801 0.78354

O. I 1989 0.14478 0.09183 0.07613 0.04288 0.02173 0.09724 0.08353 1.00431

44.01 30.07 44.10 58.12 58.12 72. I5 72.15 86.18 107.00

End of flash calculation

0.4141 3.6052 6.3846 5.3370 4.4247 3.0935 3.7322 8.3805 8.9377

0.0093 0.08 I4 0.1441 o. I204

0.0698 0.0842 0.1891 0.2017

616.0 527.9 550.6 490.4 48.6 436.9 378.7 SOY.?

HIGH BOILING OIL FRACTIONS

DATA FOR NONHYDROCARBONS

Other useful versions may be written as Eq. 9 KiNi

I;Ki Ni = 1.0 (bubble point) and