High Pressure Hydrocarbons VLE: De Priester Nomograms

K i = yi / xi = f (T , P )

Use Raoult’s Law algorithms

2
Illustration for Bubble Pressure Calculation by PR-EOS

System: Methane (1) / Butane (2)

T = 310K; x1 = 0.20
To compute P and y1

Substance Tc (K) Pc (bar) ω

Methane 190.6 45.99 012
Butane 425.1 37.96 0.20

Generalized cubic EOS:

RT a
P= − 2
V − b V + ubV + wb 2

For PR-EOS:

u = 2, w = – 1
0.45724 R 2Tc2 2
a= ⎡1 + f w (1 − Tr1/2 ) ⎤ ; fω = 0.3746 + 1.54226ω − 0.26992ω 2 )
Pc ⎣ ⎦
b = 0.07780 RTc / Pc

Mixing rules:
am = y12 a1 + 2 y1 y2 (a1a2 )1/ 2 + y22 a2
bm = y1b1 + y2b2 ,
ωm = y1ω1 + y2ω2

Cubic EOS Solution:

aP bP
Putting A = 2 2 and B = an equivalent form of the above cubic EOS obtains
RT RT
Z 3 − (1 + B − uB) Z 2 + ( A + wB 2 − uB − uB 2 ) Z + (− AB − wB 2 − wB 3 ) = 0
Or, Z 3 + α Z 2 + β Z + γ = 0
Where, α = (1 + B − uB); β = ( A + wB 2 − uB − uB 2 ); γ = − AB − wB 2 − wB 3
bi am ⎡ bi ai ⎤ ⎡ Z + B (1 + 2) ⎤ bP
ln φli = ( Z − 1) − ln( Z − B ) + ⎢ −2 ⎥ ln ⎢ ⎥;B =
bm 2 2bm RT ⎢⎣ bm am ⎦⎥ ⎣⎢ Z + B (1 − 2) ⎦⎥ RT

Note: Here we do not show the previous iterations, but a set of calculations near the converged
values of P and y1.

The basic phase-equilibria criterion to be used is:

1
yiφˆiV = xiφˆiL
y φˆ L
K i = i = iV
xi φˆ i

yi = K i xi
For Bubble Point computations:
∑ y =∑ K x
i
i
i
i i =1

Bubble Pressure Calculation at high pressures using Cubic EOS (Note that
this may be rewritten for Bubble T, and Dew T & P with suitable changes)
Read T, xi
physical constants, Print P, yi
estimates of P and yi
If ΣKixi > 1
then Yes
P (new)=P(old) ΣKixi
Estimate species No
fugacity coeff. If ΣKixi < 1 Is ΣKixi=1
for both phases and Ki then
P(new)=P (old)ΣKixi

Calculate ΣKixi No
{φiV }

Calculate all Yes

Has ΣKixi changed?
yi=Kixi/ΣKixi

Recalculate all species

fugacity coeff, and
{Ki}, ΣKixi

For computing species fugacity coefficients for the two phases the cubic EOS needs to be solved
separately with corresponding phase compositions to obtain ZL and ZV, which then are used in the
common expressions for species fugacity coefficients.

Solution:

P (guessed): 40.8 bar

y1 (guessed) = 0.85; y2 = 0.15;

First consider calculation of the species fugacity coefficients for the liquid phase as T, P and x1
(=0.2) are all know. For this one needs to solve for the cubic EOS with liquid phase compositions.
T = 310K, P = 40.8bar

2
For each species the following estimates are made:

Table 1
Parameter Methane (1) Butane (2)
fω 3.9310 x 10-3 6.7229 x 10-3
a (Pa.m-6/mol2) 0.198207 1.811717
b (m3/mol) 0.000027 0.000072

With x1 = 0.2, it follows that

am = x12 a1 + 2 x1 x2 (a1a2 )1/2 + x22 a2 = 1.3592 Pa.m −6 / mol 2
bm = x1b1 + x2b2 = 0.000063 m3 / mol
am P
Am = = 0.8304
R 2T 2
b P
Bm = m = 0.10
RT

With the above values of A and B solve the cubic PR-EOS. The roots are as:
Z1 = 0.1471
Z 2 = 0.3764 + 0.5899i
Z 3 = 0.3764 − 0.5899i
The feasible root for the liquid phase is: ZL = 0.1471

Now using the generalized expression for species fugacity coefficients for PR-EOS:
b am ⎡ bi ai ⎤ ⎡ Z + B (1 + 2) ⎤
ln φli = i ( Z − 1) − ln( Z − B ) + ⎢ −2 ⎥ ln ⎢ ⎥
bm 2 2bm RT ⎣⎢ bm am ⎦⎥ ⎣⎢ Z + B (1 − 2) ⎦⎥
Using: Z= ZL = 0.1471; B = Bm
b1 L am ⎡ b1 a1 ⎤ ⎡ Z L + Bm (1 + 2) ⎤
ln φl1 = ( Z − 1) − ln( Z L − Bm ) + ⎢ −2 ⎥ ln ⎢ ⎥
bm 2 2bm RT ⎢⎣ bm am ⎥⎦ ⎢⎣ Z L + Bm (1 − 2) ⎥⎦
whence : φˆ L = 4.0271
1

Similarly: φˆ2L = 0.0932

Next compute the fugacity coefficients for the vapour phase. The calculations are the same as above
except that xi is replaced with yi. (Note that the pure component properties remain the same as in
Table 1, since the T and R are the same, i.e, 310K and 40.8bar, respectively.

With y1 = 0.85, it follows that

am = y12 a1 + 2 y1 y2 (a1a2 )1/2 + y22 a2 = 0.3323 Pa.m −6 / mol 2
bm = y1b1 + y2b2 = 0.000033 m3 / mol
am P
Am = = 0.2030
R 2T 2

3
 bm P
Bm = = 0.0528
RT

With the above values of A and B solve the cubic PR-EOS. The roots are as:
Z1 = 0.8537
Z 2 = 0.0467 + 0.0833i
Z 3 = 0.0467 − 0.0833i
The feasible root for the liquid phase is: ZV = 0.8537

Now using the generalized expression for species fugacity coefficients for PR-EOS:
b am ⎡ bi ai ⎤ ⎡ Z + B (1 + 2) ⎤
ln φli = i ( Z − 1) − ln( Z − B ) + ⎢ −2 ⎥ ln ⎢ ⎥
bm 2 2bm RT ⎣⎢ bm am ⎦⎥ ⎣⎢ Z + B (1 − 2) ⎦⎥
Using: Z= ZV = 0.8537; B = Bm
b1 V am ⎡ b1 a1 ⎤ ⎡ Z V + Bm (1 + 2) ⎤
ln φl1 = ( Z − 1) − ln( Z V − Bm ) + ⎢ −2 ⎥ ln ⎢ ⎥
bm 2 2bm RT ⎢⎣ bm am ⎦⎥ ⎣⎢ Z V + Bm (1 − 2) ⎦⎥
whence : φˆV = 0.9399
1

Similarly: φˆ2V = 0.5184

Therefore:
y1 φˆ1L 4.0271
K1 = = = = 4.2846
x1 φˆ1V 0.9399
y1 = K1 x1 = 0.8569
y φˆ L 0.0932
K 2 = 2 = 2V = = 0.1798
x2 φˆ 2
0.5184
y2 = K 2 x2 = 0.1438
Thus : ∑ yi =1.0007
i

Therefore we may terminate the iteration at this point.

Bubble Pressure = 40.8bar

y1 = 0.8569