Gas Properties III

PETE 444

Sept. 13
FORGAS Training (Schlumberger)

Availability on any Friday in November?

 Z Factor Determination
The Standing & Katz Z-factor chart is still the “gold
standard.” However it is inconvenient for modern use where
repetitive or iterative calculations are involved.

Two chief approaches have been devised to represent the chart

numerically:

1. Interpolation
2. Correlations
a) best efforts curve fit
b) based on an equation of state

A few of these methods will be presented…

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 Z Factor Determination
• Utterly Unjustified and Uninformed Guess: Z=0.9
• van der Waals EOS (1873)
• Gray and Sims’ tabular interpolation of Standing
(1959, 1961)
• Dranchuk & Abou-Kassem (DAK) correlation
(1975)
– Based on a Starling EOS
And many more, too numerous to mention…

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 Z-Factor from VDW EOS
An old thermodynamics text presents a Z-factor based
on van der Waals’ EOS as

The derivation is actually somewhat messy…

Skip This?

Van Wylen and Sonntag, “Fundamentals of Classical Thermodynamics, 1972 5

 Z-Factor from VDW EOS
The Z-factor may be obtained by numerically solving the
VDW EOS in several ways:

• random guesses (frustrating and not recommended)

• iteration by bisection (slow but stable)
• Newton-Raphson iteration (fast, potentially unstable)
• “Goal Seek” function built into Excel spreadsheets

In all cases, the problem reduces to solving for the real

roots of a cubic equation:
æ p ö æ 27 p ö 27 p 2
f (z) = z 3 - ç r + 1÷ z 2 + ç r
÷ z - r
3 =0
è 8Tr ø
2
è 64 Tr ø 512 Tr

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 Newton Raphson Solution

Initial guess, x0

Stark, Introduction to Numerical Methods, 1970 7

 Newton Raphson Solution
1. Provide an initial guess, x0. The value of the function here is
f(x0), and its slope, f´(x0), is obtained by evaluating the derivative
of f(x0). Note that the slope can be approximated by:
f´(x0)=[f(x1)-f(x0)]/[x1-x0]

2. We want to get closer to the root of the equation by projecting

to the x-axis, and solving for x1. Therefore rearrange the equation
above to obtain:
x1=x0-f(x0)/f´(x0)

Now x1 is the new guess for the root of the equation.

3. Evaluate the next guess for the root, x2, by using the equation
above.
4. Iterate until desired accuracy is obtained
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 Z-Factor from VDW EOS
Example. Using the expression for Z-factor from van der Waals’
EOS, evaluate Z for Tr=1.5, pr=2, with Newton Raphson iteration.

First we need to obtain the derivative of the equation,

æ p ö æ 27 p ö 27 p 2
f (z) = z 3 - ç r + 1÷ z 2 + ç 2 ÷z -
r r
3 =0
è 8Tr ø è 64 Tr ø 512 Tr
d æ p ö 27 pr
¢
f (z) = f (z) = 3z - 2ç
2 r
+ 1÷ z +
dz è 8Tr ø 64 Tr
2

Now to find the roots of f(z):

1. Initial guess, z0=1 because the first set of calculations go
much quicker (we also know that z >0)
2. Evalulate f(z0)=f(1)=
æ 2 ö 2 æ 27 2 ö 27 22
(1) - ç + 1÷(1) + ç ´ 2 ÷(1) - ´ 3 = 0.145833
3

è 8 ´1.5 ø è 64 1.5 ø 512 1.5

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 Z-Factor from VDW EOS

æ ö
2 27 æ 2 ö
3(1) - 2ç
ç + 1÷(1) + ç 2 ÷ = 1.04166
÷
2

3. Evaluate f´(z0)= è 8(1.5) ø 64 è 1.5 ø

4. Now find the new guess for the root of f(z),

f (z0 ) 0.145833
z1 = z0 - = 1- = 0.86
f ¢(z0 ) 1.04166

5. Return to step 2 and continue to iterate until desired accuracy

is reached.

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Z-Factor from VDW EOS

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 Z-Factor from VDW EOS
The VDW equation of state is no longer of practical use, however it
demonstrates the manipulation of any EOS into an expression for z
and solving for it. Since modern EOS are more elaborate, an explicit
derivative is not always easy to obtain. Therefore the derivative can
be evaluated numerically:
d f (z  z)  f (z)
f (z)  f (z)  lim z0
dz z

Substituting into the Newton Raphson expression gives,

f ( z0 ) f ( z0 ) f ( z0 ) z
 z1  z0   z0   z0 
f ( z0 ) f ( z 0   z )  f ( z 0 ) f ( z0  z )  f ( z0 )
z

While the definition of the derivative requires that z be vanishingly

small, it can be calculated with reasonable accuracy by selecting
some finite value of z << z
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 Dranchuk Abou-Kassem (1975)

Dranchuk & Abou-Kassem, JCPT July-Sept., 1975, 34-36 13

 Dranchuk Abou-Kassem (1975)
• Employed a Starling EOS (much longer than VDW)
• Fit the equation to 1500 data points on the Standing-Katz
chart
• Used Kay’s mixing rule + Wichert-Aziz to correct for sour
gases
• Used an error minimization criteria to determine 11
coefficients
• Considered to be the best representation suitable for
computer use

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 Dranchuk Abou-Kassem (1975)
• The Starling EOS
(note there are 11 parameters!)

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Starling, Fluid Thermodynamic Properties for Light Petroleum Systems, 1973
 Dranchuk Abou-Kassem (1975)
The Starling EOS was The Constants
arranged as a function of A1 = 0.3265
z-factor as follows: A2 = -1.07
A3 = -0.5339
A2 A3 A4 A5
z  1  ( A1   3  4  5 ) r A4 = 0.01569
Tr Tr Tr Tr A5 = -0.05165
A7 A8 2 A6 = 0.5475
( A6   ) r This is reduced density,
Tr Tr 2 A7 = -0.7361
defined below.
A7 A8 5 A8 = 0.1844
 A9 (  ) r
Tr Tr 2 A9 = 0.1056
 r2 A10 = 0.6134
 A10 (1  A11  )
2
r 3
exp( A11  r2 ) A11 = 0.7210
Tr

 r  0.27 pr / ( zTr )

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 Dranchuk Abou-Kassem (1975)
The reduced density term seems unfamiliar, so let’s see
where it comes from. Just as with other reduced
parameters, we define

r 
c

But what is critical density? Clearly it’s the density at

the critical point. Therefore we can use a
 rearrangement of the real gas law as follows,
 pM zc RTc p 1 Tc pr
r     zc  zc
c zRT pc M pc z T zTr

Now we need to give a value for the critical z-factor, zc.


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 Dranchuk Abou-Kassem (1975)
The critical z-factor, zc, is defined at Tr = pr = 1. If we
solve the van der Waals equation for these conditions
we find that after many iterations, zc= 0.375. A z-factor
chart published by Lewis in 1936 gives zc values
between 0.2 and 0.3. The Standing and Katz chart only
goes as low as Tr = 1.05, however Katz (Handbook of
Natural Gas Engineering, 1959) appears to have
arbitrarily given zc = 0.27.

This value was adopted by Peter Dranchuk and his

colleagues at the U of Alberta resulting in the reduced
density expression,
0.27 pr
r 
zTr

Lewis, W.K.: “Application of Physical Data to High-Pressure Processes,” Ind. Eng. Chem., V28 (2),257-262, 1936. 18
 Dranchuk Abou-Kassem (1975)
1. Obtain Tr, Pr

2. Provide initial guess for Z

æ A2 A3 A4 A5 ö
3. Calculate C1 as ç A1 + + 3 + 4 + 5÷
è Tr Tr Tr Tr ø
æ A7 A8 ö
4. Calculate C2 as ç A6 + + 2÷
è Tr Tr ø

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 Dranchuk Abou-Kassem (1975)
æA A8 ö
5. Calculate C3 as A9ç + 2 ÷
7

è Tr Tr ø

---- Start of Iterations ---

6. Calculate reduced density, rr = 0.27pr /(zTr )

r r2
7. Calculate C4 as A10(1+ A11rr2 ) 3
exp(- A r 2
11 r )
Tr

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 Dranchuk Abou-Kassem (1975)
8. Calculate f (z) = z - [1+ C1rr + C2rr2 - C3rr5 + C4 ] = 0

9. Calculate f´(z) from

or take the derivative of f(z)

C r 2C r 5C r
2 5
f '(z) = 1+ 1 r + 2 r - 3 r
z z z
2A10 rr
2
+
Tr z
3
1+[A r
11 r
2
- (A r
11 r
2 2
) ]exp(-A r 2
11 r )

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 Dranchuk Abou-Kassem (1975)
10. Calculate new Z using f (z)
newZ = Z -
Newton Raphson, f '(z)

11. Compare new Z with old Z.

If the change is less than 0.0001 (or desired accuracy),
then stop; otherwise take new Z and start over at step 6.

Also refer to description of procedure in Appendix A

of Lee & Wattenbarger’s SPE textbook, Gas Reservoir Engineering.

NOTE: You can implement this as an Excel spreadsheet.

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 Dranchuk Abou-Kassem (1975)
Example

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Dranchuk Abou-Kassem (1975)

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 Z-Factor for Tr=1.5

VDW EOS Dranchuk Abou-Kassem (DAK) correlation

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 Gas Viscosity
• Bicher and Katz (1943)
– Viscosity could be determined from molecular weight alone
• Carr, Kobayashi and Burrows (1954) graphic method
• Measured viscosity directly for 3 different gas mixtures, plus 50:50
mixtures of C1:C2, C1:C3, and C2:C3
• Correlation based on pseudo-reduced properties
• Estimate gas viscosity at one atmosphere pressure
• Obtain viscosity ratio at higher pressure
• Presented as a graphical solution (good for exams)
• Lee, Gonzalez and Eakin (1966) equations
• Used 4 mixed gas samples
• Empirical correlation based on 116 measured data points
• Equations suitable for use in computer (good for homework)

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 Gas Viscosity: Carr et al (1954)
Example Let’s use the metric version of Carr et al charts to determine
the viscosity of a gas mixture with a specific gravity of g = 0.632 (MW =
18.3) at 37.8°C, 34474 kPa.

First use an older Sutton correlation to obtain pseudo-critical properties:

ppc (kPa) = 5218.1 - 903.2 g - 24.8 g2
= 5218.1 - 903.2(0.632) - 24.8(0.632)2
= 4637.4 kPa

Tpc (°K) = 94 + 194.2g - 41.1 g2

= 94 + 194.2(0.632) = 41.1(0.632)2
= 200.3K

Then the pseudo-reduced values are:

p 34474 T 37.8 + 273.15
p pr = = = 7.43 Tpr = = = 1.55
p pc 4637.4 Tpc 200.3

Carr, Kobayashi and Burrows: “Viscosity of Hydrocarbon Gases Under Pressure,” Trans.
27
AIME (201) 264-272.
 Carr et al: 1st Step

Note: Corrections required for N2, acid gases

A = 0.011 mPa-s

37.8°
C

MW=18.3 from GPSA SI Engineering Data Book 28

 Carr et al: 2nd Step

/A = 2.5
ppr = 7.43

Tpr = 1.55 29
 Gas Viscosity: Carr et al
Example
From the first chart we find that the viscosity at one
atmosphere is
A = 0.011 mPa-s

From the second chart for the given conditions, we read

/A = 2.5

Therefore
 = A  /A = 0.011  2.5 = 0.028 mPa-s = 28 Pa-s

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 Gas Viscosity: Lee et al
Xr Y
m = Ke
(9.379 + 0.01607 M)T1.5
K=
209.2 + 19.26M + T
986.4
X = 3.448 + + 0.01009 M
T
Y = 2.447 - 0.2224 X

 is viscosity, micropoise
T is absolute temperature, °R
 is gas density gm/cc
M is molecular weight

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 Gas Viscosity: Lee et al
Example
Let’s check one of the data points on Lee’s viscosity chart of “Gas Sample 4”:
1. Select conditions: T=100°F, p=5000 psia
2. Calculate Tpc, ppc from gas analysis or from correlations (e.g. Sutton)
Lee’s paper gives the complete analysis, so we can use Kay’s method,
Crit. Temp, Crit. Pres,
Component
Sample 4 Tci Pci Mol. Wt.
Mole Frac,
Species Name Abbr. yi °R psia Mi yi*Tci yi*pci yi*Mi
nitrogen N2 0.0055 227.27 493.00 28.013 1.25 2.71 0.15
carbon dioxide CO2 0.017 547.57 1071.00 44.010 9.31 18.21 0.75
helium H2 0 9.8 33.2 4.003 0.00 0.00 0.00
methane C1 0.915 343.04 667.80 16.043 313.88 611.04 14.68
ethane C2 0.031 549.76 707.80 30.07 17.04 21.94 0.93
propane C3 0.014 665.68 616.30 44.097 9.32 8.63 0.62
normal butane n-C4 0.005 765.32 550.70 58.123 3.83 2.75 0.29
iso-butane i-C4 0.0067 734.65 529.10 58.123 4.92 3.54 0.39
pentanes C5 (iso) 0.0028 845.37 488.60 72.150 2.37 1.37 0.20
hexane C6 0.0026 913.37 436.90 86.177 2.37 1.14 0.22
heptanes+ C7+ (use C8) 0.0008 1023.89 360.60 114.231 0.82 0.29 0.09
TOTAL 1.0004 365.11 671.62 18.33
Tpc, R ppc, psia MW
Note: NOT corrected for acid gas content - some error introduced
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 Gas Viscosity: Lee et al
3. Calculate reduced properties and Z-factor
T 100 + 460 p 5000
Tr = = = 1.53 pr = = = 7.44
Tpc 365.1 ppc 671.6

Using the Standing & Katz chart, z(Tr=1.53, pr=7.44) = 0.957

4. Calculate gas density from the general equation r = pM / zRT

Since the Lee correlation uses units of gm/cc, we insert some conversions thus:

p, psia · M,lb /lb - mole 454g æ 1 ft ö

3

r= · ·ç ÷
z · 10.73psia - ft3/lb - mole - °R · T,°R lb è 30.48cm ø Note this equation
r = 1.494 ´ 10 -3 pM /(zT)[ gm /cm 3 ]
uses English units:
P, psia
1.494 ´ 10 -3 (5000)(18.33)
r= = 0.255[ gm /cm ]
3
T, R
0.957(560)

(Lee obtained 0.257 gm/cc)

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 Gas Viscosity: Lee et al
5. Calculate constants K, X, and Y from Lee’s equations (T is in °R)

(9.379 + 0.01607 M)T1.5 (9.379 + 0.01607(18.33))(560)1.5

K= = = 114.23
209.2 + 19.26M + T 209.2 + 19.26(18.33) + 560
986.4 986.4
X = 3.448 + + 0.01004 M = 3.448 + + 0.01004(18.33) = 5.393
T 560
Y = 2.447 - 0.2224 X = 2.447 - 0.2224(5.393) = 1.247

6. Calculate gas viscosity, in micropoise,

Xr Y
m = Ke =114.23e 5.393(0.255)1.247
= 305mP

(Lee calculated 304 P)

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 Gas Viscosity
A comment on units of viscosity:

With liquids, the units commonly used are:

1cP = 1 mPa-s

With gases, which have a much lower viscosity, we tend to use the following
units for convenience:

1P = 10-4  10-2P = 10-4cP = 10-4mPa-s

= 10-4  10-3Pa-s= 10-1  10-6Pa-s
= 0.1Pa-s

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 Next Week
• Gas Reserves I and II
– Contours and volumetrics
– Material balance equation
– Gas reservoir types
– Water influx

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