A new equation of state for

KENNETIf R. HALL Chemical Engineering Dept.

University of Virginia Charlottesville, Va.

LYMAN YARBOROUGH Amoco Production Co.

Tulsa

Compressibility factor

(V,- reduced 1"'11" .. 1

2 Pa 3 4

-- Equation 7

- - Extropolotion

Original volues

Fig. 1

OG!

THE STANDING-KATZ' Z-factor chart, accepted standard for reservoir gas and gas-condensate systems, can now be produced by a new equation of state.

Excluding the low-temperature isotherms of T R = 1.05, 1.10, and 1.15, the augmented hard-sphere equation is accurate within an average of 0.3%.

Only 11 points, of 289 in a condensed table of values read from the chart, deviate by more than 1 % with a maximum value of 2%. This is within the accuracy of the original values.

For the three low-temperature isotherms, the tabulated values are physically suspect.

Fig. 2

Graph of Equation 7

°O~--L-~~--~~~--~--~O.76--~ Y

OGJ

Z-factor calculations

The equation has been tested wj,th 12 reservoir gas systems-both sweet and sour-giving an overall average deviation of 1.21 %.

The equation can be extrapolated well beyond the Pa = 15 maximum of the Standing-Katz chart. Temperature extrapolation below TR = 1.00 is not recommended.

The approach. Alfter three decades of existence, the Standing-Katz- Z-factor chart still is widely used as a practical source of gas-phase compressibility factors, so there was an apparent need for a simple, closed-form equa tion of state which represents the chart.

In addition, a method for accurately calculating compressibility factors for sour gases is required. The equation of state should be applicable at pressures well above the limit of the Standing-Katz chart (PR = 15).

In this study a hard-sphere equation was used as the basis for the equation of state. The hard-sphere equation was selected because it approximates real-fluid behavior at high pressures in the limit of high temperature. For this reason an augmented hard-sphere equation should provide a reasonable extrapolation above the pressure limit of the data used to develop the equation.

The hard-sphere equation was augmented by a real

Fig. 3

Low-temperature isotherms, expanded

z

. ..

1.1

- Equation 7

• Orlglnol vnlues

0.5

°O~----~O.~I----~O.~!----~O.I------~O.~----~O.S Y

OGJ

THE OIL AND GAS JOURNAL-JUNE 18, 1973

fluid deviation function, and the final equation was generalized by fj·tting it to the Standing-Katz Z-factor chart.

The 12 reservoir gas systems used to test the equation were selected to cover fluids from abnormally pressured reservoirs (PR up to 20,5), both rich and lean gas condensates, and fluids which contained significant . amounts

Comparisons

.2.0
~,~~
1.8
1.6
Z1.4
1.2 I
L1mll of
1.0 $tandlng.Katz
Z churt
0.8
4,000 6,000 8,000 10,000 12,000 14,000
Pressure, psia OGJ Comparisons with gas system 4

Sour gas-condensare well stream -lquatlon 7

---- Modified Redlich-Kwong

equation

1.4

Z

1.0

0.8

0.6 !;---'-:;=:--'--;-:=-....L..=:--'---:-::'::::-~~:-'-~

o 4,000 6,000 8,000 10.000 12,000

Pressure, psia

OGJ

Fig. 4

Fig. 5

of nonhydrocarbon components (up to 33% N2, 8.5% C02, and 40 % H2S).

Augmented hard-sphere equation. The hard-sphere equation of state describes a fluid composed of rigid, inelastic spheres rather than real molecules. While this seems hopelessly idealized, such a model provides definite advantages. In the limits of high temperature and high pressure, real fluids behave similarly to hard-sphere fluids. Moreover, having a simple model enables theoretical development of simple, closed-form equations of state.

Several hard-sphere equations have been proposed recently. 3 0 6 7 8 9 Of these, the la tter three are most accurate, but the Carnahan-Starling? equation is simplest and will be used in the present development.

Given the hard-sphere equation, it seems logical to use it as a basis for real-fluid equations. If such an effort is to be successful, the extension must he performed in a theoreticaHy sound manner.

Haar and Shenker"? noted that the virial equation of state has a precise theoretical foundation and chose to use it to augment the hard-sphere equation. Their development follows.

The vi rial equation of state is simply an infjnite series in density:

z

P pRT

where the coefficients, B}(, are functions of temperature only. Equation 1 may be rewritten as

where the superscript, hs, denotes "hard-sphere." In this formulation the first term is a hard-sphere equation of state and the second term is a real-fluid deviation function. Haar and 'Shenker then argued that, for supercrttlcal temperatures, the effect of virial coefficients higher than the second was small, and was, in fact, provided for by the hard-sphere equation 'Used. They chose the Reiss, Frisch, and Lebowitz hard-sphere equation and obtained

1 + y + y2 B2

Z == + 4(- - 1) y (3)

(1-y)8 b

y == bp/4

Here y is essentially a reduced density being the product of a van der Waals covolume and density.

More recently, Bienkowski, Denenholz, and Chaoll have reformulated Equation 3 in terms of the reduced density

(1)

1 + apR + (aprY (l-apn)3

+ (BR - 4a) pn (5)

(4)

00

z

Percent deviations between original values and those of Equation 7

Table 1

PR/TR 1.05 1.10 1.15 1.20 1.25 1.30 1.35 1.40 1.45 1.50 1.60 1.70 1.80 1.90 2.00 2.20 2.40 2.60 2.80 3.00

0.4 -0.1 0.2 -0.1 0.1 0.3 -0.0 -0.0 0.0 -0.2 -0.1 0.0 0.1 0.0 -0.1 0.0 0.0 0.1 0.1 0.1 0.2

0.7 -0.5 -0.6 -0.3 0.3 0.4 0.1 -D.O 0.0 -0.0 -0.0 0.0 0.2 0.2 0.1 0.0 -0.0 -0.0 0.1 0.2 0.3

1.0 -1.2 -1.2 -0.2 0.3 0.4 0.3 0.1 0.2 0.0 0.0 0.1 0.2 0.1 -0.1 0.0 -0.0 -0.0 0.1 0.2 0.5

1.2 -1.9 -2.4 -0.3 0.3 0.4 0.3 0.2 0.1 0.1 0.0 -0.0 0.3 0.2 -0.0 -0.1 -0.1 -0.1 0.1 0.3 0.5

1.3 -3.1 -3.2 -0.4 0.3 0.4 0.4 0.3 0.1 0.1 0.1 -0.1 0.2 0.2 -0.0 -0.0 -0.0 -0.0 0.1 0.2 0.6

1.4 -13.1 -5.0 -0.8 0.2 0.2 0.4 0.3 0.2 0.2 0.2 -0.1 0.2 0.2 -0.0 -0.0 -0.1 -0.1 0.2 0.2 0.6

1.5 -23.4 -5.6 -1.3 0.1 -0.1 0.4 0.4 0.2 0.3 0.1 -0.1 0.2 0.2 -0.0 -0.1 -0.1 -OJ 0.1 0.3 0.6

1.6 -31.5 -5.1 -1.5 -0.1 -0.2 0.5 0.5 0.1 0.3 0.1 -0.2 0.1 0.2 -0.1 -0.2 -0.2 -0.2 0.1 0.3 0.6

1.8 -43.8 -5.0 -1.3 -0.3 -0.4 0.2 0.5 0.0 0.4 0.2 -0.1 -0.0 0.2 0.0 -0.2 -0.2 -0.2 0.0 0.3 0.6

2.0 -48.2 -5.1 -1.3 -0.9 -0.5 0.2 0.3 0.1 0.4 0.3 -0.0 0.1 0.2 -0.1 -0.2 -0.3 -0.3 -0.0 0.4 0.6

2.5 -43.3 -10.0 -2.8 -0.5 -0.3 -0.2 0.0 -0.0 0.2 0.4 0.0 0.0 0.1 -0.1' -0.2 -0.5 -0.6 -0.2 0.3 0.7

3.0 -37.5 -12.7 -0.3 1.1 1.0 0.2 0.1 -0.2 0.1 0.3 -0.1 -0.0 0.0 -0.2 -0.2 -0.7 -0.7 -0.4 0.2 0.7

4.0 -23.6 -5.1 -0.3 0.2 1.6 -0.7 0.2 -0.3 0.0 0.4 -0.5 -0.8 -0.3 -0.6 -0.4 -0.8 -0.7 -0.5 -0.0 0.4

5.0 -3.3 -2.9 -0.4 -0.1 0.6 -1.3 -0.6 -0.8 0.2 0.7 OJ -0.4 0.0 -0.2 -0.4 -0.3 -0.1 -0.2 -0.1 0.2

7.0 5.4 3.2 2.3 1.5 -0.0 -0.6 -0.6 -0.3 0.1 0.2 0.3 0.2 0.7 0.4 0.4 0.2 0.1 -0.1 -0.2 -0.4

10.0 3.7 1.5 0.3 -0.6 -0.5 -1.1 -0.7 -0.3 -0.5 -0.7 -0.3 -0.1 0.1 0.2 -0.1 0.5 -0.1 -0.2 -0.2 -0.0

15.0 1.4 2.6 1.3 -0.1 0.6 0.7 -0.5 -2.0 -1.9 -0.8 1.] 0.5 0.9 0.6 0.2 -0.8 -0.6 0.3 1.2 2.0

THE OIL ANn OAS. JOHRNAl._TllNF 111 10'7~

and introduced reduced correlations for the Bn term. This equation was then applied to the Pitzer Z tables with excellent results.

For the present work, Equation 2 is generalized in a slightly different manner. In this case, the CarnahanStarling hard-sphere equation is used and a third term is added to the real-fluid deviation function:

z =

1 + y + y2 - y3 (l - y)3

+ By + CyD

where B, C, and D are functions of temperature.

The choice of this form had the effect of making the temperature dependence of these parameters quite simple and, when applied to the entire P, p, T surface represented by the Standing-Katz Z-factor chart, the new equation becomes

1 + y + y2 _y3

Z - (14.76 t - 9.76 t2 + 4.58 t3) Y +

(1 - y)3 (7)

(90.7 t - 242.2 f2 + 42.4 P) yO.18+2.82 t)

with

bPc

-- = 0.245 exp [-1.2(1- t)2] (8)

RTc

The y formulation has been retained, although it is less familiar than Plh because the equation remains somewhat simpler and easier to use.

Comparison chart. Table 1 and Fig. 1 present the detailed comparison of Equation 7 with a condensed table of Z factors read from the Standing-Katz chart.> Fig. 2 is merely a graphical representation of Equation 7 and will be discussed further. Fig. 3 illustrates the suspect nature of the original values of Z for T R = 1.05, 1.10 and 1.15.

Close scrutiny of Table 1 would revea. that, excluding the isotherms 1.05, 1.10, and 1.15, Equation 7 reproduces the original values with an average deviation of 0.3%. Of the 289 points in the condensed table, only 11 have deviations exceeding 1.0% and none exceed 2.0%. Thus, excluding the lowest three isotherms, the fit is within the accuracy of the correlation.

Deviations for the suspect isotherms are large near the minimum Z and will be discussed at the end of this section.

Fig. 1 presents the normal plot of Z YS. PRo The Jines represent Equation 7 while the points are values from the condensed table. The dashed lines represent extrapolations which are made to produce a Tit = 1.00 isotherm and PR values above 15 for all isotherms. Note that the original values show physically unrealistic inflections for T R = 3.00 in the range 1 < PR < 2.

Flg, 2 illustrates why most equations of state, including Equation 7, are density explicit rather than pressure explicit. Note the much Simpler form of the curves and the smoother progression over the surface. Most significant is the finite slope of Z vs. y at the critical point compared with infinite slope for Z vs. PH at the critical point.

The infinite slope is very difficult to fit with fewer than infinity empirical parameters. The fact that no two sotherms cross makes this plot easier to read as an added advantage.

Now to the problem of the suspect paints. Fig. 1 reveals

THE OIL AND GAS JOURNAL-JUNE 18, 1973

(6)

Table 2

Comparison with data and with modified Redlich-Kwong Equation, System 1

Component Mol fraction
System No. 1 at 2750 F. Nitrogen 0.0019
Methane 0.7512
Gas gravity = 0.9876 Carbon dioxide 0.0092
Ethane 0.0857
T,,, = 446.650 R. Propane 0.0453
i-butane 0.0171
P,,, = 651.88 psia n-butane 0.0128
i-pentane 0,0066
n-pentane 0.0041
n-hexane 0.0087
Heptanes plus 0.0574 ].0000
Modified
Tn = 1.645 Equation 7 Redlich-Kwong
,-<----.., ,-<----.., ~
P, psia p" Z (obs) Z (call % Error Z (cal) % Etror
11,918 18.283 1.6470 1.6627 -0.957 1.6670 -1.214
11,032 16.923 1.5620 1.5760 -0.898 1.5822 -1.293
10,068 15.445 1.4690 1.4811 -0.827 1.4896 -1.402
9,038 13.685 1.3670 1.3793 -0.905 1.3905 -1.719
8,132 12.475 1.2770 1.2897 -0.998 1.3033 -2.060
7,204 11.051 1.1860 1.1983 -1.040 1.2143 -2.386
6,536 10.026 1.1250 1.1332 -0.734 1.1508 -2.293
6,006 9.213 1.0760 1.0824 -0.600 1.1011 -2.333
5,611 8.607 1.0330 1.0453 -1.196 1.0645 -3.049
Average absolute % error: 0.906 1.972 Table 3

Comparison with data and with modified Redlich-Kwong Equation, System 2

Component Mo I fraction
System No. 2 at 2760 F. Nitrogen 0.0010
Methane 0.9118
Gas gravity = 0.7964 Carbon dioxide 0.0143
Ethane 0.0264
T". = 386.130 R. Propane 0.0095
i-butane 0.0026
PI" = 666.36 psia nbutane 0.0024
i-pentane 0.001I
n-pentane 0.0009
n-hexane 0.0013
Heptanes plus 0.0287 1.0000
Modified
. TIl := 1.905 Equation 7 Re dli ch·Kwong
,----"---.. ,.----A------., ,----"---..
P, psia Pn Z (obs) Z (call % Error Z (cal) % Error
13,683 20.534 1.7230 1.6964 1.542 1.7155 0.435
13,209 19.823 1.6750 1.6587 0.970 1.6778 -0.167
12,621 18,940 1.6280 1.6118 0.989 1.6308 -0.172
1I,ll8 17.585 1.5530 1.5397 0.855 1.5587 -0.367
11,334 17.009 1.5230 1.5089 0.922 1.5281 -0.335
Average absolute % error: 1.056 0.295 85

Table 4
Comparison with data and with
modified Redlich-Kwong Equation,
System 3
Component Mo r fractio n
System No. 3 at 2750 F. Nitrogen 0.0007
Methane 0.7776
Gas gravity = 1.1833 Garbon dioxide 0.0153
Ethane 0.0339
T,>< = 464.580 R. Propane 0.0189
i-butane 0.0139
p,). = 637.89 psia n-butane 0.0069
i-pentane 0.0060
n-pentane 0.0044
Hexanes 0.0142
Heptanes 0.0191
2500 F. avg, BP 0.0184
3000 F. avg, BP 0.0158
3500 F. avg. BP 0.0133
4000 F. avg, BP 0.0086
4500 F. avg, BP 0.0046
4750 F. + fraction 0.0284
1.0000
Modified
Tn = 1.581 Equation 7 Redlich-Kwong
~ ,..---'-----, ~
P, psia Pn Z (obs) Z (cal) % Error Z (cal) % Error
12,300 19.282 1.7980 1.7569 2.281 1.9000 -5.673
12,000 18.812 1.7640 1.7257 2.169 1.8662 -5.794
11,500 18.028 1.7070 1.6735 1.962 1.8095 -6.005
11,000 17.244 1.6500 1.6210 1.752 1.7527 -6.224
10,500 16.461 1.5930 1.5684 1.539 1.6958 -6.453
10,000 15.677 1.5380 1.5157 1.449 1.6387 -6.547
9,500 14.893 1.4830 1.4627 1.363 1.5814 -6.635
9,000 14.109 1.4280 1.4097 1.280 1.5241 -6.730
8,500 13.325 1.3730 1.3565 1.198 1.4665 -6.810
8,000 12.541 1.3190 1.3033 1.187 1.4088 -6.808
7,500 11.758 1.2640 1.2501 1.095 1.3510 -6.883
7,000 10.974 1.2100 1.1970 1.066 1.2930 -6.868
6,500 10.190 1.1560 1.1443 1.010 1.2353 -6.860
6,000 9.406 1.1020 1.0920 0.902 1.1776 -6.860
5,360 8.403 1.0370 1.0264 1.018 1.1042 -6.480
Average absolute % error: 1.418 6.509 nothing unusual about either Equation 7 or the original values except that they are in substantial disagreement for low values of T R. Fig. 3 now presents an expanded view of these isotherms on a Z vs. y plot. Note first that Fig. 2 shows thes 3 isotherms merging smoothly with the other isotherms for Equation 7.

Now note that the smooth progression is upset by the original values. There appears to be a sharpening of the original points toward the right, forming, in the case of TR = 1.05, an "elbow" at the minimum. This is not what we expect from normal experience, but there are other reasons to reject this behavior.

Based upon molecular arguments, which are beyond the scope of this article, such "elbows" or sharpenir e curves represent physically unrealistic situations. Moreover, the high-density inflections for the plots of the original values are forbidden by any reasonable molecular hypothesis.

While these observations do not establish the validity of Equation 7, they certainly cast serious doubt upon the validity of the original values. Had the original data been

90

Table 5

Comparison with data and with modified Redlich-Kwong Equation, System 4

Component Mol fraction
System No.4 Nitrogen 0.1191
Methane 0.3836
Gas gravity = 1.0994 Carbon dioxide 0.0849
Ethane 0.0629
Tpc = 465.67° R. Hydrogen sulfide 0.2419
Propane 0.0261
P, .• = 763.74 psia i-butane 0.0123
n-butane 0.0154
i-pentane 0.0051
n-pentane 0.0047
n-hsxane 0.0067
Heptanes plus 0.0373 1.0000
Modified
Equation 7 Redlich Kwong
~ ~ ~
P, psia Pit Z (ohs) Z (caO % Error Z (call % Error
T" = 1.646 30r F.
10,017 13.116 1.3080 1.3308 -1.745 1.3170 -0.688
8,115 10.625 1.1540 1.1711 -1.486 1.1660 -1.040
6,098 7.984 0.9980 1.0084 -1.044 1.0113 -1.333
4,207 5.508 0.8830 0.8817 0.146 0.8865 -0.396
2,035 2.665 0.8460 0.8527 -0.798 0.8448 0.142
Tn = 1.530 2530 F.
9,942 13.018 1.3260 1.3460 -1.510 1.3382 -0.920
8,094 10.598 1.1590 1.1747 -1.358 1.1758 -1.450
6,138 8.037 0.9910 0.9970 -0.605 1.0059 -1.504
4,175 5.467 0.8390 0.8407 -0.207 0.8507 -1.395
Tn = 1.447 214° F.
10,015 13.113 1.3530 1.3740 -1.552 1.3699 -1.249
8,102 10.608 1.1660 1.1832 -1.482 1.1888 -1.955
6,171 8,080 0.9830 0.9919 -0.914 1.0056 -2.299
4,216 5.520 0.8130 0.8140 -0.130 0.8294 -2.017
3,139 4.l10 0.7440 0.7469 -0.·,93 0.7526 -U56
Tn = 1.359 1730 F.
1O,0~4 13.138 1.3820 1.4042 -1.607 1.4044 -1.621
8,087 10.589 1.1820 1.1946 -1.070 1.2050 -1.946
6,126 8.021 0.9780 0.9824 -0.450 1.0016 -2.413
4,198 5.497 0.78~0 0.7826 0.041 0.8045 -2.746
3,147 4.121 0.6980 0.6967 0.181 0.7095 -1.648
Average absolute % error: 0.880 1.469 Nomenclature

b "van der Waals type" covolume

Bk vidal coefficients

B, C, D = temperature dependent parameters

P pressure

Pit reduced pressure

P, = critical pressure

Ppc pseudocrltical pressure

R = universal gas constant

t reciprocal reduced temperature

T = absolute temperature

TR reduced temperature

To critical temperature

Tpc pseudocritical temperature

Z = compressibility factor

a scaling parameter for b

p density

pn = reduced density

THE OIL AND GAS JOURNAL-JUNE 18, 1973

Table 6
Comparison with data and with
modified Redlich-Kwong Equation,
System 5
Component Mo I fractio n
System NO.5 Nitrogen 0.0943
Methane 0.3036
Gas gravity"" 1.1153 Carbon dioxide 0.0672
Ethane 0.0498
TI'(· = 499.330 R. Hydrogen sulfide GAOOO
Propane 0.0207
P,n' = 852.56 psia l-butane 0.0097
n-butane 0.0122
i-pentane 0.0040
n-pentane 0.0037
n-hsxane 0.0051
Heptanes plus 0.0295
1.0000
Modified
Equation 7 Re dl ich·Kwong
r-----'----, ~ ~
P, psla PH Z (obs) Z (caf) % Error Z (cal) % £rror
Tn = 1.421 2500 F.
10,039 11.775 1.2520 1.2774 -2.036 1.2684 -1.310
8,025 9.413 1.0780 1.0932 -1.415 1.0962 -1.688
6,150 7.214 0.9260 0.9245 0.157 0.9m -1.199
4,163 4.883 0.7680 0.7673 0.089 0.7823 -1.862
2,585 3.032 0.7130 0.7233 -1.454 0.7193 -0.884
Tn '" 1.267 173° F.
10,022 11.755 1.3050 1.3185 -1.041 1.3275 -1.724
8,078 9.475 1.1070 1.1141 -0.645 1.1337 -2.412
6,123 7.182 0.9080 0.9065 0.165 0.9355 -3.029
4,158 4.877 0.7110 0.7035 1.041 0.7364 -3.572
3,284 3,852 0.6360 0.6272 1.379 0.6542 -2.862
Average absolute % error: 0.942 2.054 scrutinized on a density basis, this discrepancy would undoubtedly have been noticed and resolved.

Comparisons with real gas. Tables 2-6 and Figs. 4 and 5 present comparisons of Equation 7 with natural systems. The pseudocritical temperatures and pressures were calculated using Kay's molar average" rule and were corrected for CO2 and HzS using the method developed by Wichert and Aziz> fo rthe Standing-Katz Z-factor chart.

Also shown are comparisons of the modified RedlichKwong equation of state. I. This equation of state was selected because Wichert and Aziz-" reported it to be the best overall method for predicting compressibility factors for sour natural gases. The modification to the RedlichKwong equation proposed by Wichert and Aziz were not tested because it reduces to the original Redlich-Kwong equation at pressures above 2,500 psia when CO2 and HzS are not present, and considerable testing by the authors at these conditions shows the modified Redlich-Kwong equation to be superior to the original Redlich-Kwong equation.

Comparisons were made with data measured on 12 reservoir gas and gas-condensate systems which covered the following conditions and compositions: 100° to 3070 F., 2,000 to 13,683 psia, up to 33.4 mol % Nz, up to 8.5 mol % COz, up to 40 mol % HzS, and up to 10.8 mol % heptanes plus. The modified Redlich-Kwong equation showed good agreement with the data for the gases and lean gascondensate systems, but its accuracy decreased when compared with the data on the richer gas-condensate systems (above 5 mol % heptanes plus).

Equation 7 had about the same magnitude of errors for all systems and had lower errors than the modified Redlich-Kwong equation for 9 of the 12 systems tested. Equation 7 produced an overall average absolute percentage error of 1.21 %. The modified Redlich-Kwong equation showed an overall average absolute percentage error of 2.51 % for the same data.

The superior behavior of Equation 7 results mainly from its good extrapolation properties. The Standing-Katz chart, upon which it is based, extends only to Pn = 15. Because Equation 7 has a sound theoretical basis, it can be extrapolated at least to Pit = 25 thus covering the practical high pressure/density range. However, temperature extrapolation cannot be expected to be good, especially below Tn = 1.

Acknowledgments

This report is the result of work begun at the University of Virginia, continued at Amoco Production Co. and the Katholieke Universiteit Leuven (Belgium), and completed at the National Bureau of Standards (Washington). A North Atlantic Treaty Organization postdoctoral fellowship provided most of the financial support for K. R. Hall in Belgium and at NBS. Amoco Production Co. furnished all data for the natural systems.

References

I. Standing, M. B. and D. L. Katz, AIME Pet. DeI'. Tech.,

146, 140 (1942).

2. Gray, E. H. and H. 1. Sims, OGJ, 57, No. 30, 80 (1959).

3. Reiss, H. el a1., J. Chern. Phys., 31, 369 (1959).

4. Thiele, E., J. Chem. Phys., 39, 474 (1963).

5. Ree, F. H. and W. G. Hoover, J. Chern, Phys., 46, 4181 (1967).

6. Mansoori, G. A. and F. B. Canfield, J. Chern. Phys., 51, 5295 ([969).

7. Carnahan, N. F. and K. E. Starling. J. Chern. Phys., 51, 635 (1969).

8. Lef-evre, E. J., Nature, 235, 20 (1972).

9. Hall, K. R., J. Chern. Phys., 57, 2252 ([972).

10. Haar, 1. and S. H. Shenker, J. Chern. Phys., 55, 4951 (1971). II. Bienkowski, P. R. et al., A. 1. Ch, E. Journal, accepted

for 1973.

12. Michels, A. et al., Physica, 15, 627 (1949).

13. Kay, W. B., Ind. Eng. Chem., 28, 1014 (1936).

14. Wichert, E. and K. Aziz, Hydroc. Proc., 51, 119 (May 1972). 1 S. Robinson, R. 1. and R. H. Jacoby, Hydroc. Proc., 44, 141

(April 1%5).

J 6. Wichert, E. and K. Aziz, Can. Gas J., 20 (Jan.-Feb. 1971).

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THE OIL AND GAS JOURNAL-JUNE 18 1973

How to solve equation of state for Z-factors

LYMAN YARBOROUGH Amoco Production Co. Tulsa

K. R. HALL

Univ. of Virginia Charlottesville, Va.

A PREVIOUS publication presented an equation of state t hat accurately represents the Standing-Katz Z-factor chart.l

This publication triggered correspondence seeking Information on proper use of this equation, so we now present a method for calculating Z-factors using this equation of state.

For those who perform occasional calculations and do not desire to solve the equations, a plot of the extended Standing-Katz Z-factor chart is included (Fig. 1). This chart terminates at a reduced pressure of 24, but the equation provides reasonable results at even higher pressures.

To calculate Z-factors using the closed form, augmented hard-sphere equation of state requires use of Equations 1, 4, 7, and 8 of Reference 1:

z = rpt'RT

y = bp/4

z = - (14.76t-9.76t2+4.58ts) y+ (3)

(1-y)3

(90.7t-242.2t2+42.4t8) Y (l.18~.82t)

bPrJRTc = 0.245 exp [-1.2(I-t)2J

By solving Equation 4 for b and substituting into Equation 2, then rearranging to solve for the densIty p, we find that

p = -----------

0.06125 RTc exp [-1.2(1-t)Z]

Substituting this expression for the density into Equation 1 gives the following expression for z in terms of y (which is a temperature-dependent "reduced" density)

0.06125 Prt exp [-1.2(1_t)2]

z = ----------

y

Substitution of Equation 6 into Equation 3 produces an equation for y In terms of reciprocal reduced temperature and reduced pressure.

0.06125 Prt exp [-1.2(1-t)2] l+y+y2_y3

---------- + ----

Y (1-y)3

(7)

(14.76t - 9.76t2 + 4.58tS)y +

(90.7t -242.2t2 + 42.4t3) y(1.18+U2t) :::: 0

Equation 7 is simplified somewhat if we multiply by y.

Furthermore, we shall designate the resulting equation by F for ease of discussion

F :::: -0.06125 Prt exp [-1.2(1-t)2] + (8)

y+y2+y3_yC

----- - (14.76t - 9.76t2 + 4.58t3) y2 +

(l-y§f

(90.7t .- 242.2t2 + 42.4t3) yC2.18+2.82t) :::: 0

(1)

This equation is nonlinear and must be solved by a trial-and-error method-the Newton-Raphson technique.

The Newton-Raphson technique is quite simple. Initially, a guess is made for the value of y, call it y (0). Using this value in Equation 8, F(O) can be evaluated, but, because yeo) is only a guess. F(o) will not equal zero as required. We now approximate F by a first-order Taylor's series expansion about F(o)

(2)

dF(O)

o = F """- F(o) + -- (y-y(Q») dy

(9)

Solving this equation, we obtain a new value for y which can be used to re-evaluate F and iterate until F (0) is less than some small number

(4)

dF(o) y :::: yCQ) _ F(o) / __

dy

(10)

The required derivative is

-:=;--------

(11)

dy

(5)

(29.25t - 19.52t2 + 9.16ts) y +

(2.18 + 2.82t) (90.7t - 242.212 + 42.4t8) y(l.18+2.82t)

(6)

These equations can be solved at all conditions by startmg with a small y and converging to the answer.

A method which would be more work at first but which would result in fewer iterations is to select the initial value of y close to the final answer based on the reduced-

) temperature and reduced-pressure values. We should note further that the gas constant, R. does not appear in any of the required equations (3, 6, 8, 11) so any consistent units may be included for pressure, volume, and temperature.

Extended Standing-Katz Z-factor chart

Reduced pressure

6 8

2

10

12

4

T4

Fig. 1

1.2

2.6

1.0
N
..::
j 2.4
.~ O.B
~
'"
E
c. 2.2 N
E
Q l5
'-'
0.6 t
.E
.~
:is
2.0 .~
E
0.4 c...
E
Q
'-'
1.8 1.6

OGJ

1.4

1.2

14

16

24

Reduced pressu're

THE OIL AND GAS 10URNAL-FEBRUARY 18.1974

Table 1

Example calculation for a gas condensate with high nitrogen content

Temperature "" 272° F. "" 7320 R.

Mol fraction Component

Component

Mol fraction

Nitrogen Methane Carbon dioxi de Ethane Propane

0.3343 l-butane

0.3095 n-butane

0.0317 i-pentane

0.0673 n-pentane

0.0551 Hexanes

Heptanes +

0.0223 0.02Bl 0.020B 0.0175 0.0262 O.OB72

H

~ XI "" 1.0000

I: 1

CW~ = 120 [(XC<>2 + XHn)O.9 - (xeD2 + XIIn)l.6J +

15 [Yxms - X· 1m] "" 4.89

11

Tmo:= }: Xi T.I "" 462.74° R.;Tpc := T",. - CWA := 457.85° R.

1= 1

"

P •• := (T., 2:: x,P"l / IT m a + XIl2>l (1 -XIl2.) CWA] := 574.39 psia

J = 1

"

gas gravity = (~ x,MW,) / 2B.966 := 1.3565

J:.1

t := 457.B5/732 := 0.62574

-0.06125 t exp I -1.2(1 -t1'1 = - 0.0323966

14.76t - 9.761' + 4.58P

:= 6.536537

90.7t - 242.2F + 42.4F := -27.690704

2.18 + 2.82t 3.944589

Test case: P := 6,532 psia p,:= 11.372

Guess yrO} ee- 0.001

po) ee -0.0323966(11.372) +

0.001 + (0.001)2 + (O.OO1)l - (0.001)' (1-0.001)3

6.536537(0.001)2 - 27.690704(.001)3.9"45e9 ;:; -0.367413

dpO} 1 + 4(0.001) + 4(0.001)2 - 4(0.001)3 + (O.OOll·

-:=---------------

(] -0.001l" 3.944589[27.690704)(0.001l2-9"W9 := 0.994957

0.36741

v := 0.001 + --:= 0.370275

. 0.99497

dy

Iteration F(o} dy y
1 0.34525 7.39370 0.32358
2 0.08191 4.19544 0.30406
3 0.00884 3.32632 0.30140
4 0.00014 3.22403 0.30136
5 0.00000 3.22244 0.30136 Using y := 0.30136 in Equation 3 or 6 gives Z 0= 1.2225
Complete results for this condensate:
,.-Equation 3 or h Zfrom
P, psia p, Z(obs) Z(eale) % Error chart
6532 11.372 1.2104 1.2225 -1.001 1.220
5599 9.748 1.1018 1.1149 -1.189 1.112
4927 8.578 1.0268 1.0392 -1.208 1.038
4485 7.808 0.9794 0.9911 -1.191 0.990
4298 7.483 0.9609 0.9713 -1.083 0.970 Fig. 2

Sample computer program

An example calculation is outlined in Table 1. The pseudocriticaJ constants are calculated by the mol fraction average of the pure component criticals and corrected for CO2 using the method developed by Wichert and Aziz, ~ Once the pseudocriticals and reduced parameters have been calculated, the Z chart can be used.

The values from the chart are included for comparison.

If gas gravity is the only composition parameter available, it can be used to obtain the pseudocritical constants using correlations available in the literature.

Fig. 2 presents a listing of the computer program we use for this problem. I/O statements are deleted because they are machine speciflc.

Acknowledgments

Lyman Yarborough wishes to thank Amoco Production Co. for releasing this article for publication. K. R. Hall wishes to acknowledge support from the National Science Foundation, Grant GK-37467.

References

1. Hall, K. R., and L. Yarborough, OGJ, 71, No. 25, 82 (June 18, 1973).

2. Wichert, E., and K. Ariz, Hydroc, Proc., 51, 119 (May 1972).

Nomenclature

b = "van del' Waals type" covolume, eu ft/lb mol CWA =-= correction from Wichert and Aziz

MW = molecular weight

P = pressure, psla

Pc = critical pressure, psia

Ppc = pseudocritical pressure, psi a

Pr = reduced pressure, PIPe or P/Ppc R = universal gas constant

T = absolute temperature, "R. To = critical temperature, "R,

T po = pseudocritical temperature, "R.

t = reciprocal reduced temperature, TofT or Tpc/T

x == mol fraction

y = "reduced" density defined by Equation 4 z = compressibility factor

p = density, lb mol/cu ft