Heriot-Watt University

DEPARTMENT OF PETROLEUM ENGINEERING

Equilibrium Ratio Prediction and

Calculation
Adrian C Todd

Introduction

Previous section we introduced the concept of

vapour-liquid equilibrium and its application in
predicting multicomponent behaviour with
respect to reservoirs.
In this section we will review the methods
used to determine K values, which are at the
foundation of VLE prediction methods.

Introduction

Compared to process facility calculations in

petroleum engineering detailed definition of
the composition of the fluid is not available.
Some of these undefined components may
have significant impact on VLE behaviour.
The fluid in a reservoir is unique from its
composition perspective.

Process versus reservoir compositional

modelling
Process Engineering
Reservoir Engineering

Calculations for a single

unit or a few in series.
Full compositional data
is available.
Calculations to predict
detailed compositional
outcome.

Calculations part of a multigrid block simulation. Hundred

or thousand of process units.
Limited compositional data.
Calculations to predict phase
volumes and physical
properties.

Petroleum Engineering Vapour Liquid

Equilibrium Challenge

Prediction of properties based on limited data

Applicable to multi-component mixtures

Accurate at predicting thermodynamic and volumetric

properties over a wide range of pressures and
temperatures and around and beyond critical point.
Be able to use pure component or binary mixture data
which is available from literature or generated.

Importance of Critical Point

Critical point is unique condition where liquid and

vapour phases are defined.
Has therefore theoretical as well as practical
significance.
In hydrocarbon processing knowledge of critical
condition important since many of operations are
near to the critical condition.
Behaviour near the critical point difficult test of
prediction methods.

Equilibrium Ratio, K

Empirical methods

Based on Thermodynamic principles

Equilibrium Ratio, K

A range of approaches
Black Oil System.
Two components, stock tank oil & solution
gas.

Experimental Data through K values.

Methods based on Equations of State

Experimental Data through K values

In a reservoir the
distribution of
components is not just a
function of T & P but
also influenced by
composition.
Reservoir fluids are
unique in composition.
No one has tested this
fluid before!!

Compositional Model
Reservoir fluid
Gas at surface conditions

Oil at surface conditions

Distribution of
compounds a
function of
pressure,
temperature and
composition

Empirical K values

Kj

yj
xj

Oil industry has relied on experimentally determined K values where

K is plotted versus pressure for a constant temperature.
The K values are generated from specific compositions.
The challenge is to determine which K values are appropriate to our
specific mixture.

At high pressure the K values are a function of T, P and composition.

The compositional influence is of great significance.

Pure component K values from one mixrure cannot be accurately

applied to another

Empirical K values

The K values converge to unity at different pressures.

This is called the convergence pressure

Empirical K values-Convergence pressure

The K values converge to unity at different

pressures.

This is called the convergence pressure

K values at particular P&T are different.

Convergence pressure is a measure of the

composition of the mixture.

Empirical K values-Convergence
pressure
K Value
for a binary system

Empirical K values-Convergence
pressure
K Value for a light oil at 200oF

Empirical K values-Convergence
pressure

Comprehensive set of K value data provided

by NGPSA
Presented as a function of convergence
pressure.
Challenge is to select convergence pressure
for new fluid.

Empirical K
values-NGPSA

Calculating Convergence Pressure

How do we select convergence pressure which is

applicable to our fluid ?
Trial and error method.
Procedure is to convert the mixture into an equivalent two
component mixture, usually based on methane and a
heavier component.
Heavy component selected according to the composition of
the non methane components and the weight fraction
weighted critical properties.

Calculating Convergence Pressure Procedure

Step 1 - Assume liquid composition

Step 2 - Identify the lightest component > 0.1mole%.

Step 3 - Calculate weight average critical properties to identify an equivalent

component to define the binary.
Step 4 - Trace the critical locus of the binary.
Step 5 - Read the convergence pressure at the temperature of the desired flash
calculations.
Step 6 - Using K values for indicated convergence pressure carry out VLE, flash
calculations to generate new liquid composition.
Step 7 Repeat steps 2 to 6 until assumed calculated convergence pressure is the
same as calculated.

Convergence pressure for hydrocarbons

Convergence pressure for various oils.

Convergence Pressure Procedure Example

The gas-liquid
equilibrium of a high
shrinkage oil has been
calculated.
The composition of the
liquid formed at 75oF
and 100psia is given.
A convergence pressure
of 2000psia was used.
What value of the
convergence pressure
should be used

Convergence Pressure Procedure Example

Composition of the liquid expressed as weight fraction

Convergence Pressure Procedure Example

Weight fraction excluding methane and calculated weight
average critical properties

Equation of State Based Equilibrium

Calculations

Equations of state can be used for the following purposes.

Representing PVT data to assist smoothing and improving
interpolations
Prediction of vapour-liquid equilibria of mixtures.
Prediction of gas phase properties of pure fluids and their
mixtures using minimum experimental data

Most favoured EOS

Peng Robinson & Soave, Redlich Kwong.

Equation of State Based Equilibrium

Calculations

It is important to note that these calculations

take place within each grid block in the finite
element based compositional reservoir
simulator.
They use therefore considerable computer
load.

Equation of State Based Equilibrium

Calculations
- Procedure
Determine
K values
using quick method. e.g.Wilson equation

Determine phase volumes etc using VLE equations.

Solve cubic EOS written in terms of Z.

Three roots lowest -liquid highest -vapour.

Calculate fugacity coefficient for vapour & liquid

Calculate Kj= ratio of fugacity coeff. in liquid/ fugacity coeff. in

liquid.
Iterate till convergence on Kjs

Equation of State
Based Equilibrium
Calculations Flowscheme

Danesh

Determination of Phase behaviour within Field

Calculations

Compositional Models
Black Oil Model

Empirical
correlations a
function of (API
Gravities, (P&T)

Flash Calculations for each

component.
K values either empirical or EOS
based.
Heavy on computing needs.
Tendency to reduce components by
defining a limited number of
pseudocomponents, say 4 or 5.