NED University of Engineering & Technology

Department of Petroleum Engineering

Workshop
on
Hydrocarbon Phase Behavior
and
PVT Analysis
July 14 -16, 2011

NED University of Engineering & Technology

Department of Petroleum Engineering

PART-1
Equation of State Fundamentals

Underlying Principles & Development

NED University of Engineering & Technology

Department of Petroleum Engineering

Need of a PVT model

Understand fluid properties at
reservoir, well & surface conditions
Predict changes under various
pressure-temperature constraints
at reservoir, well & surface facilities
Design production & development
strategies (Surface & Sub-surface)
Key is to get representative fluid
samples
Conduct relevant lab experiments
Develop predictive PVT models
over the entire range of P & T (EoS
based) which requires simulation of
PVT lab experiments (Application
of EoS with some modifications &
fine tuning)

f(P,T,zi)

NED University of Engineering & Technology

Department of Petroleum Engineering
A complete PVT model has two components, EoS model and
Viscosity model
An EoS is a continuous mathematical function describing
phase & volumetric behavior of fluid having empirical or semiempirical basis
or
Simply stated, EoS is a mathematical model that relates
pressure to volume and temperature
Generally speaking, most widely used EoS in petroleum
industry are variations of the original vdW EoS

NED University of Engineering & Technology

Department of Petroleum Engineering

Two or Three Parameter Cubic EoS

NED University of Engineering & Technology

Department of Petroleum Engineering

EoS has its basis in the Kinetic Molecular Theory (KMT) and for this reason it
had two inherent problems

The attractive forces between the molecules cause the impact pressure
or the measured pressure to be less than the internal pressure; therefore
a pressure correction was required the so called Attractive Parameter (a)
Pinternal = P + (n2 / V2)a --------------------------------- (i)

The actual free space available for compression is less than the total
volume by an amount of space occupied by the molecules; therefore a
volumetric correction was required the so called Hard-Sphere or Core
Volume Parameter (b)
V = V nb
--------------------------------- (ii)
The above corrections were applied to the ideal EoS or the KMT

Pinternal V = nRT
--------------------------------- (iii)
Resulting in the first Cubic EoS van der Waals EoS (1873 A.D.)

[ P + (1/V2)a] (V b) = RT --------------------------------- (iv)

NED University of Engineering & Technology

Department of Petroleum Engineering

The graphical form of PV relation for a pure component is

Most important observations for the critical isotherm are

[P/V]TC, PC = 0 The slope is zero at critical point ------------------- (v)

[2P/V2]TC, PC = 0 Point of inflexion lies at zero slope ------------------- (vi)

This means that First & Second derivatives may be evaluated to estimate
the Attractive & Hard-Sphere Parameters, a & b respectively

NED University of Engineering & Technology

Department of Petroleum Engineering

First & Second derivatives of van der Waals EoS (Eqn-iv)

[P/V]TC, PC = - RTC / (VC b)2 + 2a/V3C = 0 ------------------- (vii)
[2P/V2]TC, PC = 2RTC / (VC b)3 + 6a/V4C = 0 ------------------- (viii)

The simultaneous solution yields following relations for a & b parameters

a = (27/64) (RTC )2 / PC = (8/9) RTCVC ------------------- (ix)
------------------- (x)
b = (1/8) RTC / PC = (1/3)VC

Upon back substitution in (Eqniv) original van der Waals EoS is formed
[ P + (1/V2)a] (V b) = RT
--------------------- (iv)
V3 - [b + (RT/P)] V2 + (a/P)V) (ab/P) = 0 --------------------- (xi)

The original vdW EoS has Two Parameters, i.e. a & b, and Volume in expanded form
appears in first, second & third powers, hence the name Two Parameter Cubic EoS

NED University of Engineering & Technology

Department of Petroleum Engineering

Important conclusions of vdW EoS

2P cubic EoS
Application of 2nd Derivative Condition (Eqn-vi) and using a & b parameters from
(Eqn-ix & x)
PC VC = (3/8) RTC This implies that regardless of the type of component there exists a
Universal Critical Compressibility Factor ZC = 0.375

Correction terms a & b are

a = a (RTC )2 / PC
b = b RTC / PC
Magic Numbers

Where a & b are (27/64) & (1/8) respectively for vdW EoS each EoS has
distinct set of a & b

Limitations of vdW EoS

Experimental studies have shown that ZC = (0.23, 0.31) & ZC = 0.2 < C7+ to C1 < 0.29

Very Important

Experimental studies have shown that b = (0.24, 0.28)

Qualitatively vdW EoS is perfect but quantitatively it is not accurate enough to be used for
design purposes (Both volume & density)

NED University of Engineering & Technology

Department of Petroleum Engineering

Redlich & Kwong EoS (1949), first major modification to vdW EoS
The Attractive Parameter, a, was made function of Temperature
a(T) = aC(T)
and
(T) = Tr-1/2
----------------------- (xii)
P = [RT/ (V b) ] - [a/ V(V + b) ]
----------------------- (xiii)

Important Features of RK EoS

2P Cubic EoS
ZC = 0.333,
Correction terms a & b are
aC = a (RTC )2 / PC,
b = b RTC / PC

Where a & b are (0.42748) &

(0.08664) for RK EoS

Strengths & Limitations of RK EoS

Simple in formulation & reasonable for predictions

Good predictions at low densities & reliable for higher in the supercritical region
RK EoS ZC = 0.333 is reasonable for lighter but unsatisfactory for heavier components
since ZC ranges from 0.29 for C1 to <0.2 for C7+ and for this reason predicted liquid
volumes & densities are usually poor
Lacks volumetric behavior description around critical point

NED University of Engineering & Technology

Department of Petroleum Engineering

Soaves Modification to RK EoS (1972)

Introduced additional functionality into parameter by making it a function of both
Acentric Factor & Reduced Temperature, thus improving VLE predictions of RK
EoS
= (,Tr)
and 1/2 = 1 + m()(1 - Tr-1/2)
----------------------- (xiv)
m() = 0.480 + 1.574 0.1762
----------------------- (xv)

Important Features of SRK EoS (Same as RK)

2P cubic EoS
ZC = 0.333,
Correction terms a & b are
aC = a (RTC )2 / PC,
Where a & b are (0.42748) &
b = b RTC / PC
(0.08664) for RK EoS

Strengths & Limitations of RK EoS

Simple in formulation & reasonably accurate for predictions

Improved predictions in vapour phase
SRK EoS grossly overestimates liquid densities & under estimates liquid volumes
Lacks volumetric behavior description around critical point

NED University of Engineering & Technology

Department of Petroleum Engineering

Peng & Robinson EoS (1976)

Modified form of the original vdW EoS
P = [RT/ (V b) ] - [a/ {V(V+b) +b(V - b)} ]
----------------------- (xvi)
or
P = [RT/ (V b) ] - [a/ {(V+m1b)*(V + m2b)} ]
----------------------- (xv)
Where, m1 = 2 + 2 & m2 = 2 - 2
Important Features of RK EoS
2P Cubic EoS
ZC = 0.307
Correction terms a & b are
aC = a (RTC )2 / PC,
Where a & b are (0.457235) &
b = b RTC / PC
(0.077796) for RK EoS
Strengths & Limitations of PR EoS

Simple in formulation & reasonable for predictions

Largest improvement in PR is a lower Universal Z C = 0.307, relatively close to 0.29 for
heavier HC
PR EoS liquid density & volumetric predictions are much improved
Lacks volumetric behavior description around critical point

NED University of Engineering & Technology

Department of Petroleum Engineering

EoS Comparison for vdW, RK, SRK & PR

Universal Gas Compressibility Factor Z C = 0.29 for C1 to <0.2 for C 7+

NED University of Engineering & Technology

Department of Petroleum Engineering

There are a few requirements for an acceptable EoS

Must be a continuous function of volume
Volumetric representation in the entire range (i.e. liquid & gas phases)
Unfortunately none of the EoS discussed produce satisfactory results in terms of volumetric
behavior around the critical point
Martin (1979), Peneluox et al (1982) and Jhaveri & Youngren (1988) introduced the concept
of Volumetric Translation which resolved this problem (3P Cubic EoS)
Simple mathematical form with volume translation equation

VL VL

EOS

xi ci
i 1

VV VV

EOS

yi ci
i 1

ci V EoS ( PST , TST ) V Obs ( PST , TST )

Peneloux et al show that the multi-component is EoS unaltered by introducing the

correction term as mole fraction average or it may be simply thought of as mole fraction
weighted volume correction on component basis
Finally the Translation Factor is defined as si = ci / bi

NED University of Engineering & Technology

Department of Petroleum Engineering

Considerations for pure substance to mixtures (Single & Multi Component EoS)
Daltons Law of Partial Pressure
The total pressure exerted by a mixture of gas is equal to the sum of pressures exerted by its
components
PTotal = PA + PB + PC +
PTotal = nART/V + nBRT/V + nCRT/V + = (RT/V) (nA + nB + nC + ) = (ni) (RT/V)
Amagats Law of Partial Volume
The total volume occupied by a gas mixture is equal to the sum of the volumes that the pure
components would occupy at the same P & T
VTotal = VA + VB + VC +
VTotal = nART/P + nBRT/P + nCRT/P + = (RT/P) (nA + nB + nC + ) = (ni) (RT/P)
Law of Corresponding States
Simply stated, Substances behave alike at the same reduced states. This means as long as
two gases are at same reduced state they behave similarly regardless of the constituent
components
PR = P/PC , TR = T/TC & VR = V/VC
Kays Mixing Rule
It is the simplest of all pseudoization techniques allowing estimation of aggregate mixture
properties using mole fractions as weighting factors for grouping
Pc,m = xiPci , Tc,m = xiTci , MW m = xiMW i , etc.
More sophisticated rules were later proposed by Hong (1982), Mehra et al (1982), Whitson
(1983), Gonzalez et al (1986) etc. (Imp.: These are all empirical)

The above rules are employed in constituting an EoS for mixture from individual component basis

NED University of Engineering & Technology

Department of Petroleum Engineering

PART-2

EoS Model Guide

NED University of Engineering & Technology

Department of Petroleum Engineering

No unique characterization exists for a

reservoir fluid, therefore it is important
to determine the quality of
characterization by comparing the EoS
based predictions of the fluid behavior
against experimental or measured data
Key is to get representative fluid
samples
Conduct relevant lab experiments
Develop predictive PVT models
over the entire range of P & T (EoS
based) which requires simulation of
PVT lab experiments (Application
of EoS with some modifications &
fine tuning)

f(P,T,zi)

NED University of Engineering & Technology

Department of Petroleum Engineering

Development of predictive PVT models (Fluid Characterization)

step by step approach

Essential PVT lab data

QC PVT lab data
Build experimental data base
Define pseudo components (C7+ Characterization, Splitting)

Estimate/Calculate PVT properties using EoS

Match estimated PVT data with lab data (Regression)
Fine tune and re-group pseudo components (Simulation, Regrouping)
Predict PVT properties

f(P,T,zi)

NED University of Engineering & Technology

Department of Petroleum Engineering

Essential PVT lab data

Oil Reservoir
Full stream composition of hydrocarbon up to C 7+
Constant composition expansion (CCE, CME or CMS) for P B & o @ PB
Multistage flash separation for GOR & o, stock tank @ various PSEP & TSEP
Viscosity @ TRes & P = (Pi, P< PB)

Gas-Condensate & Volatile Oil Reservoirs

As for oil reservoir above
Constant volume depletion (CVD or DS) for liquid dropout curve

f(P,T,zi)

NED University of Engineering & Technology

Department of Petroleum Engineering

Defining Pseudo Components (C7+ Characterization) (Liquid Drop Out & Envelop)
TBP data is needed which is not available most of the time than we use any of the
following methods for the purpose, which must satisfy the following constraint equations

MWn z n MWC7

z C7
z n zc
MWn z n MWC zC

SG
Pedersen
et al (1989) correlation
for C7+ characterization which basically
relies
onSG
theC7
n 7
n 7
n 7
n

principle of Exponential Molar Distribution

Aconstraints
BMWn
Where A & B are required to satisfy the aforementioned
(SRK EoS)
n
Whitson (1983) proposed the use of a three parameter Gama Function to describe molar
distribution with in C7+ fraction (PR EoS)

z e

zn

z C7

( )
Where, = (92, 14n-6),

y
j 0

j y
n 1
n 1

j
n

e yn

( j 1)and
yn

MW
n

MW
C7

NED University of Engineering & Technology

Department of Petroleum Engineering

Defining Pseudo Components (C7+ Characterization)

NED University of Engineering & Technology

Department of Petroleum Engineering

Once the pseudo components are defined any suitable mixing rule may be
used to convert the component properties to mixtures properties
This will be the basis of initial prediction of the EoS
Now the initial results may be regressed since
PD or PB may be off by 10%
Phase densities may be off by 5% or even higher
Compositions by several mole percent

Simple rules for regression

Vary properties of poorly defined components, i.e. plus fractions &
associated to plus fractions
Choose as few properties as possible RMS or SSQ
Ensure monotonicity of variables

NED University of Engineering & Technology

Department of Petroleum Engineering

Fine Tuning the EoS

NED University of Engineering & Technology

Department of Petroleum Engineering

Once the fine tuning is complete, it is recommended to re-group the

pseudo components and re-run experimental simulations

Results of experimental simulations should then be compared with single

pseudo, i.e. C7+ or re-grouped, with the multi pseudo component original
fine tune model to reduce the number of components

Comparative results may be extracted and finally the complete predictions

can be obtained as Black-Oil or Compositional model

The information may then be utilized to develop inputs to simulation

models or extracting basic parameters to be used in well performance
models etc

NED University of Engineering & Technology

Department of Petroleum Engineering

PART-3

EoS Model Sample

NED University of Engineering & Technology

Department of Petroleum Engineering

Separator Samples were Collected in Well-01 During

DST in Sand Reservoir (CGR 96.41)
Compositional Analysis up to C7+
Constant Composition Expansion
Constant Volume Depletion
Saturation Pressure ~5191psia

NED University of Engineering & Technology

Department of Petroleum Engineering

Recombined well stream sample composition

Component

Mole Fraction

N2

0.0671

CO2

0.0286

C1

0.7322

C2

0.0471

C3

0.0243

iC4

0.0073

nC4

0.0129

iC5

0.0069

nC5

0.0071

C6

0.0110

C7+

0.0555

Saturation pressure determined in the

lab was 5176psi which is same as
initial pressure

C7+ molecular weight was ~129

NED University of Engineering & Technology

Department of Petroleum Engineering

A 3P-PR EoS with LBC-Correlation was Used to Match Lab Data

STEP-1
Properties Adjusted for Initial Match:
BIP b/w C1 & C7+ (0.0499 to 0.224) (Chauh-Prausnitz)
MW of C7+ Fraction (92.28 to 215)
Re-Grouping of C7 to C12+ to C7+ Only
STEP-2
Regression Variables for Fine Tuning:
Critical Properties and Accentric Factor for C7+
Omega A & Omega B for C7+ Fractions

NED University of Engineering & Technology

Department of Petroleum Engineering

NED University of Engineering & Technology

Department of Petroleum Engineering

NED University of Engineering & Technology

Department of Petroleum Engineering

NED University of Engineering & Technology

Department of Petroleum Engineering

NED University of Engineering & Technology

Department of Petroleum Engineering