Day 2 Part 2: Equation of State Models.

Cubic Equation of State models.

Two-phase flash calculations (VLE).
Stability Analysis
Saturation Pressure Calculations.
Gradient Calculations
Introduction to PVT Simulators

Exercise 2-1

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Equation of State Calculations
Problem Definition Equation of State Models
Equation of state models (EOS) are
? Vapor
simple equations relating pressure,
volume and temperature.
Fluid Mixture
An EOS model accurately describes
Liquid
the multi-phase thermodynamic
(zi, p, T) (Fv, xi, yi) equilibrium of a multi-component
system, as well as the PVT
Given an overall fluid composition at properties of any given phase.
given pressure & temperature:
Combined with a mass-balance
Determine relative amount of equation (Rachford-Rice) the EOS
equilibrium oil and gas. model gives the equilibrium phase
Determine equilibrium oil and split of a multi-component fluid
gas compositions (K-values). mixture.
Determine essential fluid phase
properties.

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EOS Applications

Reservoir simulation
Generation of black-oil tables
Compositional simulations
Gas injection.
Near critical fluids.
Conversion from black-oil to compositional.

Pipeline calculations
Pressure loss, liquid dropout, etc.

Surface process calculations.

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Cubic Equation of State Models
General 2-parameter cubic EOS
The cubic EOS equation is generally
RT a expressed in terms of Z-factor (v=ZRT/p)
p
(v b) (v b b)(v b b)
Z 3 C2 Z 2 C1Z C0 0
The parameters and are fixed
numbers, but varies in the various EOS
formulations. where the constants C0, C1, and C2 are
given by a and b.
The constants a and b are defined for
pure components by the critical criteria: An EOS is extended to multi-component
mixtures by applying appropriate Mixing

p 2
p Rules to its parameters, and introducing
2 0 binary interaction coefficients (BIPs) to
v pc ,Tc ,Vc v pc ,Tc ,Vc improve the vapor-liquid equilibrium
In its simplest form, the constants a and (VLE).
b are only function of reduced- pressure
Continued
and temperature (pr=p/pc, Tr=T/Tc).

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Cubic Equation of State Models, cont.
With any cubic EOS, the typically
General 2-parameter cubic EOS poor liquid density predictions can
be greatly improved by Volume
RT a Translation, which should therefore
p always be used.
(v b) (v b b)(v b b)
The Vapor-Liquid Equilibrium (VLE )
The parameters and are common of a fluid system is determined by its
for all components, but are different Thermodynamic Properties, which
in the various EOS model can be derived analytically from any
formulations. cubic EOS.
Some of the most commonly used Viscosities are usually calculated
EOS models are: using correlations.
Van der Waals EOS
Soave-Redlich-Kwong EOS The EOS combined with material
Peng-Robinson EOS balance equation forms the basis for
two-phase flash calculations.

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Van der Waals Critical Criteria
General cubic EOS form

RT a
p
(v b) (v b b)(v b b)

Criteria to determine a and b

for single components:

p 2 p
2 0
v pc ,Tc ,Vc v pc ,Tc ,Vc

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 Volume Translation (Volume Shift)
General 2-parameter cubic EOS General 3-parameter cubic EOS

RT a RT a
p p
(v b) (v b b)(v b b) (v c b) (v c b b)(v c b b)

Problem: The prediction for v is For a given component, c is usually

usually quite accurate for gases
(when v is large), but can easily
be
expressed as sb, where s is a
dimensionless parameter less than 1
10% in error for liquids (when v is (typically between 0.2 and -0.2).
small).
Note that c can be a linear function of
Solution: Subtract a component and composition and an arbitrary function
temperature dependent molar volume of temperature without affecting any
correction, c, from v. equilibrium calculations (aside from
the phase densities).

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Multi-Component Properties Mixing Rules

RT a
p
(v c b) (v c b b)(v c b b)
Nc Nc
a (1 kij ) xi x j ai a j
i 1 j 1 N c the number of components
Nc ai a for component i
b xi bi bi b for component i
i 1
ci c for component i (usually expressed as si bi )
Nc
xi the mole fraction of component i
c xi ci
i 1
kij the binary interactio n parameter (BIP) for
component i with component j (or vice versa)

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Vapor-Liquid Equilibrium (VLE)
Thermodynamic Equilibrium occurs A components chemical potential is
when the systems Gibbs Free determined by depth, temperature
Energy is at its minimum. and fugacity.

Chemical Potential
For a multi-component, multi-phase
system, the Gibbs Free Energy is the
mole-weighted sum of the Chemical
ki 0 RT ln f ki Migh
Potentials of all components in all
phases At uniform depth, equilibrium occurs
only if the fugacity of any given
Gibbs Free Energy component is the same in all
phases.

G
Np Nc
nkiki
k1 i1
Continued

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Vapor-Liquid Equilibrium (VLE), cont.
Within a given phase, a components The fugacities can easily be
fugacity is its Partial Pressure calculated by the EOS, and are given
multiplied by a Fugacity Coefficient, by the Z-factor, and the particular
which is given by the relationships EOS constants A and B
between temperature, pressure,
volume and composition
Therefore, an EOS can determine
Fugacity the multi-phase thermodynamic
equilibrium of a multi-component
f ki ki xki p isothermal system, as well as the
PVT behavior of any given
phase.
1 p RT
ln ki
RT
n V dV ln Z
Vk ki

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Fugacities for Different EOS Models
Peng-Robinson

Soave-Redlich-Kwong

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Lorentz-Bray-Clark Viscosity Calculations

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Two-Phase Flash Calculations
Simplified Algorithm:
Problem Definition
1. Estimate initial K-Values.

? Vapor
2. Calculate equilibrium phase
compositions xi and yi , by
Fluid Mixture solving Rachford-Rice material
Liquid balance.

3. Calculate Z-factors and fugacities

Given an overall fluid composition at for each phase using, the EOS
given pressure & temperature: model.
Determine relative amount of 4. Check equilibrium constraint:
equilibrium oil and gas.
a) Stop if convergence is reached
Determine equilibrium oil and
gas compositions. b) If convergence is not reached,
update K-values and re-do
step 2-3

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Estimating K-Values
Wilsons K-Value Equation:

Can be used for initial estimate for the two-phase flash.

Not accurate for high pressures.
Many iterations might be needed before convergence, and potentially
the two-phase flash might even converge to a false solution.
Simulation models use estimated K-values based on a converged
flash of the same liquid at related temperature and pressures, or K-
value estimate from a stability-test.

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Rachford-Rice Material Balance
Material Balance

(1) (3)

(2) (4)

Rachford-Rice Equation

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Solving Rachford-Rice Equation

With composition, zi, and K-values,

Ki, known, the only unknown is Fv
(vapor mole fraction.)
The only physical solution for Fv lies
in the region given by:

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Solving Rachford-Rice Equation, cont.

The Rachford-Rice equation is usually solved for Fv using a Newton

Raphson solution algorithm
After solving for Fv, the phase compositions are calculated from the
material-balance equations

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Two-Phase Equilibrium
Thermodynamic Equilibrium Updating K-values

Vapor yi If convergence is not reached,

Ki=yi/xi the K-values must be updated
Liquid xi by successive substitution

The chemical potential of each

component in each phase are equal

Convergence criteria:

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Stability Analysis
One of the most difficult aspects
Problem Definition of VLE calculations is to
? determine whether a fluid is
Single
phase stable at given conditions, or if it
is unstable and will split into
? P1 several phases.
Fluid
Mixture P2 Traditionally this questions has
been solved by conducting a two-
? P1 phase flash or saturation
P2 pressure calculation. However
P3 this approach is slow and not
always reliable.
Given an overall fluid composition, More robust approaches are
pressure and temperature: based on Gibbs Tangent Plane
Will the fluid mixture split into Criteria.
two (or more) phases?

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Stability Analysis - Gibbs Tangent Plane Criteria
The thermodynamic equilibrium of a
fluid is determined by the condition Problem formulation:
at which the Gibbs energy is at its
minimum for all possible Is Gz < Gmix for all possible phase
combination of phases and combinations?
component distributions.

Gibbs energy, homogeneous phase: For a binary mixture the tangent-

N plane criterion can be interpreted
Gz n (ni i ) z graphically:
i 1

Gibbs energy, mixture (two-phase): Michelsen has proposed a fast and

robust algorithm based on the
N
Gmix n [ Fv yi (1 Fv ) xi ] i
tangent plane criterion (Michelsens
stability test).
i 1

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Graphical Stability Analysis (from Baker et. al)

False solution

Two-phase V-L1 Three-phase V-L1-L2 Two-phase V-L2, L1-L2

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Michelsens Stability Test Algorithm
The method is based on detection of Simplified Algorithm:
possible second phase
compositions with Gibbs energy 1. Calculate mixture fugacities fgi
tangent planes parallel to the (with multiple Z-roots, select the
mixture composition. solution with the lowest g).
Conducts two separate tests; one 2. Estimate initial K-values (Wilson).
assuming the second phase is
vapor-like, and the other assuming a 3. Calculate second phase mole
liquid-like second phase. numbers:

Michelsen shows that the criteria for

a parallel tangent plane is given by:

f zi 4. Calculate sum of mole numbers:

Const.
f yi

Course in Advanced Fluid Phase Behavior. Pera A/S

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Michelsens Stability Test Algorithm, cont.
5. Normalize mole numbers to get 8. Check for convergence:
second-phase compositions:

9. If convergence not achieved,

update K-values:
6. Calculate second-phase fugacities
using the EOS model.

10. Check for trivial solution:

7. Calculate fugacity correction
factors for updating the K-values:

11. If trivial solution not indicated, go

to step 3 for another iteration.

Interpretation of results

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Michelsens Stability Test - Interpretation

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Saturation Pressure Calculations
Problem Definition
A simple method for determining
the saturation pressure is to do a
iterative search in pressure until
the vapor fraction Fv=0 (bubble-
point) or Fv=1 (dew-point). This
Liquid Psat = ? Gas method however is slow!

A faster approach is to apply the

stability test to determine the
Given an overall fluid composition at saturation pressure.
given temperature:
Determine pressure where the Algorithm
mixture is in equilibrium with an
infinitesimal amount of the
incipient phase.

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Saturation Pressure Algorithm
In terms of stability analysis, finding Simplified Algorithm:
a saturation pressure corresponds
to finding a second-phase with a 1. Guess saturation type: bubble-
tangent plane equal to the mixture point or dew-point (guess will not
tangent plane (zero distance affect pressure convergence, only
between them). the final K-values).

This corresponds to the sum 2. Guess starting pressure, p*

incipient phase mole numbers equal
3. Perform Michelsens stability test
to unity:
at p*
a) If a stable solution is found, p*
represent the upper bound.
Return to step-1 and guess a
where
lower pressure.
b) If an unstable solution is
found, this represents the
lower bound for the upper
curve of the phase envelope.

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Saturation Pressure Algorithm, cont.
4. Use K-values from stability test to 6. Update incipient-phase mole
calculate incipient-phase mole numbers using fugacity correction
numbers (if multiple-solutions factors:
where found, use the one with the
biggest mole number sum):

7. Update saturation pressure

5. Calculate incipient-phase
fugacities using the EOS model,
and fugacity-ratio correction
factors:

Course in Advanced Fluid Phase Behavior. Pera A/S

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Saturation Pressure Algorithm, cont.
7. (cont.) If searching for an upper 9. Check for trivial solution using:
saturation pressure, the new
estimate must be higher than p*,
otherwise use a higher estimate of
p* and go to step-1.
8. Check for convergence, the 10. (a) If convergence is not achieved,
following two criteria is suggested go to step-4. (b) If convergence is
by Zick: achieved, determine saturation
type by comparing mole fraction
of the heaviest components in the
mixture and incipient phase. (More
heavy components in incipient
phase indicates bubble-point, less
indicates dew-point).

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PVT Simulators - Introduction

Equation of State Calculations

Input Output
Component description Equilibrium calculations
(critical properties) PVT (phase split & compositions)
Fluid composition Simulator Fluid PVT properties (e.g.
Thermodynamic density, viscosity, etc.)
conditions (p, T)

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PVT Simulators - Introduction
Generation of Fluid Characterizations
Input
Component description
(critical properties)
Result
Fluid compositions
EOS characterization
PVT Measurements:
model (compositional
DLE PVT model).
CCE
CVD
Simulator Black oil PVT models
SEP (black oil tables).
VISCOSITY

Tuning (Regression)
Updated component properties.
Modified compositions.

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PhazeComp State of the Art, by Zick Technologies

Building and tuning multiple EOS fluid characterizations

simultaneously.
Manipulating fluid compositions.
Simulating user-defined experiments.
Matching user-defined data.
Predicting MMPs and MMEs.
Detecting three-phase equilibria.
Gravitational segregation experiments.
User-defined process calculations.
Black-oil table generation.

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The PhazeComp Approach

Virtual phase behavior laboratory.

User-programmed sequence of events.
Results from any calculation may be carried over to any other
calculation.
Almost any parameter or independent variable can be modified to
improve the predictions of experimental data.

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PhazeComp Typical Sequence of Events

Build a fluid characterization.

Define regression variables.
Assign temperatures, pressures, and any number of fluid
compositions.
Perform calculations and experiments.
Repeat the above steps as necessary.
Cycle through instructions, regressing on variables to optimize
predictions.

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PhazeComp Building Characterizations

Input tables of components and their non-default properties.

Initialize certain missing properties from a base characterization, a
component library, and/or a Gamma distribution.
Apply regression variables to properties.
Apply defaults and correlations to define any remaining undefined
properties.

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PhazeComp Regression Variables

Defined by name, along with initial and optional bounding values.

May be used to Multiply, Divide, Increase, Decrease, or Replace any
parameter or independent variable, in any specified sequence.

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PhazeComp Temperatures and Pressures

Specify manually.
Use, store, and/or restore previously calculated values.
Modify by constants or variables.

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PhazeComp Mixing Fluids

By mole, mass, or tankful.

Individual components.
Previously defined fluids (including those resulting from prior
calculations).
Gamma fitting and splitting.
Convert from other characterizations.
Modify by constants or variables.

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PhazeComp Basic Calculations

Two-phase (and negative) flashes.

Saturation pressures (upper and lower).
Vapor and pseudo-vapor pressures.
Convergence pressures.
Three-phase detection.
Two- and three-phase boundaries in temperature, pressure and
composition.

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PhazeComp Basic Experiments

Nearly any user-defined single-cell PVT experiment, including, but

not limited to: CCEs, DLEs, CVDs, Separator Tests, Multicontact
Vaporization and Swelling.

Hundreds of predefined and user-definable quantities can be

calculated and compared with experimental data.

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PhazeComp Specialty Experiments

Rigorous MMP and MME experiments.

Gravitational segregation experiments.
User-defined process calculations.
Black-oil table generation.

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PhazeComp User Interaction
PhzGUI.xls
2004-05-04

PERA
PhzGUi MS Excel
Create Launch
Plot Phz Results
Project PhazeComp

Generate PVT & Convert Between Plot

CNV Tables Different Formats Black Oil Tables

Pre & Post Processor For PhazeComp

(c) Copyright Pera a/s, 2004

Input File (Ascii) Result File (Ascii)

-Characterization -Sim results
-Compositions -EOS properties
-Experiments
PhazeComp -PVT properties
etc.

*.phz PhazeComp.exe *.out

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Exercise-3-1
Comp Mole frac
N2 0.0016
CO2 0.0091
C1 0.3648
Vapor C2 0.0967
C3 0.0695
Liquid I-C4 0.0144
N-C4 0.0393
I-C5 0.0144
Separator Conditions
Tsep Psep
N-C5 0.0141
Fluid Mixture C6 0.0432
F Psia
50 100 C7C10 0.1113
C11C15 0.0867
C16C22 0.0652
C23C30 0.0322
C30P 0.0374

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