Methods/Algorithms for Bubble/Dew point calculation

PETR 5328

By

Team 13:

Oluwatosin Ogundipe

Samuel Apetuje

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Contents
INTRODUCTION.......................................................................................................................................3

METHODS.................................................................................................................................................5

Mixture Saturation Points from Cubic Equations of State (3)....................................................................5

Bubble Point Pressure Calculations.....................................................................................................5

Dew Point Pressure Calculation...........................................................................................................6

CONVENTIONAL SUCCESSIVE SUBSTITUTION METHOD..........................................................7

MVNR METHOD...................................................................................................................................8

SATURATED LIQUID AND SATURATED VAPOR.......................................................................8

SELECTION OF ITERATION VARIABLES..................................................................................10

DEFINING EQUATIONS.................................................................................................................11

THE CORRECTION STEP...............................................................................................................12

STARTING ESTIMATES FOR SATURATION PRESSURE CALCULATIONS..........................12

CONCLUSIONS AND RECOMMENDATIONS.....................................................................................17

REFERENCES..........................................................................................................................................18

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INTRODUCTION

Determination of reservoir fluid properties, such as bubble and dew point cannot be

overemphasized for reservoir engineering calculations such as material balance, inflow

performance, reservoir simulation and reserves estimation. A small error in the calculation of

pressure-volume-temperature (PVT) properties, can lead to very significant errors in a reservoir’s

model design, operation and control, such subsequently leads to the development of

inappropriate reservoir simulation model and ultimately inaccurate reservoir performance

prediction. In an ideal situation, we would love to able to always obtain actual measurements of

PVT properties such as bubble and dew points, from laboratory experiments/analysis. However,

such procedures are very costly and time consuming. Alternatively, these properties can be

determined with the aid of empirical correlations or iteratively using an equation of state (EOS).

While empirical correlations are very easy to use, they do not include phase behavior of mixture,

whereas an EOS consists of detailed thermodynamics of the fluid but presents the challenge of

having to provide a good initial estimate.

Bubble point is defined as the pressure and temperature conditions at which the first bubble of

gas comes out of solution in oil (1). Dew point is defined as the pressure and temperature

conditions at which the first liquid droplet forms (2).

Due to the significance of these properties, we have been tasked with determining different

methods/algorithms with which to calculate the bubble/dew point.

The condition for thermodynamic equilibrium between phases is described by the following

mathematical equations:

1. The overall material balance:

L + V = 1; (1)

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 Where L is the moles of liquid and V is the moles of vapor per mole of mixture.

2. The component material balance:

zi = Lxi + Vyi (2)

where zi is the mole fraction composition of the initial fluid and xi and yi are the mole

fraction compositions of the liquid and vapor phases respectively.

3. Mole fraction constraints:

∑ z i=1 (3)
i=1

nc

∑ x i=1 (4)
i=1

nc

∑ yi =1 (5)
i=1

4. Finally the criteria for thermodynamic equilibrium

^f li= ^f vi (6)

where f li is the fugacity of component i in the liquid phase, and f vi is the fugacity of

component i in the vapor phase.

Combining (1)-(5), and solving for xi and yi yields,

zi
x i=
1+ V ( K i−1)

(7)

and

K i zi
y i= (8)
1+V ( K i−1)

yi
where K i=
xi

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From the mole fraction constraints,
nc

∑ ( y ¿ ¿ i¿ −xi )=0 ¿ ¿ (9)

This leads to
nc
( K ¿¿i−1)
F ( V ) =∑ zi =0 ¿
i=1 1+V (K i−1)

(10)

(10) is called Rachford-Rice Equation.

When V0, no vapor is present this means bubble point. (10) becomes,
nc

∑ z i K i=1 (11)
i=1

When V1, no liquid is present. This means dew point. (10) becomes,
nc
z
∑ Ki =1 (12)
i=1 i

The methods investigated in this paper include; using cubic equations of state, the conventional

successive substitution method, and the minimum variable newton-raphson (MVNR) method.

METHODS

Mixture Saturation Points from Cubic Equations of State (3)

Bubble Point Pressure Calculations

1. Provide an estimate of the bubble point pressure

2. Estimate the K-factors using Wilsons Correlation

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 T c ,i

K i=
[
Pc ,i exp 5.37(1+ ωi)( 1−
T
) ]
P

(13)

Where,Tc,i is the critical temperature of component i

Pc,i is the critical pressure of component i

ωi is the acentric factor of component i

3. Estimate vapor phase composition from y ij+1=z i K ij, i = 1,2,…,nc, where j is an iteration

counter

4. Calculate the vapor and liquid phase fugacity coefficients [(φ vi , i = 1,2,…,nc) and (φ li, i =

1,2,…,nc)] using current estimates for bubble point pressure and vapor phase

composition. The liquid composition equals the feed composition.

5. Calculate new K-factors from,

ln K i=ln φiL−ln φVi (14)

nc
6. Evaluate F=∑ z i K i −1 (15)
i=1

n
dF ∂ ln φiL −∂ ln φVi
c

7. Evaluate =∑ zi K i ( ¿ )¿ (16)
dP i=1 ∂P ∂P

8. Calculate the (j+1)th estimate of the bubble point pressure from

Fj
P j+1=P j−
d Fj (17)
dP

9. If not converged return to 3

Dew Point Pressure Calculation

1. Provide an estimate of the dew point pressure

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 2. Estimate the K-factors using (13)

j +1 zi
3. Estimate liquid phase composition from x i = , i = 1,2,…,nc, where j is an iteration
K ij

counter

4. Calculate the vapor and liquid phase fugacity coefficients [(φ vi , i = 1,2,…,nc) and (φ li, i =

1,2,…,nc)] using current estimates for dew point pressure and vapor phase composition.

The liquid composition equals the feed composition.

5. Calculate new K-factors from (14)

n
dF z i ∂ ln φVi −∂ ln φiL
c

7. Evaluate =∑ ( ¿ )¿ (19)
dP i=1 K i ∂ P ∂P

8. Calculate the (j+1)th estimate of the dew point pressure from (17)

9. If not converged return to 3

Bubble and dew points may also be calculated for a specified pressure, that is, temperature is the

unknown parameter.

These calculations are complicated by the fact that it is not generally known in advance if the

saturation points of the mixture actually exist at a specified temperature and pressure. For

example, a bubble point calculation for a temperature higher than the critical temperature would

not converge because the bubble point line ends in the critical point. Also, the mixture may have

two dew points as in the case of gas condensates. This may cause convergence problems in the

calculations. At best, either the upper or lower dew point will be located with this method.

This method converges easily from low to medium pressure than at high pressures.

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CONVENTIONAL SUCCESSIVE SUBSTITUTION METHOD

The phase equilibria equations that incorporate the most commonly used equations of state

(Soave-RedlichKwong and Peng-Robison) in the petroleum engineering industry, are nonlinear

and must be solved iteratively. The method of successive substitutions is one of the most widely

known and used methods in saturation point calculations involving EOS. Here we give an

illustration of the algorithm.

1. Estimate initial value of Ki from (13)

2. Compute F(V=0) and F(V=1) (10). If F(0) > 0 and F(1) < 0, two phases exist and

equation 10 is solved using Newton Raphson for V. If F(0) < 0 or F(1) > 0, then most

likely a single phase is present, in which case a value of V= 0.5 is assumed and the

calculation done.

3. Calculate xi and yi respectively from (7) and (8).

4. Compute f li and f vi from derived expressions for fugacity, and evaluate

f li F y
F i= v and K i= i i
fi xi

nc
5. Check for convergence using the criterion ∑ ( F i−1 ) 2 ≤ ε, (ε =10−7 ) (20)
i=1

If (20) is satisfied stop, if not proceed to step 6

6. Compute F(0) and F(1)

If F(0) < 0 set V= 0, i.e single phase liquid

If F(1) > 0 set V = 1, i.e single phase vapor

If F(0) > 0 and F(1) <0 solve (10)

7. Update xi and yi from (7) and (8) respectively, then go to step 4

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 In the single phase region, where V= 0 or V =1, the Fi’s may converge to a value

different from unity. Nghiem et al(4) suggested iterating until (20) is satisfied even in

single phase cases.

This method however, almost always diverges for bubble and dew point calculations near

the critical region; a region of high importance when studying multiple-contact, miscible

oil recovery methods involving CO2 or rich-gas injection because the path of the over-all

fluid mixture passes through this region. Also, this method almost always diverges for

some mixtures near their saturation pressure at conditions way from the critical region.

MVNR METHOD

SATURATED LIQUID AND SATURATED VAPOR

At a given temperature the pressure at which an infinitesimal amount of vapor first appears is

known as the bubble point pressure. Thus, for a saturated liquid the overall material balance is

simply

L=1 (21)

and the component material balances are

xi = zi ; (22)

Similarly, at a given temperature, the pressure at which an infinitesimal amount of liquid first

appears is known as the dew point pressure, and for a saturated vapor the overall material

balance is simply

V=1 (23)

and the component material balances are

yi = zi ; (24)

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The saturation (bubble and dew point) pressures are related to the fugacities of each component

in the liquid and vapor phases by

n
v l
and ps = ∑ (f i ¿) /(φi )¿, for saturated vapor (26) The
i=1

MVNR method was first presented by Fussel and Yanosik(5) as a robust algorithm for solving the

non-linear system of equations describing thermodynamic equilibrium using the RK EOS. The

single –stage separation equations 1, 2, 3, 5, 6 and the expressions for f li and f vi were considered,

which make up a 4n + 2 equations which are to be solved simultaneously in order to determine

L, V and n liquid phase compositions, xi, n vapor phase compositions, yi, n liquid phase

fugacities, f li, and n vapor phase fugacities, f vi . These equations are non-linear and have to be

solved iteratively. One way of handling the iterative sequence is to correct all 4n +2 unknowns at

each iteration, which would be very time consuming. The minimum variable Newton-Raphson

(MVNR) provides an efficient way of organizing the iterative sequence, as it reduces the size of

the correction step by eliminating as many unknowns as possible from the correction step . This

is achieved by breaking the unknown variables into 2 groups. The first group contains the

iteration or independent variables which are the unknowns to be corrected, and the second group

contains the dependent variables. One equation must be used to define each of the dependent

variables, and all these equations are collectively referred to as the defining equations.

The remaining equations which are equal to the number of iteration variables are known as error

equations. This yields a four-step iteration process for MVNR which are

1) Select the iteration variables and assume values for them

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 2) Calculate the dependent variables using the defining equations

3) Calculate the error using the error equations, and

4) Correct the iteration variables using the Newton-Raphson method.

The solution convergences when the error in Step 3 is less than an acceptable error tolerance, ε.

If not, the process is repeated.

SELECTION OF ITERATION VARIABLES

For bubble-point liquid, (6) and (25) along with f li and f vi make up a set of 3n + 1 equations that

are to be solved simultaneously to determine the bubble point pressure, ps, n vapor phase

compositions, yi, n liquid phase fugacities, f li and n vapor phase fugacities, f vi . The iteration

variables required by MVNR is n + 1; pressure p, and n vapor phase compositions. This is

referred to as p-y iterations.

For dew point, similarly there are 3n +1 equations to be solved simultaneously to determine the

dew point pressure , ps, n liquid phase compositions, xi, n liquid phase fugacities, f li and n vapor

phase fugacities, f vi , with n + 1 iterations variables (just like for bubble point liquids) which are

pressure p, and n liquid phase compositions. This is referred to as p-x iterations.

Initial estimates for p and yi and p and xi for p-x and p-y iterations respectively are required.

Fussel and Yanosik(5) used the component K values calculated by the empirical correlation (6)

K i=
[ (
exp 5.37 ( 1+ ωi ) 1−
T ri )] (27)
p ri

to flash the overall fluid mixture at the system temperature and an estimated saturation pressure,

yielding liquid and vapor compositions. Depending on the iteration used (p-x or p-y), the

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appropriate phase compositions are used as initial estimates of the iteration variables, xi and yi.

The other phase composition is equal to that of the fluid mixture (22).

DEFINING EQUATIONS

Next is to solve the defining equations for the dependent variables. The iterative steps for p-x and

p-y are,

1) Calculate by solving the Redlich-Kwong EOS, the compressibility factors for the liquid

and vapor phases ZL and Zv

2) Calculate n times(i.e for each of the n-components) f li and f vi

Error Determination

The error equations representing the residual of the thermodynamic phase equilibria equation (6)

is written as

∅ i=f li−f vi (28)

As stated previously the error equations are those remaining after selecting the defining

equations

For the p-y iteration, there are n + 1 iteration variables. (30) represents n error equations and the

remaining error equation is the residual of (25), which is written as

n
f li
∅ n +1=p s−∑ (29)
i=1 φ vi

Similarly, the additional error for the p-x iteration is

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THE CORRECTION STEP

The correction step is necessary to obtain the improved estimates of the iteration variables that

will reduce the residuals calculated by the error equations. The correction step reduces to a

matrix problem with an order directly proportional to n + 1 for the p-x and p-y iterations.

Even though the MVNR method has proved to be a good upgrade on the traditionally known

successive substitution method, experience has shown that the MVNR still requires for an

improve estimate of initial iteration parameters ( i.e pressure and phase compositions) for the

bubble and dew point pressure solutions. It was observed that the K-value correlation used for

the initial estimates usually gave satisfactory results when the fluid system contained significant

amounts of heavy components ( C7+), but was often unsatisfactory when dealing with fluid

systems containing only light components, for example fluids in dry gas-rich zones or CH4, CO2

or N2 rich mixtures.

STARTING ESTIMATES FOR SATURATION PRESSURE CALCULATIONS

In addition to the above stated shortcomings of the MVNR method, the correlation cannot be

used to determine all the K-values required for more complex CO2/hydrocarbon systems, such as

those in which three or more phases form.(7)

For these reasons Baker and Luks(8), employed a more self-consistent method of estimating

starting values of the iteration parameters, in which the EOS is used to obtain both the initial

estimates of saturation pressure and phase composition as well as the final converged solution.

The method is based on approximation of the phase compositions at progressively higher

pressure until a pressure region is reached in which the saturation pressure conditions are

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satisfied. This pressure and the corresponding phase compositions are then used to start the

MVNR solution. Employing the fugacity criteria for phase equilibrium, (6) and noting that

f li=x i p φli (31)

and

f vi = y i p φvi (32)

For a bubble point calculation the xi’s are known and the vapor phase composition is

p φli xi φli
y i=
p φ vi
=
( )
φvi
xi (33)

For a dew point calculation the yi’s are known and the liquid phase composition is given by

p φli y i φli
x i=
p φvi
=
( )
φvi
yi (34)

Initially both the pressure and second phase compositions are unknown. The estimation involves

the following steps,

1) Choose a low staring pressure ( e.g. 1 psi)

2) Compute φ vi and φ li at the pressure of the new iteration level using the composition from

the old iteration level. For the first iteration an approximation of φ li and φ vi ( for dew point

and bubble point respectively) must be used.

3) Evaluate the unknown phase composition using (33) for bubble point or (34) for dew

point. If the sum of the calculated phase compositions is less than 1 then the assumed

pressure is greater than the saturation pressure. If otherwise, the assumed pressure is less

than the saturation pressure.

4) Correct the pressure with the direction indicated in step 3. Baker and Luke(8)

recommended an increment of 100 psi to 300 psi for each iteration until the saturation

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 pressure is exceeded. At this stage, the half interval type method may be used to narrow

the search range.

5) Correct the unknown phase compositions by normalizing. Repeat step using these

corrected compositions to recalculate the fugacity coefficients at the new estimated

pressure.

As Fussel and Yanosik(4) have shown the MVNR method generally results in more rapid

convergence once the region of the saturation pressure is estimated reasonably well. Thus the

iteration above is stopped once the saturation pressure is within a reasonable range (say 20 psi).

The resulting phase compositions and pressure are then used as initial estimates for the MVNR

method. As mentioned in Step 2 above an estimate of φ li and φ vi must be made for the first

iteration. Using φ vi =1, is a good estimate at low pressures, for a bubble point calculation. For a

dew point calculation, φ li can be estimated as

φ li=φio exp [Z oL ¿( p/ psi −1)]¿ (35)

where φ oi is the pure component fugacity coefficient evaluated at the pure component vapor

pressure, psi, which can be estimated from the Clausius-Clapeyron equation(9) as

∆ H vi T ci
psi = p ci exp [ ( )(
T ci
1−
T )] (36)

The procedure described above for dew points also can be applied to calculate lower dew points,

below which only vapor exists. The only modification required is in Step 4, where
n n

∑ x i <1 indicates the pressure is less than the lower dew point pressure, and ∑ x i >1, indicates
i=1 i=1

that the estimated pressure is too high.

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It is worth noting that a variation of this technique is applicable to estimation of phase

compositions for a flash calculation in the two phase region.

The procedures described above use only the equation of state for iteration, the fugacity

coefficients are valid for any two-phase region. Also, the same EOS used to obtain the estimated

pressure and phase compositions, is used to calculate the final solution, thus fewer MVNR

iterations are required. Even though this method requires more CPU time to obtain the initial

estimates of phase compositions than the K-value used by Fussell and Yanosik(4), the fewer

MVNR iterations results in an overall faster and, most importantly, more reliable calculation

method.

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 T, xi

Initial guess for P

New value of P

Initial guess for φ vi

φ vi =φiv (T , P , x )

φ li=φli (T , P , x)

yes no

φli
y i=
( )
φvi
xi

First iteration

no

yi = yi’ yi'=yi ? Σy’I = 1

yes

Correct Calculated Bubble point and composition

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CONCLUSIONS AND RECOMMENDATIONS

In determining the saturation points (bubble and dew point pressure) of hydrocarbon fluids, the

use of equations of state offer a more convenient and time saving path as opposed to having to

rely squarely on expensive and laborious laboratory experiments. However, as we have discussed

in this paper, the methods available through the use of EOS have issues unique with whatever

technique one decides to adopt. The Conventional Successive Substitution Method has been

known to exhibit, very slow convergence rate at high pressures and possible divergence near the

critical point, for bubble and dew point calculations. The MVNR method, which relies on a

minimization of the number of unknowns and converges for near critical fluid mixtures, presents

a useful alternative to the CSS method as it also converges faster reducing CPU time. Still, the

MVNR method requires improvement on the estimation of its initial iteration parameters

(pressure and phase compositions), as discussed in the body of this paper.

In deciding what method to employ in bubble in dew point calculations, the following should be

considered;

a. CPU time and expense required

b. Sophistication of computer software

c. The fluid mixture to be analyzed especially in miscible oil recovery processes

There exist computer soft-wares that can switch from say CSS method to MVNR or

another preferred method, if CSS method is exhibiting very slow rate of convergence or

begins to diverge near critical regions.

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REFERENCES

1. Schlumberger Oilfield Glossary, http://www.glossary.oilfield.slb.com/en/Terms.aspx?

LookIn=term%20name&filter=bubble%20point, November 5, 2013.

2. Elementary Principles of Chemical Processes, Richard M. Felder, Ronald W. Rousseau,

Pg. 259 – 260.

3. Phase Behavior of Petroleum Reservoir Fluids, Karen S. Pedersen, Peter L. Christensen,

Pg. 119

4. Nghiem, L.X., Aziz, K. and Li, Y.K.:"A Robust Iterative Method for Flash Calculations
Using the SoaveRedlich-Kwong or the Peng-Robinson Equation of State," SPEJ, June
1983,521-530.
5. Fussell, D.O. and Yanosik, J.L.: "An Iterative Sequence for Phase Equilibrium

Calculations Incorporating the RedlichKwong Equation of State," Soc. Pet. Eng. J. (June

1978) 173- 182.

6. Wilson, G.M.: "A Modified Redlich-Kwong Equation of State, Application to General Physical

Data Calculations," paper presented at the 65th National AIChE Meeting, Cleveland, 1969.

7. Shelton, J.L. and Yarborough, L. “Multiple-Phase Behavior in Porous Media during CO2

or Rich-Gas Flooding” J. Pet Tech (Sept. 1977) 1171-1178.

8. Baker, Lee E. and Luks, K. D., :" Critical point and Saturation pressure Calculations for

Multipoint systems," SPEJ 1980, 15-24.

9. Himmelblau, D.M.: Basic Principles and Calculations in Chemical Engineering, Prentice-

hall Inc., Englewood Cliffs, NJ (1962) 242.

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