Are you sure?
This action might not be possible to undo. Are you sure you want to continue?

z.
APPLICATION OF THE BtiRS EQUATION TO NATURAL GAS SYSTEHS
Scott W. Hopke Chenjung Lin
Esso Production Research Company
Houston. Texas
Pape r to be presented at 76 th National AICh£': Heeting. ~Iarch 1013, 1974. Tulsa. Oklahoma
APPLICATION OF THE BWRS EQUATION TO NATURAL GAS SYSTEMS
by
S. w. Hopke C. J. Lin
ABSTRACT
This paper presents optimal BWRS state equation (a modified BWR equation introduced by Starling) parameters for isobutane, nbutane, isopentane, npentane and carbon dioxide. A correlation that can be used to obtain parameters for heavy hydrocarbon (hexanes plus) fractions based upon their critical temperatures, critical densities and acentric factors i9 also described. The parameters presented here plus optimal BWRS parameters for methane, ethane, propane and nitrogen that were published in an earlier paper can be used to compute all thermodynamic properties of interest for natural gases. The accuracy of the BWRS equation for natural gas systems is verified by comparing computed thermodynamic properties with laboratory data for pure, binary, and multicomponent systems and by comparing the results of simulations using BWRS properties with turboexpander plant performance data.
The optimal BWRS parameters, which were obtained using a previously reported multiproperty regression analYSis procedure, are based on over 16,000 data points for pure components and for binary mixtures. The data include densities, enthalpies, vapor pressures and Kvalues for temperatures from 340op to 700°F and pressures from near zero to 10,400 psia. As an indication of the accuracy that can be obtained over this wide range of conditions, average absolute deviations for density, enthalpy departure and vapor pressure data are 1.07%, 1.49 BTU/lb. and 1.35% respectively. The accuracy of Kvalue predictions is reported on a system by system basis.
INTRODUCTION
The BWRS equation of state is anllparameter, modified BWR equation proposed by Starling.l,2 Stariing and Wolfe3 also proposed the use of multiproperty regression analysis to determine optimal state equation parameters. Multiproperty regression analysis is a procedure by which a leastsquares
fit is made simultaneously to experimental data for several different types of thermodynamic properties.
There are two basic approaches to applying multiproperty regression analysis. The first approach that was used is to determine state equation parameters for a given component from multiproperty data for only that component. Thus, the mixing rules are considered to be exact. In practice, this approach can yield predictions for mixture properties that are much worse than predictions for pure component properties due to inaccuracies in the mixing rules.
The second basic approach uses multiproperty data for mixtures and pure components simultaneously to yield component parameters. This approach, although more empirical than the first, usually produces parameters that
result in better overall thermodynamic property predictions for the systems
of interest. Our recent work on the development of multiproperty analysis procedures has used this second approach. Lin, et al.2 used density, enthalpy, vapor pressure and Kvalue data to determine optimal BWRS parameters for methane and propane. Lin and Hopke4 determined optimal BWRS parameters for methane, ethane, propane and nitrogen by regressing on density, enthalpy, vapor
pressure and Kvalue data for the pure components and binary mixtures. In
both of these analyses, binary interaction parameters and pure component parameters were determined simultaneously.
I
In our regression work, we found that attempts to fit pure component
and binary mixture data alone will not yield a unique set of optimal BWRS parameters for a given component. On the contrary, many widely different parameter sets can give about the same fit to the data. Moreover, the different parameter sets will yield different results when used to predict thermodynamic properties at conditions outside of the temperature and pressure range of the data base used to determine the parameter sets. Also, extrapolation of light hydrocarbon parameters to obtain estimates of parameters
for heavier hydrocarbons is impossible unless a unique set of optimal parameters is obtained.
In this work we developed a new regression procedure to obtain a unique set of optimal parameters for isobutane, normal butane, isopentane, normal pentane and carbon dioxide. This new procedure, which is described in this paper, involves using mUlticomponent Kvalue data to determine one of the eleven BWRS pure component parameters, and then regressing on the remaining ten parameters using density, enthalpy, vapor pressure and Kvalue data for pure components and binary mixtures. Including these multicomponent data has the effect of extending the temperature range of the data base to lower temperatures.
1
Also described in this paper is a correlation that can be used to obtain BWRS parameters for heavy hydrocarbo~ fractions (hexanes plus). Pure component and mixture data for' the normal paraffins from hexane through decane and for benzene, toluene, cyclohexane and methylcyclohexane were used in the development of this heavies correlation. The correlation has the
same form as the HanStarling generalized correlation,S giving parameters
as functions.of critical temperature, critical density and acentric factor. Although this correlation could be used to obtain BWRS parameters for all components, we strongly recommend using this correlation for only the heavy hydrocarbon fractions. Discrete, optimal parameters should be used for the light hydrocarbons and nonhydrocarbons.
The BWRS Equation of State
The BWRS equation is an IIparameter modified BWR equation:
p  pRT + (B RT  A  C IT2 + D IT3
000 0
+ (bRT  a  d/T) p3 + a (8 + d/T) p6 + cp3/T2 (1 + yp2) exp (_yp2),
(1)
where p is the absolute pressure, T the absolute temperature, p the molar density, and R the universal gas constant. Mixing rules used to obtain mixture parameters for the BWRS equation are:
m
A _ .... (:.ll) A l/2A 1/2
o ~~ 2 xixj oi oj
ij
and
m11 4 1/2 1/2
DO • ~~ ( 2) x1xj 001 DOj ,
m11 5 1/2 1/2
EO  ~~ ( 2) x1xj Eol Eoj ,
2
_bIll _ .. b 1/3
l. Xl 1 ' 1
(2)
The BWRS equation can be written in reduced form as:'
where xi is the mole fraction of the "ith" component for the homogeneous phase under consideration, and parameters with subscript "i" refer to the "ith" pure component. The binary int~raction parameters "mij" are equal to 2.0 for i~j. Thus, the interaction parameters form the elements of a symmetric matrix with diagonal elements equal to 2.0.*
*
c * 2 * ?
+ T 3 (1 + Y Pr ) exp (Y Pr),
r
where Z is the compressibility factor, Tr is the reduced temperature (T/Te), and Pr is the reduced density (pIPe). The dimensionless BWRS parameters are defined as:
(3)
*  BO{P c}'
BO
* 3
Co  CO{p IRT r.
c c
* 2
b  b{pc },
* _ a{p 3},
a
c
* 4
DO  Do{p /RT },
c c
* 5
and EO  EO{P IRT },
c c *
AO  AO{pc/RTc}'
* 2
Y  y{p c },
* 2
a ." a{pc IRTc}'
c*  c{p 2/RT 3}, c c
(4)
where R is the universal gas constant.
Multiproperty Analysis
The general mathematical framework for using a leastsquares technique
for multiproperty regression analysis has been presented previously.2 To obtain optimal estimates of the parameters for the BWRS equation, the following objective function must be minimized:
(5)
*
These interaction parameters are related to Han and Starling's interaction
parameters kij by the following equation:
mij • 2(1  kij)
3
In this relationship, 9ij and 9ij are the calculated and expe~imental values, respectively, at the "jtn" data point for the "Lth" type of thermodynamic property; Wi is a weighting factor for the "Lth" property. ~ij is a nonlinear function of the BWRS parameters. Q, the objective function, depends upon not only the mathematical model through ~ij' but also upon the selection of experimental data, 6ij' and the weigh t Lng fac tors, Wi' One mus t select the most accurat~ experimental data available over wide ranges of temperature, pressure, and composition. If accurate data are used, the values of the optimal BWRS parameters are not very sensitive to the weighting factors selected.
Data for all measurable properties that arc later to be predicted should be included in the regression analysiS. In general, the less accurate the experimental data are, the smaller the value that Wi should have. Otherwise, the regression procedures would attempt to force a fit with the lessaccurate data while detracting from the fit with the moreaccurate data. Experimental data for density, enthalpy, and vapor pressure are usually much more accurate than Kvalue data. For PVT data, a weighting factor of unity was assumed in this work. In most cases, we also set the weighting factors equal to unity
for enthalpy and vapor pressure data. However, the weighting factors for Kvalue data were frequently set to values less than unity, with the specific values depending upon the accuracy of the particular data involved.
Regression Procedure for Pure Components
Binary interaction parameters and pure component BWRS parameters were determined simultaneously by regressing upon data for pure components and
for binary and multicomponent mixtures. During the course of early regression work based upon pure component and binary data, we found that several "optimal" BWRS parameter sets existed. In other words, each parameter set would reproduce the experimental data to about the same degree of accuracy. We further found that these different parameter sets, when applied to Kvalues
for multicomponent systems at low temperatures, varied in accuracy over
a wide range.
To attempt to determine a unique set of state equation parameters, a separate procedure was developed to determine optimal BWRS parameters by regressing on multicomponent Kvalue data. However, the optimal parameters for mUlticomponent Kvalues turned out to be very poor for pure component property predictions. Therefore, to arrive at one set that was optimal for all types of data, we devised the following scheme:
1. Starting with a parameter set that is good for pure component and binary data, regress on multicomponent data to determine Eo. the dominant parameter at low temperatures.
2. Holding Eo fixed, regress on pure component and binary data to determine the other ten parameters.
3. Repeat the above two steps until a parameter set is found that is best for both types of data.
4 
This procedure led to a uniqut~ set of parameters for each pure component. These parumeters do a good joh of predicting both pure component and binary mixture properties and multi~umponent phase behavior. Furthermore, because the reduced BWRS parameters for hydrocarbons show definite trends when plotted versus acentric factor, the development of a correlation for heavier hydrocarbon parameters was much easier. Finally, the inclusion of mUlticomponent data in the ~egression has the effect of extending the temperature range
of the data for a particular component to lower temperatures. Carbon dioxide
is a good example. No density and vapor pressure data were found at temperatures below 70°F. However, because the multicomponent Kvalue data for C02 systems extend down to 200°F, the temperature range of the data is extended by well over lOOoF.
Regression Procedure  Heavie~ Correlation
A generalized correlation of BWRS parameters as functions of critical temperature, critical volume and acentric factor was determined based upon data for the normal paraffins hexane through decane and for benzene, toluene, cyclohexane and methylcyclohexane. Initially, the dimensionless parameters were all assumed to be linear functions of acentric factor,
(6)
where Pi and Qi are correlation constants for the "ith" BWRS parameter, and A* i,j is the "Lth" dimensionless parameter for component "j". It ~.,as subsequently found that one of the parameters, a*j' is required to be a quadratic function of the acentric factor to adequately reproduce the data.
The determination of the constants (Pi and Qi) in the parameters correlation was simplified by requiring the correlation to reproduce the methane parameters exactly. This reduced the number of constants to be determined from 23 to 12. These 12 correlation constants, plus the binary interaction parameters for heavy components with other components, were determined simultaneously by regreSSing on pure component data for hydrocarbons heavier than pentane and on data for binary mixtures containing at least one heavy hydrocarbon component. Good initial guesses for the constants and iteraction parameters were obtained by extrapolating a plot of the reduced
BWRS parameters for the lighter components versus acentric factor.
The values of critical temperature, critical density and acentric factor used in the regression work for the pure components are given in Table 1.
Experimental Data
The experimental pure component and binary mixture data used in the regression work are summarized in Tables 28. Where there are enough data points of sufficient accuracy in a given data set, we selected a number of data points that are evenly distributed over wide ranges of temperature, pressure and composition.
5 .
Most of the data used in the regression are highly accurate. However, in some cases, the accuracy of the Kvalue data for heavy components at low temperatures is so poor, that we used very low weighting factors for those data. In a few cases, we even used a weighting factor of zero for the heavy component; in other words, we regressed only upon the Kvalues for the light component.
Data for normal butane and normal pentane are plentiful. For both components, density and vapor pressure data are available at temperatures as low as 200°F. The temperature range of the enthalpy data extends only to +75°F, however. The recent Rice University data on the dew points of methanenormal pentane mixtures26 were included in the regression. "Experimental" Kvalues for these data were generated by dividing the measured vapor mole fractions by calculated liquid mole fractions. Data for isobutane and iso~entane are limited. There are no enthalpy
data, and density data for iC4 and iCS extend to temperatures only as low
as llO°F and 60°F, respectively. Also, vapor pressure data are not available at low temperatures. There are no measured enthalpy data for carbon dioxide. The "data" used in the regression were derived from density data.
The multicomponent Kvalue data70are unpublished data for a 1.38 GPM natural gas. The composition of the gas is given in Table 12. We estimate the accuracy of the data to be 2% for methane, 5% for ethane. lOXfor propane and butanes and 20% for pentanes. No Kvalues were given for the C6+ component. Data were taken at temperatures from +20°F to 200°F and pressures from 100 to 1200 psia.
The generalized correlation of BWRS parameters for heavy hydrocarbons is based upon over 5400 data points for the normal paraffins hexane through decane. and for benzene, toluene, cyclohexane and methylcyclohexane. The lowest temperatures for which there are density, enthalpy, vapor pressure and Kvalue data are 130°, 7So, 1400 and 100°F, respectively.
Definitions of Statistical Measures
In this study, we define the deviation of a calculated thermodynamic property from the measured value as:
D _ 'ij  1
1j 81j ,
(7)
where +ij and 9ij are calculated and experimental values. respectively, at the "jtb" data point for the "ith" type of thermodynamic property and Dij is the deviation expressed as a fraction. For enthalpies, it is the accepted practice to express deviations as absolute deviations in BTU/lb. Thus, the enthalpy deviation is defined as
(8)
6
where Hj is the enthalpy at the given temperature and pL:ssure.and HO 1s the ideal gas enthalpy at the same temperature. hfh~l1 compar rng calculated results with data for various data sets, the rootmeansquare deviation (RMS). the average absolute deviation (AAD) and the bias (BIAS) are shown for each pure component and binary mixture. These quantities are defined for thermodynamic property "i" as!
(RMS) a ~/N E Dij , j
(AAD)i  lIN rlDijl , j
(9)
where the Dij are the deviations and N is the number of data points. Results of the Regression Analysis
The optimal BWRS parameters for isobutane, normal butane, isopentane, normal pentane and carbon dioxide are given in Table 9. Parameters previously determined for methane, ethane, propane and nitrogen are included in Table 9 for completeness. These parameters are consistent with the numerical value of R .. 10.7335 (psia) (cu. ft.)/ (lblI!Ole)(OR). The optimal interaction parameters are given in Table 10; the values in parentheses
are estimated values. The form of the correlation of BWRS parameters for heavy hydrocarbons is shown in Figures 14.
Tables 28 present the results of comparisons between the BWRScalculated properties and experimental density, enthalpy and vapor pressure data. Good agreement is evident over the entire temperature and pressure region. For the butanes, pentanes, carbon dioxide and the heavy hydrocarbons, overall average absolute deviations in density, enthalpy departure and vapor pressure predictions are 1.19%, 2.01 BTU/lb and 1.50%, respectively. If predictions for methane, ethane, propane and nitrogen are included, the average absolute deviations for density, enthalpy departure and vapor pressure predictions are 1.07%, 1.49 BTU/lb and 1.35%, respectively.
Generally, the agreement between BWRS calculations and experimental binary Kvalue data is good. In most cases where there is a large bias
(for example, the decane Kvalue predictions for the nitrogendecane system), the data are not highly accurate. The deviations between the calculations
and the data are largest for Kvalue predictions for heavy components at law temperatures. Heavy component Kvalues are difficult to measure accurately due to the very small concentrations of the heavy component in the vapor phase.
Figures 58 show typical results of BWRS calculations of vaporliquid equilibrium. A very good fit to the normal butane  normal decane system
is evident in Fig. 5. Figure 6 compares calculated and measured C02 Kvalues for the isopentanecarbon dioxide system. The calculated C02 Kvalues
7
appear to be about 67. too high. Predicted vapor and liquid compositions
for the propanebenzene system agree.very well with data at the lower pressures (Fig. 7). At higher pressures the calculated concentration of benzene in the vapor phase is too low. The BWRS equation reproduces the temperature  composition diagram very accurately for the methylcyclohexanenormal pentane system (Fig. 8).
A componentbycomponent summary of comparisons of BWRS calculations with the binary Kvalue data used in the regression is given in Table 11. The overall average absolute percent deviation is only 6.13% in spite of some very large deviations for heavy component Kvalues.
Table 12 shows deviations between calculated and smoothed experimental Kvalue data for the multicomponent system used in the regression. Results are shown for two sets of interaction parameters for C6+ with the other components. As might be expected, the normal heptane interaction parameters do not give the best results. The second set of interaction parameters, termed "better" on Table 12, do result in a better overall fit. We don't use the term "optimal" to describe these parameters because we might choose any number of objective functions to optimize. For example, if we wanted to have the lowest average deviation for methane K~values, another set of interaction parameters could lower this deviation to 1.8%.
The errors for propane Kvalue predictions seem high, but the average difference between smoothed and experimental Kvalues for propane is 9%. Thus, there appears to be_an unusually high degree of uncertainty in the propane Kvalues for these data. The Kvalue predictions for components at reduced temperatures below 0.5 are consistently lower than the experimental data. This trend has been noticed on several other data sets also. The bias can be reduced by using smaller values for the Eo parameters. However, we found that the higher values for Eo were required to accurately predict vapor pressures.
The recentlypublished experimental Kvalue data by Kahre76 for the methanenormal butane binary indicate that the low temperature nbutane Kvalues are Significantly smaller than those measured by Elliot, et al.15 Figure 9 compares BWRS calculated Kvalues with both of these data sets. The BWRS predictions match the Kahre data extremely well, in spite of the fact that these data were not used in the regression analysis. The data
by Elliot, et al. were included in the regression analysis, but the agreement is not as good as that for the Kahre data. Although it is not possible to say which of these data sets is more accurate, it appears that the Kahre data
are more consistent with the other data used in the regression.
!WRS Predictions
In the previous section, we demonstrated that the SWRS state equation with optimal parameters determined by multiproperty regression analysis, can accurately match densities, enthalpy departuresp vapor pressures and Kvalues for pure components and binary mixtures over wide ranges of temperature, pressure and composition. To further test the applicability of the method,
8 .
we must compare BWRS predictions with data that were not included in the regression. In this section, we compare BWRS calculations with two types of such data: Kvalues for multicomponent systems; and derivativetype thermodynamic properties such as specific heat, JouleThomson coefficient and velocity of sound.
Wang et al.73 have shown that a pressure explicit equation of state, such as the BWRS equation, may not accurately predict the derivatives (ap/3T)p and (ap/3p)T even when multiproperty regression on vapor pressure, enthalpy and density data is used to obtain state equation parameters. Only
if enough highly accurate data are available, if the data are evenly distributed over the ranges of temperature and pressure of interest, and if an excellent
fit of the data can be obtained, will the predictions for derivativetype thermodynamic properties be accurate. Futhermore, if all these conditions
are met, predictions for the derivativetype thermodynamic properties may
still be inaccurate at conditions near the extremes of the temperature and pressure ranges of the data.
Thus, the comparison of state equation calculations with data for derivativetype thermodynamic properties is a very stringent test of the applicability of the equation. Figure 10 compares BWRS predictions with velocity of sound data for C02 in the region of the critical point.71 Since the data base for C02 did not contain any experimental enthalpy data (only values derived from density data), the BWRS state equation might be expected to do a poor job of predicting the velocity of sound or specific heat for C02. Actually, the predictions ~re very good. The BWRS equation comes remarkably close to predicting the discontinuites near the critical point. To further test BWRS predictions for CO2' we compare predicted specific heats for two mixtures of C02 and methane with data by Bishnoi and Robinson75 (Figure 11). Agreement is very good except near the maxima where the predicted values are too low. Average absolute deviations between BWRS predictions and the data are 1.4% and 0.4% for the 14.49 and 42.3% methane mixtures. respectively.
The maximum deviation is only 7.2%. Our values for Cpo. which actually are specific heats at about 30 psia, agreed with those used by Bishnoi and Robinson75 to within 0.3%, with an average deviation of 0.13%. Based upon the comparisons with data sets containing derivativetype data. it appears that BWRS predictions for derivativetype data are reasonably accurate. However, it is possible that BWRS parameters superior to those obtained to date could be determined if the data base for the regression analysis was expanded to include data for derivativetype properties.
To evaluate BWRS predictions for Kvalues for multicomponent systems other than those included in the regression. we compare calculated Kvalues with the extensive set of Kva1ue data recently published by Yarborough.72 Yarborough gave no estimates of accuracy of his Kva1ue determinations. Estimated accuracy of the chromatographic analyses ranged from 05% for mole fractions larger than 0.5 to 510% for mole fractions of about 0.01. Yarborough stated that the measured compositions of nitrogen and methane in the liquid phase and of ndecane in the vapor phase were often more erratic than expected. based on the estimated precision of the chromotagraphic analysis.
9 
Comparisons for two of Yarborough's systems are given iq Figures 12 and 13. The pure component BWRS parameters for toluene were obtained from the dimensionless correlation with critical temperature, critical pressure and acentric factor. Toluene interaction parameters with methane, pentane,
and heptane were determined from binary Kvalue data. The interaction parameters for toluene with other hydrocarbons were obtained by interpolation; inter
action parameters for toluene with N2 and C02 were set equal to those for nheptane. As can be seen from Figures 6 and 7, agreement between data and predictions is excellent.
Table 13 gives overall average deviations between m{RS predictions and the Yarborough Kvalue data for systems without HZS. The agreement generally is good for all components, with the possible exception of C02. However, more than half of C02 Kvalues were measured for systems containing about
0.2 mole percent CO2. Therefore they may not be as accurate as the other measurements. If systems with less than 0.5 mole percent C02 are excluded, the average error for C02 Kvalue predictions drops to 8.0% with a small positive bias of 0.8%.
As a final check of BWRS predictions with multicomponent data, we use Kvalue data obtained by Hanson and Brown74 for two quinary mixtures of
the normal paraffins methane through hexane. Figures 14 and 15 compare BWRS calculations with these data. The agreement between ffiiRS calculations and the Hanson and Brown data is excellent.
In almost all cases, BWRS predictions agree well with laboratory data
for all thermodynamic properties of interest. However, any final verification of the m~RS method requires successful application to practical engineering problems. The primary reason for developing the method was to improve our ability to predict the performance of gas handling and gas processing facilities, particularly low temperature turboexpander gas plants.
Comparison With Plant Performance Data
Figure 16 compares plant performance data with the results of a plant simulation using thermodynamic properties calculated by the m{RS method.
The simulation was performed by fixing the composition, temperature and pressure of the inlet gas, all process pressures, and the reboiler duty
for the demethanizer. The calculations assume that equilibrium conditions prevail everywhere. The column was simulated using a rigorous traytotray calculation procedure. The number of equilibrium trays for the column was determined from the actual number of trays and the average tray efficiency. The expander and compressor calculations were performed assuming isentropic expansion or compression of the gases, and then using an isentropic efficiency to obtain an energy balance. With BWRScalculated thermodynamic properties, the match between the calculated performance and the actual plant performance data is excellent. calculated temperatures agree very well with measured temperatures everywhere except immediately after the throttle valve between
the expander inlet scrubber and the demethanizer. The product rate was predicted within 0.6% of the rate actually measured.
10
CONCLUSTO~~S
Optimal BlolRS parameters f~r Lso+bu t ane , normal butane, isopentane, normal pentane and carbon dioxide were dete~ined using a new multiproperty regression analysis procedure wh i ch employs, not only pure component and binary mixture data, but also (~I'.llticomp0ncnt mixture data. The multicomponent data were used to extend the tt!~.lpcrature range of the data base to lower temperatures.
We have developed dimensicClless correlations of BWRS parameters for heavy hydrocarbon components based upon the critical temperature, critical density and acentric factor. This correlation should be used only for components
or hydrocarbon fractions for wh Lch optimal Bt.JRS parameters have not been determined.
Comparison of B\>lRS calculations trlth laboratory data have shown that the BWRS method accurately predicts the thermodynamic properties of natural gas systems over a wide range of conditions. The method was verified for field applications by comparing a plant simulation using BWRScalculated properties with plant performance data for a turboexpander plant.
ACKNOWLEDGMENT
The authors wish to thank Esso Production Research Company for permission to publish this paper. We also express appreciation to Exxon Company, U.S.A. for supplying the plant performance data and to Mr. D. R. Massengill, who performed the simulation of the turboexpander plant.
REFERENCES
1. Starling, K. E. and Powers, J. E., lEC Fundamentals, ~. 531 (1970).
2. Lin, C. J., Kwok, Y. C., and Starling, K. E., Can. J. Chern. Eng., .22., 644 (1972).
3. Starling, K. E. and Wolfe, J. F., paper presented at Detroit AIChE meeting, 1966.
4. Lin, C. J. and Hopke, S. W., paper presented at New Orleans AIChE meeting, 1973.
5. Starling, K. E. and Han, M. S., Hydrocarbon Processing, 1, 129 (1972); Ibid, i, 107 (1972).
6. API Research Project No. 44, "Selected Values of Physical and Thermodynamic Properties of Hydrocarbons and Related Compounds", Carnegie Press, Pittsburg (1953).
7. Canjar, L. N. and Manning, F. S .. "Thermodynamic Properties and Reduced Correlations for Gases", Gulf Publishing Company, Houston (1967).
11':
8. Sage, B. H. and Lacey, W. N., "Thermodynamic Properties of the Lighter Paraffin Hydrocarbons and'Nitrogen", API Research Project 37, New York (1950).
9. Carruth, G. P., Thesis, Ph. D., Rice University, Houston (1970).
10. 0lds, R. H., Sage, B. H. and Lacey, W. N., IEC, 34, 1008 (1942).
11. Barsuk, S. D., Skripka. V. G. and Benyaminovich, O. A., Gazovaya Prom., .2" 38 (1970).
12. Robinson, D. B. and Besserer, G. J., NGPA Research Report RR7, June, 1972.
13. Ripkin, H., AIChE Journal, ll, 484 (1966).
14. Wang, R. H. and McKetta, J. J., J. Chem. Eng. Data, .2., 30 (1964).
15. Elliot, D. G., .chen, R. J. J., Chappelear, P. S. and Kobayashi, R., J. Chem. Eng. Data, 12, 71 (1974).
16. Kay, W. B.,.Yf_,l1, 353 (1940).
17. Kay, W. B., J. Chem. Eng. Data, 15, 46 (1970).
18. Nysewander, C. N., Sage, B. H. and Lacey, W. N., 1£f, 32, 118 (1940).
19. Isaac, R., Li, K. and Canjar, L. N., lEC,~, 199 (1954).
20. Silberberg, I. H., McKetta, J. J. and Kobe, K. A., J. Chern. Eng. Data, !O, 323 (1959).
21. Amick, E. H., Jr., Johnson, W. B. and Dodge, B. F., Chern. Eng. Prog.
Symp. Ser., No. 3, ~, 65 (1952).
22. Prodany, N. W. and Williams, B., J. Chem. Eng. Data, 16, 1 (1971).
23. Vaughan, W. E., and Collins, F. C., ~, li, 885 (1942).
24. Lenoir, J. M., Robinson, D. R. and Ripkin, H. G., J. Chern Eng. Data, 19, 23 (1970).
25. Reamer, H. H., Sage, B. H. and Lacey, W. N., J. Chern. Eng. Data, 1, 44 (1960).
26. Chen, R. J. J., Chappelear, P. S. and Kobayashi, R., J. Chern. Eng. Data, 12., 58 (1974).
27. Sage, B. H. and Lacey, W. N., "Some Properties of the Lighter Hydrocarbons, Hydrogen Sulfide and Carbon Dioxide", API Research Project 37, New York, (1955).
12~
28. Din, F., "Thermodynamic Functions of Gases", Vol. 1, Batterworths, London, (1962).
29. Reamer, H. H., aIds, R. H., Sage, B. H. and Lacey, \.[, N., lEC, 1§., 88, (1944).
30. Donnelly, H. G. and Katz, D. L., IEC, 46, 511 (1954).
31. Akers, \.[. W., Kelley, R. E. and Lipscomb, T. G., lEC, 46, 2535 (1954).
32. Robinson, D. B. and Besserer, G. J., Progress Report Presented to CNGPA Research Committee, 1972.
33. Muirbrook, N. K. and Prausnitz, J. M., AlChE Journal, 11, 1092 (1965).
34. Zenner, G. H. and Dana, L. I., Chern. Eng. Prog. Symp. Ser., No. 44, ~ 36 (1963).
35. Stewart, D. E., Sage, B. H. and Lacey, W. N., 1]£, 46, 2529 (1954).
36. Nichols, W. B., Reamer, H. H. and Sage, B. H., !lif, 47, 2219 (1955).
37. Reamer, H. H., Sage, B. H. and Lacey, W. N., Chern. Eng. Data Ser., 1, 29 (1956).
38. Reamer, H. H., aIds, R. H., Sage, B. H. and Lacey, W. N., lEC, 34, 1526 (1942).
39. Glanville, J. W., Sage, B. H. and Lacey, W. N., lEC, 42, 508 (1950).
40. Reamer, H. H. and Sage, B. H., Chern. Eng. Data Ser., ~, 9 (1957).
41. Lenoir, J. M., Robinson, D. R. and Hipkin, H. G., J. Chem. Eng. Data, 15, 26 (1970).
42. Lenoir, J. M. and Hayworth, K. E., J. Chem. Eng. Data, ]&, 280 (1971).
43. Lenoir, J. M., Kuravila, G. K. and Hipkin, H. G., J. Chern. Eng. Data, 16, 271 (1971).
44. Shim. J. and Kohn. J. P •• J. Chern. Eng. Data, I, 3 (1962).
45. Zais, E. J. and Silberberg, ~. H., J. Chern. Eng. Data, 15. 253 (1970).
46. Kay, W. B., J. Chern. Eng. Data, li, 137 (1971).
47. Cummings, L. W. T., Thesis, Sc. D •• Mass. lnst. Tech. (1933).
48. Chang, H. L., Hurt. L. J. and Kobayashi, R., AlChE Journal, ~, 1212 (1966).
49. Hehra, V. S. and Thodos, G., J. Chem. Eng. Data, lQ, 211 (1965).
13";
50. Cummings, L. W. T., Stones, F. W. and Volante, M. A., IEC,11, 728 (1933).
51. Kohn, J. P. and Bradish, W. F., J. Chern. Eng. Data, 2, 5 (1964).
52. Rodrigues, A. B. J., McCaffrey, D. S., Jr., and Kahn, J. P., J. Chern.
Eng. Data, 11, 164 (1968).
53. Reamer, H. H. and Sage, B. H., J. Chern. Eng. Data, I, 161 (1962).
54. ~,11, 17 (1966).
55. ~, 2, 24 (1964).
56. Azarnoosh, A. and McKetta, J. J., J. Chem. Eng. Data, i, 494 (1963).
57. Reamer, H. H. and Sage, B. H., J. Chern. Eng. Data, i, 508 (1963).
58. E1bishlawi, M. and Spencer, J. R., lEC, 43, 1811 (1951).
59. Kay, W. B. and Nevens, T. D., Chem. Eng. Prog. Symp. Ser., No.3, ~, 108 (1952).
60. Li, I. P. C., Wong, Y. W., Chang, S. D. and Lu, B. C. Y., J. Chern. Eng. Data, 17, 492 (1972).
61. Nielson, R. L. and Weber, J. H., J. Chem. Eng. Data, i, 145 (1959).
62. Sieg, L., Chem. Ing. Tech., ~, 322 (1950).
63. Black, C., 1!£, 51, 211 (1959).
64. Heertjes, P. M., Chern. Proc. Eng., 385 (1960).
65. Reamer, H. H., Sage, B. H. and Lacey, W. N., ~ Eng. Data Ser., 1, 240 (1958).
66. Clerk. G. A., Thesis, M. S., Univ. Texas, Austin, (1949).
67. Kay, W. B. and Albert. R. E., lli£, 48, 422 (1956).
68. Myers, H. S., Petroleum Refiner, ]2, No.3, 175 (1957).
69. Myers, H. S., 1]£. 48, 1104 (1956).
70. Unpublished Kva1ue data for a 1.38 GPM Natural Gas System.
71. Herget, C. M., J. Chem. Phys., i, 537 (1940).
72. Yarborough, L., J. Chem. Eng. Data, 12, 128 (1972).
73. Wang, J. 5., Van Dae1, W. and Starling, K. E., paper presented at Vancouver AIChE Meeting, 1973.
14
74. Hanson, G. H. and Brown, G. G., .IEC, 37, 821 (l945).
75. Bishnoi, P. R. and Robinson, D. B., Can. J. CbE::n. En, .• 49, 657 (1971).
76. Kahre, L. C., J. Chem. Eng. Data, 19, 67 (1974).
15
TAELE 1
Physical Properties of Pure Components
Molecular Critical Critical Density Acentric
Component Weight Temp. ! of Lb+mo Le Zcu . ft. F;:tctor,:.l
Hethane 16.042 116.[.3 0.6274 0.0130
Ethane 30.068 90.07 0.4270 0.0987
Propane 44.094 205.99 0.3121 0.1524
IButane 58.121 274.96 0.2457 0.1848
NButane 58.121 305.60 0.2448 0.1872
IPentane 72.146 369.00 0.2027 0.2223
NPentane 72.146 385.77 0.2007 0.2518
NHexane 86.172 453.60 0.1686 0.2993
NHeptane 100.198 511.69 0.1457 0.3466
NOctane 114.224 564.10 0.1283 0.3839
NNonane 128.250 610.84 0.1146 0.4412
NDecane 142.276 651. 90 0.1035 0.4885
Benzene 78.108 552.10 0.2415 0.2132
Toluene 92.134 605.40 0.1980 0.2668
Cyc10hexane 84.156 535.60 0.2027 0.2147
l'le thy 1
Cyc10hexane 98.182 570.20 0.1808 0.2510
Nitrogen 28.016 232.60 0.6929 0.0400
Carbon Dioxide 44.011 81.80 0.6641 0.2250 16
TAtlLE 2
Results of Regression  Butanes
Second No. of Temperature Pressure Deviations*
Property Component Data Points Range (OF) Range (psia) Ref. Components _!lliL MJL BIAS
ISOBUTANE
P 351 110/460 11 •• 7/5000 6,7,8 1. 34 .0.93 0.68
p C1 555 100/460 200/5000 10 0.96 0.73 0.32
VP 67 125/215 0.2/529 6,7,8 1.14 0.80 0.31
K C1 85 103/220 71/1422 11 IC4 15.4 8.58 7.43
C1 4.15 2.93 1.22
K Cz 34 101/250 155/719 12 IC4 4.15 3.21 2.80
C2 5.00 3.47 2.08
K C3 50 20/250 19/575 13 IC4 1.62 1.26 0' .19
I C3 1.84 1.52 0.33
....
"
I NBUTANE
p 426 200/460 14.7/10,000 6,7,8 1.64 0.98 0.14
P C1 200 100/400 200/5000 8 1. 70 1.07 0.83
H 198 100/460 200/9000 8 1.66 1.30 1.17
VP 95 216/306 104/551 6,7,9 1.27 0.76 0.22
K C1 110 140/250 50/1800 8,14,15 NC4 5.76 4.15 1.17
C1 5.42 4.04 0.77
K C2 16 150/250 450/750 16 NC4 1.11 0.76 0.44
C2 0.81 0.58 0.,19
K C3 36 130/280 100/590 17,18 NC4 5.02 2.78 1.91
C3 5.46 3.67 3.45
'I< except for entha1p1es, where deviations are in BTU/lb.
Percent Deviations, TABLE 3
Results of Refref,sigD  Penranes
Second No. of Temperature Pressnre Deviations*
Property Component Data Points Range (OF) Range (psia) Ref. Components .JQ1L !BL BIAS
ISOPENTANE
P 313  60/600 14.7/3127 6,19,20 2.7'2 2.13 0.49
p C1 271 160/400 200/1500 21 1.49 1.09 0.39
VP 70  70/360 0.2/453 6,8 0.72 0.61 0.12
K C1 18 160/280 499/2191 22 IC5 10.0 7.92 6.11
C1 4.41 3.01 1.85
K C3 72 32/356 14.7/647 23 ICS 4.58 3.27 1.66
C3 6.08 4.97 ;4.63
NPENTANE
I
.... 472 200/460 14.7/10,000 6,8 1.61 0.92 0.32
00 P
I'
p Cl 388 100/460 200/5000 8 1.09 0.79 0.36
H 196 75/700 200/1400 24 1. 76 1.1.2 1.04
VP 99 201/386 4xl0S/490 6,8,9 3.34 1.60 0.16
K Cl 47 100/340 20/2000 8 NC5 6.91 4.77 4.14
Cl 2.38 1.92 0.24
K C2 56 40/340 50/900 25 NC5 7.10 4.26 2.07
C2 3.69 1. 74 0.70
K C3 22 194/356 300/650 17 NC5 3.73 2.83 1.37
C3 3.56 2.37 0.69
K** Cl 64 148/32 20/2195 26 NC5 17.33 11.22 9.58
Cl 0.62 0.41 0.01 **
Liquid compositions are calculated.
TABLE 4
Results of Regression  Carbon Dioxide
Second No. of Temperature Pressure Deviations·
Property Component Data Points Range (OF) Range <psia) ~ Components ~ MJL_ BIAS
P 274  76/460 14.7/8818 2.7,28 2.20. 1.60 0.69
p Cl 352 100/460 200/8000 29 0.84 0.69 0.62
p C2 100 100/460 1000/7000 27 2.09 1. 76 1. 76
p C3 200 40/460 1000/8000 27 1.90 1.58 1.43
p NC4 100 100/460 1000/7000 27 1.92 1.64 1.49
I
H 166  22/464 147/8818 28 1.99 1.48 0.92
VP 69  70/86 75/1050 27,28 2.02 1.36 0.18
K C1 52 100/40 300/1200 30 CO2 5.39 3.46 2.71
C1 7.71 5.71 1.54
I
._. C3 59 32/160 100/850 27,31 CO2 6.66 4.83 2.55
\D K
I· C3 3.87 2.04 1. 36
K 1C4 24 100/250 105/956 12 CO2 5.77 4.28 1.64
1C4 4.68 3.37 2.66
K NC4 29 100/280 100/1000 27 CO2 5.00 4.74 3.15
NC4 3.42 2.43 2.13
K lCS 37 40/220 22/1290 32 CO2 7.71 5.83 2.22
rcS 13.0 9.38 6.35
K NCS 42 40/220 33/1288 32 CO2 9.07 6.96 1.60
NC5 19.2 12.5 2,99
K N2 47  67/32 185/2015 33,34 CO2 3.82 2.81 2.39
N2 9.25 6.79 0.53 TABLE 5
Results of Mu1tiproperty Regression  Densities for Heavies
System Experimental Data Deviations I %
Coml2onents No. of Temp. Range Pres. Range
1 L Reference Data Points of psia !Y:!L A@_ lllAL
NC6 6,7,35 515 130/600 14.7/10000 1.96 1.68 1.35
NC7 6,36 209 130/460 14.7/10000 1. 72 '1.48 1.11
NC7 C1 37 479 40/460 200/10000 1. 76 1.35 1.02
NCS 6 33  70/250 14.7 0.85 0.57 0.38
NC9 6,27 323  60/460 14.7/10000 1.52 1.25 0.84
t
N  20/460 14.7/10000
~ NC10 6,8 192 1.42 1.19 0.70
NC10 C1 38 342 100/460 800/10000 1.42 1.17 0.82
Benzene 6,39 173 50/460 14.1/10000 1.63 1.42 1.36
Cyclo
hexane 40 152 100/460 200/10000 0.97 0.73 0.52
Overall 2418 130/600 14.7/10000 1.64 1.34 0.93 TABLE 6
Results of Multiproperty Regression  r..1thalpies for Heavies
System Exeerimental Data Deviations I i3TU/lb
ComEonents No. of Temp. Range Pres. i.~nge
1 L Reference Data Points of psia RMS AAD BIA.S
NCS 41 70 75/600 200/1400 3.47 2.45 0.92
NCS NCS 41 239 75/600 200/1400 4.71 3.76 3.46
Benzene 42 129 3S0/700 200/1400 1.80 1.25 0.12
CyC6 43 113 300/680 200/1400 2.72 2.16 1.02
CyC6 NCS 43 448 300/680 200/1400 2.15 1. 75 1.13
Overall 999 75/700 200/1400 3.08 2.26 1.50 21'
TABLE 7
Results of Multipropertv Regression  Vapor Pressures of Heavies
~xperimcntal Data Deviations I %
Ho. of Temp. Range Pres. Range
S~stem Reference Data Points of psia RHS M!L BIAS
NC 6,9 96 140/450 0.2xlO3/419 3.37 1.68 0.09
6
NC7 6,9 78 126/512 0.5x104/397 4.00 1. 72 0.34
NC8 6,9 74  70/550 0.3x103/324 2.90 2.33 1.28
NC9 6,9 70  57/355 0.lxlO3/30 4.64 3.64 1.64
NC10 6,9 70  21/400 0.2xlO3/30 4.37 2.47 0.23
Benzene 6,7 69 45/453 0.76/716 0.86 0.72 0.37
Toluene 6 48 45/280 0.2/30 0.30 0.25 0.12
CyC6 6,40 42 44/460 0.8/342 1.15 1.02 0.92
MeCyC6 6 .,9 25/265 0.2/31 1.44 1.28 0.21
Overall 596 140/550 0.Sxl04/716 3.18 1.78 0.36 22
TABLE 8
1~e9ults of Multiproperty Regression  r:values for Heavies
Sv~tcm Experimental Data
Campanc~ No. of Temp. Range Pres. Range
1 2 Reference Data Points·P psia
~C6
NCG NC6 NC6
NC7
NC7
NC7
NC7
jC8
NC8 NCIO
NCIO NCI0 NCIO NClO NClO Benzene
Benzene
Ben?ene
Benzene
Benzene Benzene Toluene Toluene Toluene Toluene Toluene
CyC6 CyC6 CyC6 CyC6 CyC6 CyC6 CyC6 MeCyC6 MeCyC6 MeCyC6 MeCyC6 MeCyC6
C1 C2
Cl
NC4 C1 C2 C3
NC5 C1 C2 Cl C2 Cl
NC4 N2
CO2 C1 C2 C3
NC6 NC7 NC8
Cl
NC5
NC6
NC7 Benzene
C1 C2.
NC5
NC6
HC7. Benzene Toluene
C1
NC5
NC6
NC7 Benzene
44 45 46 47
37,48 49 46 50 51 52 38 53 54 55 56 57 58 59 ?J 60 61 62 58 60 62 63 64
65.66 67 68 68
63.68 62
63.69 66 68 68 62 69
49 36 23
9 79 32 30 25 3J 42
100 95 48 57 90 77
16  16
72
32
18
17
16
45
2.5
17
15
100 19 26 .30 3.5
4 13 11 42 32 11 29
17/302 150/350 194/356 250/300
100/460 300/350 194/392 268/4ao
71/302 104/212 100/460 40/460 40/460 100/460
100/280 40/460 150 212/482 100/400 86/140
104/165 185/239 ISO
68/104 160/216 209/230 178/228
70/340
01450 102/171 1.561176 118/209 114/116 117/230
1.50 103/20.5 159/210 210/213 117/213
147/1470
25/1100 300/700 200/450 100/3000 450/1250 300/700 147/444 147/1029
59/105 20/3750
100/1100 50/1000 25/100 80/5000 50/2500
100/4600 300/1400 2O/8SO 2.5/11.0 3.5/7.7 14.1
100/5300 2.1/1~ .3 14.7 14.7 14.7
100/4000 100/1300 14.7 14.1 14.7 14.7 14.7
100/3750 14.7 14.7 14.1 14.7
Deviations ,.
K 1
18.69 13.74  6.49 24.96 17.20 15.91 3.92 3.13  I.G2 5.88 4.70  2.39 32.10 21.41 16.16
8.33 6.72 6.26
13.75 10.04  4.88
3.47 2.5] 1.05
31.97 24.81 2.3.56 40.00 33.19 23.1]
12.607.71 0.13
29.60 21.73 4.12
18.23 11.61 11.58
4.94 3.99 0.68
46.75 40.14 28.42 29.52 22.]0 10.36 22.44 18.39 3.38
8.43 6.01  5.97
15.24 7.99 2 • .30
1.01 0.76  0.06 2.29 1.88 1.02 3.69 2.51  2.16
19 .. 51 15.65  6.72 1.]4 1.38  0.94 0.89 0.16  0.18 1.83 1.1.3 1.00 2.55 1.50  0.01
17.86 11.56  6.11 23.73 13.64 10.53 1.24 0.98  0.50 1.73 1.13 0.79 1.86 1.53  0.58 2.01 1.58 1.10 1.82 1.63  1.21
23.83 22.04 21.59 2.71 2.1.; 1.19 2.11 1.66 1.26 1.83 1.61  1.36 1.53 1.40 1.24
Overall
1472
100/482
2/5300
23
2.66 1.53 0.14
12.16 10.19 6.25 2.08 1.47 0.16 0.77 0.65 0.21 5.30 4.44 1.75 2.45 2.33 0.11 3.95 2.32 0.34
2.38 2.42 2.23 3.80 5.73 3.76 3.54 9.04 8.70 3.21
10.08 6.66 1.77 1.79
1.51 1.39 1.74 v.30 1.63 0.06 2.82 0.35 4.88 2.46 3.02 L05 2.88 1. 37 7.55 1.12 6.81 1.46 2.29 0.59 B.18 2.07 5.39 2.49 1.30 0.08 1.25 0.16
6.29 4.67 4.G7 3.70 2.94 O.lO 1.61 1.38 Q.26 1.73 1.49 0.92 0.66 0.34 0.38 1.78 1.42 0.16 7.03 5.27 0.47 8.73 G.37 1.45 1.78 0.97 0.33 1.66 1.26 0.80 2.27 1.39 0.16 0.76 0.]4 0.74 1.03 0.66 0.72 6.35 5.17 2.03 2.59 1.96 0.12 1.91 1.40 1.18 1.14 1.10 0.90 1.93 1.79 1.35
/
'j(.£ ~ft(}~1
""" I
TABLE 9
The Optimal BWRS Parameters
CN4 C2H6 C3H8 IC4HlO NC4HlO lC5H12 NC5H12 N2 CO2
B 0.696663 0.940341 1.15091 1.41699 1. 38780 1.61871 1.54342 0.686293 0.473428
0
1.0/104 0.703241 1.50851 2.20325 3.01020 3.12799 3.93334 3.95713 0.424533 0.762197
Co/108 3.31272 26.0615 75.3232 13 7.356 159.698 257.683 284.646 0.974169 20.8025
Y 1.39930 3.04152 5.50137 8.82944 9.00761 12.7727 13.0384 1.19172 1. 26588
b 0.861307 2.69564 6.36610 10.6254 11. 2723 16.7246 18.8648 0.559419 0.976469
a /103 2.75239 17.3349 55.8356 101.674 113.271 184.751 207.942 0.921051 6.05085

I a 0.453145 1.03845 2.17606 4.37780 4.24116 7.10095 6.99803 0.489701 0.320386
N
~
I •
c / 109 0.508281 5.94592 23.3092 52.3431 62.8476 120.128 131. 746 0.112862 2.41003
Do/1010 1.41063 20.7312 75.6999 160.026 195.633 349.884 412.701 0.362181 15.5050
d /105 '0.684469 5.98254 18.7440 40.6431 46.7125 84.3874 97.2323 0.282061 3.48824
Eo/lOll 1. 26531 90.0981 437.431 1056.56 1381.81 2894.06 3518.30 0.327911 107.993 TABLE 10
Optimal Interaction Parameters mij
_l_ C2 _2_ rC4 NC4 rcS NCS N2 ~
1. 'iii , \ ,q~a r.q"f7 Viq7 \.~~h r , q'tb 1,'1>~ :.'N3
C1 2.00()
1.'\18 I. 'l"t8 1.1i7 1.'1Q7 1.1" I :olZS
C2 1.999 2.000 l: ,0 II
\.,\'\~ t, 'j1' I. ,"\, ( ,'~f> I.'h '3 1,'1,3
C3 1.998 2.011 2.000
IC4 1.991 1.998 1.999 2.000 1. .. 0 l.~~ l. "itt '\ 1.~83 1.8'~
NC4 1.991 1.998 1.999 (2.000) 2.000 l.~~' {,', , l.a'1 LSiS
rcS 1.996 (1.991) 1.998 (1.999) (1. 999) 2.000 2.00 "Z. t,t'2.\ 1.'100
NCS 1.996 1.991 1.998 (1.999) (1.999) (2.002) 2.000 I.~'Z.I l.i"7
N2 1.9S4 1.926 1.913 (1.883) 1.883 (1. 921) 1.921 2.000 "l..Olo)
CO2 1.943 (1.928) 1.913 1.894 1.898 1.900 L881 2.015 2.000 .
25
TAnI&.....ll
Surn..ilary of Results of Huitiproperty Regression  Bir:ary Kva1ues
Experimental Data
Temp. Range Pres. t\ange Deviationsz %
Component Kva1ues of psia R..'1S ..MlL .!?lA.L
Methane 1114 255/460 20/5300 4.25 2.86 0.17
Ethane 514 225/482 15/1760 6.67 4.22 1.03
Propane 654 225/460 15/2000 5.94 3.82 0.75
IButane 193 103/250 19/1422 10.54 5.08 4.04
NButane 278 140/460 25/3402 4.53 3.27 0.22
IPentane 127 32/356 15/2191 8.67 S.7l 3.66
NPentane 369 148/480 2/2195 10.50 5.35 2.40
NHexane 236 77/356 2/1470 13.11 6.64 0.66
NHeptane 247 100/480 3/3000 19.06 9.40 4.58
NOctane 92 77/302 15/1029 33.23 24.91 1.26
NDecane 467 40/460 20/5000 28.54 19.40 6.94
Benzene 219 86/482 2/4600 10.99 5.22 0.29
Toluene 131 68/230 2/5300 7.00 2.93 0.98
Cyc10hexane 227 0/450 15/4000 13.75 6.85 3.66
Methyl
Cyc10hexane 131 103/213 15/3750 8.83 4.41 1.95
Nitrogen 318 255/280 50/5000 7.64 5.13 0.48
Carbon
Dioxide 367 100/460 22/2500 6.97 5.05 1.03
Overall 5684 255/482 2/5300 12.43 6.13 0.06 26
TABLE 12
Results of Regression Analysis  Multicomponent Kvalues
Normal Heptane mij's for C6+ Better mij's for C6+
Mol No. of Lowest
Component Percent Kvalues TeJIlperature RMS AAD BIAS mij,C6+ RMS AAD BIAS
Cl 90.16 48 200oF 2.9 2.0 1.5 2.00 3.2 2.3 0.2
C2 4.69 48 200 12.3 9.9  9.3 1.990 7.2 4.0 2.3
C3 r.ss 46 lBO 114.3 8.9  7.0 1.992 13.6 B.6. 2.4
iC4 0.79 39 140 10.0 6.9  2.6 1.997 9.6 6.7 2.6
nC4 .51 39 140 14.4 9.7  B.4 1.993 13.6 9.5 2.7
I
N .27 35 100 15.6 12.1  9.8 1.990 13.5 10.8 2.2
..... iCS
•
nCS .18 35 100 17.7 14.1 11.8 1.990 15.0 11.5 2.5
C6+ .63 0
N2 .40 48 200 15.0 12.1  6.6 1.875 11.9 9.5 4.4
CO2 .52 46 180 16.0 8.5  8.2 1.870 7.3 4.2 2.1
C6+ properties used: 103 molecular weight, PNA  56.4/36.2/7.4 TABLE 13
Comparison of BhTRS Calculations With Nulticomponent
KVaiue Data by Yarborough
No. of
~ MlL .lH/.S Points
C1 6.7 4.6 + 2.6 99
C2 3.4 2.4  0.5 99
C3 3.9 2.9  1.9 99
nCS 9.1 4.6 + 3.1 99
nC7 7.0 6.8  0.9 99
Toluene 10.4 7.7 0 66
nC10 19.8 lS.2  6.3 99
N2 22.4 14.6  2.3 53
CO2 27.6 16.8 11.4 53 28 .
1.6
en 1.4 a:
UI
._
W
~
a: ct 0
en a: ~
II)
~ 0.8
w ~
Z o u; z
w
::E a
,.2".~,
1.0 ~
. __
. ..__,
0.6 .. 1 __ .. ~_..,.:.· __ ......
.~A..~
8 • o
• ~
0.4
 ___
.. .
. .. _._
0.2f
o
0.1 0.2
w ACENTRIC FACTOR
Fig. 1. Correlations for Ao .,80., and 'Y ••
1.8
O'O~.:, :0~.2~,j 0 w ACENTRIC FACTOR
Fig. 3. Correlations for a • and c".
1.5
In 1.4
ex:
w
._
w 1.2
~
ct
ex:
<!
0 1.0
In
a:
~
II)
In
VI
W
~
Z
0
u;
Z
w
:E
25 o
0.1 0.2
w ACENTRIC FACTO~
Fig.2. Correlations for «: b·, Co', Do ., and Eo '.
0.181
0.16
•
0.14
0.121
ct. r.~
0.10 r
0.081
•
"' .. ....._____
•
0.061
0.04
0.02
OL~0~.:'~O~.2~~O.~3~0~.4'~O~.5~ w ACENTRIC FACTOR
Fig. 4. Correlation for a·.
160'FO~
100"F~.
100
PRESSUREPSI~ perimentst Kvalues
. With ex
. lAIRS calculations
·son of B •• ,
Fig. 5. Com"." aecsn« system.
for the nbutanen
NOECANE
100r~
IPENTANE
0.01,0
PRESSURE  PSIA
Fi,. 6. CompMison of 8WRS calculations with expeimenta/ K .'a/utls for th. i"'I*f~ntI  C02 .systJtm,
,
,
,
0 TEMP DATA CALC
100°F • A
1S0°F .. B
220F a C
280~F • 0
34O"F 0 E
400°F 0 F <t in
Q. I W a: ::> en en w a:
Q.
MOLE FRACTION BENZENE
Fig. 7. ComP8riscn of BWRS calcuilltions with expt!rim.ntal Pre:;s!:reComposition dillgnm for mil bllnzenepropanllsystem.
~O~~r~~~
u.
o
,
w a:.
::> I<{ a: w Q.
:e w I
/
•
I ·1
Ji. f
I
1.
/
•
I~
~,/ .'
~
.'
./'
. /
P'
:
/
0.2
0.4
0.6
0.8
METHVLCVCLOHEXANE MOLE FRACTION
. Fig. 8. TmlPlIratureCompos;tion plot for the Methylcyclohtlxanll NC5 system at .tmospheric pressurtl.
1.0
100
en w :l ..J « >
I
~
METHANE
.~ ..~
.._:
N8UTANE
•
I
•
j
•
• ~ 0/
00 •
. ~:._....
KAHRE DATA
• L DATA
o ELLIOT, ET.A •
100 ESSUREPSIA
PR 'm Kvalutl
8WRS calculations WI
. 9 Comparison of al butantl system.
FIg. • ethanenorm
data for tlltl m .
500
~ ~
LL
> ...
8
..J W
> s z
~
o
HERGET DATA
• DATA AT 82.4°F
• DATA AT 87.8°F
BWRS
•
•
•
800 PRESSURE  PSIA
Fig. to. Comparison of BWRS calculations with eJeperimenral data for the velocity of sound in C02.
• • •
•
•
•
4.0
COMPOSITION
I 1I
14.49% 42.3%
85.51 57.7
•• BISHNOI
• 0 ROBINSON DATA
 BWRS CALCULATIONS
3.0
2.0
200 400 bOO 800 1000 1200 1400 1600 1800 2000 2200
PRESSURE  PSIA
Fig. 11. Comparison of BWRS calcularions with ~xPl1rimenral data on th~ sp«ilic heat of two merhane  C02 mixtums.
• NC5
w •
j
_, 0.1
«
>
I
~
•
COMPOSITION
C1 81.59 MOl%
C2 5.95
0.01 C3 2.98
NC5 3.39
• ' NC7 2.49
• TOl 1.87
• YARBOROUGH NC10 1.73
2000F DATA (MIXTURE 6)
BWRS
CALCULATIONS
0.001
500 800 1000 1500 2000 3000 4000
PRESSURE  PSIA C2
1 ._ •
..
• C3 , _.
• • Fir. 12. Comparison of 8WRS calculations with experimental Kvalue data flW. multicomponttnt system.
•
•
1
C2
~~. 
________ C3
.'.
w :l ~
« 0.1
~
.
0.01
COMPOSITION
•
• C1 C2
C3
I NC5 . NC7 . TOL
NC10
~02
54.90 MOL% 3.59
2.58
2.56
1.73
5.48
1.35
12.74 15.06
0.001
l00"F
• YARBOROUGH DATA (MIXTURE 20A)  BWRS CALCULATIONS
•
800
1000
1500
2000
3000
PRESSUREPSIA
. Fig. 13. Comparison of BWRS calculations with experimental Kvalue data (or a multicomponent system.
4000
COMPONENT CH4 C2HS C3HS
NCSH12 NCSH14
MOLE
FRACTION
0.6626 0.1093 0.1057 0.0616 0.0608
1.0000
0.1
&a._A_ .. ."
.'"
·~""~n
»
I·
•
OAT A OF HANSON AND BRO'NN (74)
500 1000
PRESSUREPSIA
FI,. 14. Comp.rison of calculatt!d and expt!f"imt!ntal K values for a Quinary system.
. ,
. ~ .
. .
I.
• ~'JJ
'Z /1
=r"!
o •
<.>
•
COMPONENT CH4 C2H6 C3Ha
NC4H10 NC5H12
MOLE FRACTION 0.7007 0.0669 0.0413 0.0508 0.1353
1.0000
DATA OF HANSON AND BROWN (74)_
1000 2000
PRESSUREPSIA
Fig. 15. Comparison of C6lcu/8ted and exptlrimtlnral Kvalues for a Quinary system.
INLET GAS
SALES GAS
FUEL.
DEMETHANIZER COLUMN 494P51G
PLANT TEST DATA ~ __ .... BWRSCAl.CULATIONS
Fill. 16. Comparison of measured and cal.:ulated temperalures for II Turboexpander Gas Plant.
This action might not be possible to undo. Are you sure you want to continue?
Use one of your book credits to continue reading from where you left off, or restart the preview.