GS.06.

53139
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Guide for Fluid Characterization using

C7PLUS method in HYSYS
 GS.06.53139
RESTRICTED

Guide for Fluid Characterization using C7PLUS

method in HYSYS

by

E.M. Hendriks
H. Meijer

RESTRICTED

This document is made available subject to the condition that the recipient will neither use nor disclose the contents except as agreed in
writing with the copyright owner. Copyright is vested in Shell Global Solutions International B.V., The Hague.

© Shell Global Solutions International B.V., 2006. All rights reserved.

Neither the whole nor any part of this document may be reproduced or distributed in any form or by any means (electronic, mechanical,
reprographic, recording or otherwise) without the prior written consent of the copyright owner.

Shell Global Solutions is a trading style used by a network of technology companies of the Royal Dutch/Shell Group.
GS.06.53139 3 RESTRICTED

Table of Contents

1. Introduction 5
2. Hydrocarbon Fluid Behaviour 6
2.1 Phase behaviour 6
2.2 Types of fluids 8
2.3 The effect of component distribution on phase behaviour 9
3. Experimental Data 10
3.1 Well stream composition. Analysis and recombination of separator samples. 10
3.2 Multi-stage separator tests. 10
3.3 Saturation points. 11
3.4 Constant composition expansion (CCE) 11
3.5 Differential liberation (DL) 11
3.6 Constant volume depletion (CVD) 12
4. Thermodynamic Model 13
4.1 Equations of state 13
4.2 Estimation of properties and model parameters of pseudo components 14
5. The Shell C7PLUS Procedure 16
5.1 Mode of operation 1. C7+ non-standard components (C7PLUS base procedure). 16
5.2 Mode of operation 2. C7+ standard components 17
5.3 Mode of operation 3. C7+ flexible grid components 18
5.4 Mode of operation 4. Single carbon number fraction correlation 18
6. Fluid Characterization 20
6.1 Step 1: Base composition and fluid type 20
6.2 Step 2: Inventory and selection of data 22
6.3 Step 3: Validation of the data 23
6.4 Step 4: Selection of thermodynamic method 24
6.4.1 Hysys methods 24
6.4.2 Shell methods (HYSPPTS). 25
6.5 Step 5: Simulation of the experimental data 26
6.6 Step 6: Base performance 29
6.7 Step 7. Sensitivities 30
6.8 Step 8. Tuning 31
7. Example Cases 34
7.1 Case-1 34
7.2 Case-2 36
8. Using C7PLUS in the HYSYS Process Simulation Program 40
References 44
Appendix A. Mathematical Description of the C7PLUS Procedure 45
A.1 Base procedure (operation modes 1, 2 and 3) 45
A.2 Mapping to grid: the standard components (operation mode 2 ) 50
A.3 Mapping to flexible grid of components (operation mode 3) 51
A.4 Single hydrocarbon number fraction method: mathematical description (operation
mode 4). 54
Appendix B. Sensitivity of simulated data to the C7PLUS parameters 56
B.1 Gases - Typical Liquid Content 0 - 50 m3/106 Sm3 (10 bbl/MMSCF) 56
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B.2 Gas/Condensates - Typical Liquid Content 50 - 1500 m3/106m3 (10 – 300

bbl/MMSCF) 57
B.3 Oils - Typical Liquid Content 1500+ m3/106m3 or GOR < 600 m3/m3 57
Appendix C. Figures 58
Appendix D. Phase Behaviour of Systems Showing Liquid-Liquid
Separation 72
Bibliographic Information 73
Report distribution 74
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1. Introduction
The starting point for any process design is a feed composition representative of the fluid
entering the particular processing facility. A typical well fluid may have a composition varying
over the field and over field life. A number of feed compositions are required to cover all potential
operating conditions and an analysis of the sensitivity of the proposed system to variations in
composition.
It is essential that the description of the feed stream entered into the computer model will provide
an accurate representation of the actual behaviour and properties of the fluid. Failure to do so
could result in over or under-design of the processing facilities and a subsequent requirement for
costly modifications, or in the case of optimisation studies, poor agreement with measured
operating data.
A well stream will in general contain a smaller or larger fraction of heavy hydrocarbon
components, for which the composition and properties cannot be measured in detail. That
fraction and/or these components must be represented by pseudo-components (called hypos in
HYSYS). The Shell C7PLUS procedure is a method through which these hypos can be
constructed that can be used for this purpose, based on limited input data.
The process of construction of a feed composition for a well fluid together with a thermodynamic
model that can be used in process simulation, based on experimental PVT-data is referred to as
fluid characterization . This process comprises
• the development of a component slate: library components and hypothetical components
(hypos). The C7PLUS procedure is used to generate hypos representing the heavy end
• the assignment of component amounts (for one or more feed streams)
• the selection of a thermodynamic model
• the derivation and tuning of model, component and C7PLUS parameters
• comparison of predicted and measured PVT-data
C7PLUS was originally released in 1988 as a stand alone computer program for characterisation
of the heavy fraction of hydrocarbon streams [1]. In the early 1990s the core program routines
were incorporated within the PRO/II process simulation program to allow semi automatic
characterisation using C7PLUS. In 1994 a revision of the original document came available
describing also its use within PRO/II [2]. Meanwhile, the C7PLUS procedure has been further
extended and moreover it is more often used in conjunction with the Hysys simulation program
This document provides an updated description of the C7PLUS procedure and guidelines for
carrying out characterizations using C7PLUS in particular for process engineering application
using the process simulation program Hysys
Note that throughout this guide, the heavy-end fraction of the hydrocarbon stream is generally
referred to as the C7+ fraction. In many cases, however, extended hydrocarbon analyses are
carried out resulting in heavier, residual fractions e.g. C8+ or C12+. The C7PLUS method is
equally suited to splitting and characterising these heavier fractions and this topic is covered in
the description of the method.
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2. Hydrocarbon Fluid Behaviour

In order to achieve an adequate characterization of a fluid --- which means an adequate
representation of its phase behaviour --- it is of some importance to understand what phase
behaviour actually is and what the relation is with the thermodynamic model used to predict it.

2.1 Phase behaviour

The state of a fluid at equilibrium is fully defined when its composition, pressure and temperature
are specified. The fluid may separate into a number of coexisting phases and the fluid
constituents will distribute between the phases. By phase behaviour of a fluid we mean the
dependence of the state of a fluid to composition, pressure and temperature.
For the purpose of fluid characterization we can ignore the presence of water and hence the
formation of a water-rich phase (liquid water, ice or gas hydrate). Further, we ignore the possible
formation of solids (like wax). The state of a fluid then involves:
• The number and type of phases e.g. V, L, VL, VL1L2,…
• The amount of the phases c.q. the fraction of the phase relative to the feed
• The composition of the phases
• The properties of the phases like density
For illustration purposes the phase behaviour in the binary mixture of ethane and n-octane of
a fixed overall composition is shown in the Figure 1. The behaviour of such a simple fluid is
qualitatively similar to a multi-component reservoir fluid.

120
phase boundary
critical point Dense Gas
100

80
Pressure [bar]

60 Liquid

40 Two-phase
region Gas
20

Vapour
0
-50 0 50 100 150 200
Temperature [C]

Figure 1: Phase behaviour of binary mixture of ethane and n-octane (90/10 mol/mol)
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The red curve represents the phase boundary where a phase (dis)appears:
• when a vapour phase (dis)appears, the curve is called a bubble-point curve
• when a liquid (dis)appears, the curve is called a dew-point curve; when liquid appears
after a pressure reduction then it is also called a retrograde dew-point curve.
Both curves often meet at a critical point where the compositions of two phases become identical
and hence their properties. Because of its shape, fluid phase boundary of hydrocarbon mixtures
is often called a phase envelope
Often the temperature maximum of the phase boundary curve is called maxcondentherm or
cricondentherm and the pressure maximum a maxcondenbar or cricondenbar. Note that these
points do not represent special states.
The phase envelope of the binary mixture of ethane and n-octane changes with the composition
as is illustrated in the Figure 2. In addition the location of the critical point shifts relative to the
cricondenbar.

120 Phase boundary critical points locus of critical points

100
90 70 mole% ethane

80
Pressure [bar]

50
60
100
30
40
10
0
20

0
-50 0 50 100 150 200 250 300
Temperature [C]

Figure 2: Phase behaviour of binary mixtures of ethane and n-octane

This common shape of the phase envelope of a hydrocarbon fluid changes when a second liquid
phase forms at lower temperatures. This is described in more detail in Appendix-D
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2.2 Types of fluids

The development of a field and also issues concerning the characterization depend on the base
type of fluid. Based on the relative amount of oil and gas produced (gas oil ratio, GOR), five
different types are defined and listed in Table 1.

Table 1: Different types of fluid

Dry gas Wet gas Retrograde Volatile oil Black oil

condensate

GOR [m3/m3] no liquid >2500 600-2500 300-600 <300

C7+ [mol%] < 0.7 0.7-4 4-12.5 12.5-20 >20

Type no liquid dew point dew point bubble point bubble point

The assignment of a fluid type to a given well stream depends also on operating conditions. In
Figure 3, the phase envelopes for different fluid types are drawn in relation to typical conditions
of reservoir and separator. A similar diagram taken from the previous guide [2] can be found in
Figure C-1 (in Appendix C) Note that retrograde condensate, gas condensate, retrograde gas
and retrograde gas condensate are just synonyms, which all refer to the same type of fluid.

Black oil Volatile oil Gas condensate Wet gas

Critical point Critical point Critical point Critical point
30000
Reservoir
25000
Pressure [kPa]

20000

15000

10000

5000
Separator
0
-200 -100 0 100 200 300 400 500
Temperature [degC]

Figure 3: Phase envelopes for the different types of well fluids

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2.3 The effect of component distribution on phase behaviour

For naturally-occurring hydrocarbons, three main categories of chemical species are normally
present:
Paraffins saturated chain compounds such as methane, ethane etc.
Naphthenes saturated, cyclic compounds such as cyclopentane, cyclohexane etc.
Aromatics unsaturated, cyclic compounds having a structure based on the benzene ring
such as toluene, naphthalene etc.
The types of chemical component present in a C7+ fraction have an equally dramatic effect on
the phase behaviour of the system as the actual amounts. This is clearly illustrated in Figure C-2
(in Appendix C) which, for binary 50/50 mixtures of methane and various compounds all having
a molecular weight of approximately 120, shows how the methane K-value (i.e. mol fraction of
methane in the vapour divided by the mol fraction of methane in the liquid when at equilibrium),
varies as a function of the heavy component specific gravity. Note the K-value at 50 bar and
25°C varies by a factor 3 between the methane/paraffinic binary (SG = 0.6) and the methane/di-
aromatic binary, (SG = 1.0). Translating these variations into more practical considerations, such
as separator GORs or calculated dew point or bubble conditions, the importance of correctly
identifying component type is clear.
Experimental measurements on various crudes and condensates have shown that there is
a close relationship between the distributions of chemical species. This is illustrated in
FigureC-3a (taken from research report AMGR.85.192 [4]), which shows the relationship
between molecular weight and relative density for various crudes. Figure C-4 translates these
density distributions into typical distributions of chemical species and shows that for increasing
molecular weight (and carbon number), the constituent components become increasingly
aromatic. This molecular weight/density relationship is fundamental to the calculational basis of
C7PLUS and is further described in Section 5.
Another important criterion in the make-up of heavy-end fractions is the concentration
distribution of the various components as a function of molecular weight. Examples of measured
data are given in FigureC-3b (taken from research report AMGR.85.192 [4]), which for five
crudes, shows a variation between exponential and left-skewed distributions, the latter having
peaks around C8.
From the foregoing, it is clear that component type and distribution are key factors in the
development of a realistic heavy-end breakdown. The methods employed by C7PLUS to
account for these characteristics are described in the Section 5.
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3. Experimental Data
The characterization of a well fluid has to be based on experimental data from a PVT-report,
which contain gas and liquid compositional analyses, separator tests and phase behaviour
experiments.
Contract well testing companies and PVT laboratories provide a variety of services for evaluating
the properties and phase behaviour of well fluids. The measurements undertaken during
a particular well test programme will be dictated by the type of the fluid in the reservoir and the
purpose for which the data is required e.g. simple well appraisal, process design etc. For the
purposes of fluid characterisation, certain base data are obviously required. Various other
laboratory measurements may then be used to tune the model so as to give an acceptable
match of predicted and measured data.
The complete list of recommended measurements and analyses are given elsewhere [3].

3.1 Well stream composition. Analysis and recombination of separator

samples.
During production tests, the well effluent is normally fed via a choke manifold to a test separator,
having separation conditions similar to the anticipated processing conditions. Liquid from the test
separator is then flashed down to atmospheric conditions in a tank - see FigureC-7
(in Appendix C).
Gas and liquid compositions are subsequently measured using techniques such as gas
chromatography (GLC) and distillation. Components higher up in the slate are normally grouped
by carbon number. For example, all components detected after n-C10 up to and including n-C11
will be designated C11 components. Only rarely are the molecular weight and specific gravity of
the pseudo components actually measured but are frequently estimated using standard
correlations.
Following analyses, the gas and liquid samples are physically recombined in a ratio
corresponding with the measured test separator gas oil ratio (GOR). This recombined well fluid
sample can then be used for various other PVT measurements.
The composition of the well fluid is obtained by mathematically recombining the measured gas
and liquid compositions in the ratio derived from the GOR as illustrated in FigureC-7
(in Appendix C).

3.2 Multi-stage separator tests.

Multi-stage separator tests are often carried out to obtain data required for the optimisation of
surface facilities. The first stage is usually at the saturation pressure corresponding to the
reservoir temperature. A series of flash separations is performed. The gas phase from each
separator stage is flashed to standard conditions. The liquid phase is let to a new separator in
which a new PT flash separation takes place, at a lower pressure. The last separator is at
atmospheric conditions. Principal quantities measured are gas oil ratio (GOR, volume of gas
from the actual stage at standard conditions divided by the volume of the oil from the last stage),
liquid densities and oil formation volume (the oil volume at the actual stage divided by the oil
volume from the last stage).
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3.3 Saturation points.

Saturation point data refer to bubble or dew-point data depending on the fluid-type.
A bubble point, which occurs for oil type systems, is a set of TP-conditions at which the first bit of
gas is formed from a liquid. Bubble point determinations are performed by transferring the
recombined well fluid sample to a PVT cell and conditioning the cell to the required bubble point
temperature. The bubble point is indicated by a sharp change in the measured pressure versus
volume relationship. The pressure corresponding with this transition point represents the bubble
point pressure at the cell temperature.
A (retrograde dew point) which occurs for condensate type systems, is a set of TP-conditions at
which the first bit of condensate is formed from the (dense) gas. Dew point determinations are
normally carried out in a PVT cell having a window in the cell wall. The cell is conditioned to the
required dew point temperature and the pressure varied until the presence of liquid is observed.
The measured pressure at this point represents the dew point at the cell temperature.

3.4 Constant composition expansion (CCE)

In a constant composition expansion (CCE) experiment, the phase behaviour of the fluid is
studied by charging a sample to a PVT-cell and changing the pressure. The reservoir fluid is
kept in a cell at constant temperature --- most often corresponding to the measured temperature
of the reservoir. The pressure is reduced in steps at constant temperature and the change in
volume and various other properties are measured.
At each pressure stage the following variables are measured:
• Relative volume. This is the system volume divided by the system volume at saturation
(bubble or dew point)
• Liquid volume (for condensate systems) or gas volume (for oil systems)
• Some special quantities, such as Y-factor, compressibility and compressibility factor, Z.
This experiment is also called constant mass expansion.

3.5 Differential liberation (DL)

This experiment is only carried out for oil mixtures and is also known as differential depletion or
differential vaporisation. The reservoir fluid is kept in a cell at the reservoir temperature. The
experiment is usually started at the saturation pressure (bubble point). The pressure is reduced
stepwise and all the liberated gas is displaced and flashed to standard conditions. This
procedure is repeated 6-10 times. The end point is measured at standard conditions.
At each pressure stage the following variables are measured:
• Oil formation volume factor, Bo, defined as the oil volume at the actual pressure divided
by the residual oil volume at standard conditions
• Solution gas/oil ratio, Rs, which is the total standard volume of gas liberated from the oil
in the stages to follow, divided by the residual oil volume. The volume of the liquid
condensing when flashing the gas to standard conditions is converted to an equivalent
gas volume.
• Gas formation volume factor defined as the volume of the gas at the actual conditions
divided by the volume of the same gas at standard conditions. The volume of the liquid
GS.06.53139 12 RESTRICTED

condensing when flashing the gas to standard conditions is converted to an equivalent

gas volume.
• Gas Gravity. Molecular weight of the gas divided by the molecular weight of atmospheric
air (=28.964).

3.6 Constant volume depletion (CVD)

This experiment is performed for gas condensates and volatile oils. The reservoir fluid is kept in
a cell at reservoir temperature and saturation point pressure. The pressure is reduced in steps,
and at each level as much gas is removed that the volume of the remaining gas and oil mixture
equals the saturation point volume.
At each pressure stage the following variables are measured:
• Volume of the liquid (% of the volume at the dew point)
• Percentage produced. Cumulative mole% of initial mixture removed
• Compressibility factor of the gas (z) .
• Viscosity. Viscosity of the gas in the cell
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4. Thermodynamic Model
A key element of the characterization is the representation of the experiments and the
reproduction of the results. Various types of phase equilibrium and physical property
calculations need to be performed. The essential element in this is the thermodynamic model.
Due to the relatively large pressures and pressure range encountered and phenomena such as
retrograde condensation, an equation of state is the method of choice.

4.1 Equations of state

In engineering calculations, almost exclusively cubic equations are used. They are called cubic
as the molar volume can be obtained by solving a third order polynomial equation, yielding either
one root (single phase) or three roots, two of which correspond to physically stable phases
(vapour and liquid). The reference state for both phases is the ideal gas.
The prototype is the Van der Waals equation, which in this context is of historic interest only.
A general two-parameter cubic equation of state can be stated as

RT a
p= + 2 Equation 1
v − b (v + ubv + wb 2 )

In this expression
• p is the pressure
• T is the temperature
• v is the molar volume
• a and b are parameters (depending on composition and possibly temperature)
• u and w are constants:
o u=0, w=0 produces the Van der Waals form (VdW)
o u=1, w=0 produces the Redlich-Kwong form (RK)
o u=2, w=-1 produces the Peng-Robinson form (PR)
From the equation of state, using generally valid mathematical identities, quantities such as the
chemical potential of each component can be computed and from that, the phase distributions in
equilibrium can be established.
The equation holds also for a pure component, in which case a and b are the pure component
parameters. Depending on the method, these are computed either from elementary component
properties (critical temperature, critical pressure and acentric factor) or by regressing
experimental data (component vapour pressure and densities).
The two parameters account for the deviation from ideal gas behaviour. Parameter a is related
(basically) to the attractive forces between molecules and parameter b to the repulsive forces.
They are referred to as energy parameter and volume parameter, respectively.
GS.06.53139 14 RESTRICTED

For mixtures, the equation of state parameters become functions of composition through the so-
called mixing rules. Prototype mixing rules are

bi + b j
a = ∑∑ ai a j (1 − kij ) xi x j b = ∑∑ (1 − mij )xi x j Equation 2
i j i j 2

which express the mixture parameter a and b in terms of the mole fractions x and the pure
components parameters (which now carry a subscript indicating the component). (For systems
containing a mixture of polar and non-polar components, more elaborated mixing rules may be
used).
Quantities kij and mij are called interaction parameters for the pair ij. They represent the
deviation from conformal behaviour. That means that for chemically very similar molecules (such
as pairs of hydrocarbons ) values should be small or zero ( kij <0.05), but for pairs of chemically
very different molecules (for example water-hydrocarbon) the value will be substantial ( kij of the
order 0.5). Nonzero values for mij are rare.

A positive value of kij the interaction parameter will in general increase the volatility of the
components in the mixture as compared to the pure component state, and also increase the
tendency to de-mix (liquid-liquid equilibrium).
Note that, although the phase equilibrium calculations are done with an equation of state, it is not
compulsory --- though possible --- to use that same equation to calculate physical properties
such as density and or enthalpy. In a typical calculation, the phase split is always determined in
a first step. The properties of the phases are calculated in a second step. This can be and is
often done with another method, to achieve higher accuracy at the expense of the loss of
complete thermodynamic consistency.

4.2 Estimation of properties and model parameters of pseudo components

Pseudo components introduced during the fluid characterization process are initially only defined
in terms of their base properties, i.e. MW (molecular weight) and SG (specific gravity). Several
other properties and model parameters are required however, before any calculation can be
carried out.
Hysys is equipped with property estimation methods for use in conjunction with all the
Hysys models. Hysppts uses a dedicated procedure, called Frachar [4] to generate the data for
the SMIRK and CPA models.
Frachar is applied to each pseudo-component separately. It consist of the following steps
• Estimate the normal boiling point TB of the component from the molecular weight and the
specific gravity using a correlation (Chueh)
• Estimate the critical temperature from the boiling point and the specific gravity using
a correlation (Twu)
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• Compute the molar volume VSTD at standard conditions from the molecular weight and the
density using the definition of density
• In an iterative cycle, determine the critical pressure and the acentric factor from the
requirement that the values of molar volume at standard conditions VSTD and the normal
boiling TB are reproduced with the equation of state
At this stage, the equation of state parameters are fixed, and the component can be used in
phase equilibrium calculations. A number of additional parameters are derived after this, mostly
from correlation, so that remaining properties --- for example transport properties --- can be
calculated.
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5. The Shell C7PLUS Procedure

The C7PLUS program uses a combination of measured properties for the C7+ fraction, together
with various empirical correlations to generate a heavy-end component distribution.
The C7PLUS characterization procedure in HYSYS has four different modes of operation, which
are described in the next four sections. Modes 1 and 2 correspond to the procedure as present
in previous versions of HYSYS and other programs and as documented in the previous guide
[2]. The procedure has been extended with two additional modes to better adapt it to the
possibilities that HYSYS offers and to allow more flexibility for matching the behaviour and
properties of fluids.
Detailed mathematical descriptions of the numerical procedures can be found in Appendix A

5.1 Mode of operation 1. C7+ non-standard components (C7PLUS base

procedure).
In this mode, the C7PLUS base procedure is applied. This procedure converts data for a heavy
fraction into
• a set hypothetical components (hypos, pseudo-components)
• a corresponding composition (amounts)
With other components (light ends) added --- this defines a model fluid to be used for
representing phase behaviour and properties of the (well) fluid in the simulation.
The properties of the hypos depend on the input data supplied. So in this mode of operation,
different components will be generated for different cases. Hence the term non-standard
components. The number of components can be set by the user.
The base procedure works on the following input data for the heavy fraction
• Primary input parameters
o Molecular weight MW of the heavy fraction (C7+ fraction)
o Specific gravity SG of the C7+ fraction
o Lowest component MW of the C7+ fraction
o Lowest component SG of the C7+ fraction
Note: In practice the values of the lowest component MW and SG are fixed for a specified type of Cn+ fraction,
e.g. C6+, C7+, C9+, C12+, but an option is available to adjust both values.

• Secondary input parameters (providing extra flexibility)

o Number of components in the C7+ fraction
o First distribution parameter - this parameter controls the shape of the
concentration versus molecular weight curve for the heavy component
breakdown. Acceptable values lie in the range 1.0 to 2.0 representing a transition
from exponential to left-skewed distributions respectively as shown in
Figures C-5a (in Appendix C).
Note: Measured data on crudes and gas condensates has shown that for those systems having a left-skewed
distribution, the peak normally occurs around C7/C8. Thus when characterising heavier fractions, such as C10+,
a value of 1.0 should be used

o Second distribution parameter - this parameter is used to adjust the shape of the
density distribution curve so as to vary the degree of aromaticity of the heavy
GS.06.53139 17 RESTRICTED

components. A range of values from 0.0 to 30.0 has been defined, 0.0
representing more paraffinic heavy components and 30.0 more aromatic
components. The effect of varying the value of this parameter is shown in
Figure C-5b (in Appendix C), which is a plot showing the molecular weight/density
distribution relationship introduced earlier in FigureC-4 (in Appendix-C).
Default values are available for all the variables except MW and SG. Initial values for these
parameters must be obtained from a PVT-report
A detailed mathematical description can be found in Appendix A1.
Step a)
Based on either user-specified or program default values of
C7+ average molecular weight, MW (allowable range 0.664 to 1.2)
First distribution parameter (allowable range 1.0 to 2.0)
Minimum mol weight for C7+ components
Number of components to be used in the distribution (allowable range 2 to 20)
the program calculates a concentration versus molecular weight distribution for the pseudo
components such that the average molecular weight of the C7+ fraction agrees with the
specified value. The shape of this distribution will be governed by the value of the first
distribution parameter. The spacing of the component molecular weights increases from the low
to the high molecular weight values. The component with the highest molecular weight is set to
contain 1 mol% of the total heavy fraction.
Step b)
Using the selected molecular weights of the pseudo components and their concentrations --- as
calculated in a) --- the program assigns density values to the individual components using
a typical relationship between molecular weight and density similar to those shown in FigureC-4
(in Appendix C). The distribution line is then adjusted such that the average specific gravity of
the C7+ fraction matches the specified input value. Note that the shape of this line is governed
by the value of the 2nd distribution parameter as illustrated in FigureC-5b (in Appendix C)

5.2 Mode of operation 2. C7+ standard components

In this mode, the C7PLUS base procedure is applied exactly as described before. The two steps
a) and b) are then followed by a third step, in which the hypos are replaced by a set of pre-
defined components --- called standard components --- with amounts derived from the
distribution obtained in the first step a). The amounts of the standards are obtained through
a mapping procedure, which leaves the overall molecular weight and density unchanged.
The purpose is to enable the user to characterise a number of different hydrocarbon streams
using the same components. This reduces the overall number of components required for the
process simulations involving several independently characterised hydrocarbon streams.
Where possible, these "standard" components are pure components whose properties are well
known. However, in order to cover the full range of component molecular weights and specific
gravities it has also been necessary to add some pseudo components. The term standard
component therefore only applies within the context of the C7PLUS procedure. The list of these
standard components used by C7PLUS is given in Appendix-A.
GS.06.53139 18 RESTRICTED

The number of standard components actually used in the output of the procedure varies, as
components that would receive a negligible (c.q. zero) amount through mapping are discarded.
The user can influence the number of standard components selected by varying the input value
of grid spacing. e.g. a grid spacing of 1 uses all the standard components while a value of 4 will
result in every 4th grid component being selected.
For technical reasons, this mode cannot be combined with using the HYSYS optimizer.
A detailed mathematical description can be found in Appendix A2.

5.3 Mode of operation 3. C7+ flexible grid components

In this mode, the C7PLUS base procedure is applied exactly as described for Mode-1. Also in
this case this is followed by a third step, in which the components are replaced by a set of fixed
components. As before, the reason for this is to allow for the possibility of characterizing different
fluids on the basis of a single set of components. However the fixed components are not pre-
defined in the program; the actual set can be changed by the user through the values of certain
input parameters.
The user can modify the grid used by changing various parameters:
1. Lowest grid mass
2. Highest grid mass
3. Number of mass values
4. Number of volumes per mass.
In the molar mass - molar volume plane, a maximum of four straight lines are defined on which
all grid components must lie.
All components receiving a mole fraction below a (user specified) cut off value are discarded. If
this value is set to zero, however, every grid components will appear on appear on output, even
if the corresponding mole fraction is zero. This is needed to allow optimisation in HYSYS, which
cannot operate with a varying number of components.
A detailed mathematical description can be found in Appendix A3.

5.4 Mode of operation 4. Single carbon number fraction correlation

This mode of operation is an alternate, self-contained method. It is based on a relationship
between the molar mass and volume holding for a particular set of hypothetical components,
whose properties were derived by Katz and Firoozabadi [6,8] based on what is found in typical
crudes. These components represent single carbon number fractions, i.e. SCN-fractions, boiling
in between the boiling points TB of successive n-alkanes (more precisely TB+0.5°C). We refer to
these components as Firoozabadi components. They are often used in PVT reports to represent
the heavy end composition of a fluid)
The relationship determines a central curve in the volume-mass plane. Two curves are used on
either side of the central curve. In a defined range a number of molar masses are introduced,
spaced according to a geometric or arithmetic progression. Default values are applied for the
parameters defining the range and number of masses. For each mass, there are two hypos, one
with a molar volume 5% higher and one with a molar volume 10% lower than the value obtained
from the central curve. These margins are default values that can be changed.
GS.06.53139 19 RESTRICTED

If default or otherwise fixed values are used for certain parameters, they properties of the hypos
will be a fixed. Only the associated amounts will depend on case input. Again, this allows for the
possibility of characterizing different fluids on the basis of a single set of components.
As for the other modes of operation, the primary input parameters of the heavy fraction are
average molecular weight, density and amount. Initial values for these parameters are obtained
from a PVT-report. Within certain limits, these parameters may be tuned in order to match
relevant data from the PVT-report or from the field.
Default parameter values are:
1. Lowest grid mass (84)
2. Highest grid mass (800)
3. Number of mass values (32, spaced according to a geometric progression).
4. Number of volumes per mass (2, which is also the maximum allowed)
5. Composition distribution shape parameter, γ (0. For this value, the distribution is
exponentially decreasing as a function of molar mass. For higher values of γ , the
distribution initially increases, goes through a maximum and then decreases).
6. Deltaplus (0.05. This means that the volume of the hypo with the lower density is
5% above the central value)
7. Deltamin (0.1. This means that the volume of the hypo with the lower density is
10% below the central value )
A detailed mathematical description can be found in Appendix A4.
GS.06.53139 20 RESTRICTED

6. Fluid Characterization
In this section we go in more detail through the process by which, starting from experimental
data and information on the intended application, a well stream composition is derived. The
various steps involved in this process are also illustrated in FigureC-6 (in Appendix C).
For practical reasons we will assume that Hysys is the process simulation program used in both
the characterization and the simulation of the process itself.

6.1 Step 1: Base composition and fluid type

The first step in the fluid characterization procedure is an assessment of the stream type and of
the data available. A typical PVT-report will contain various sessions with the results of different
experiments. Basic measurements and reliability tests may have been performed on various
samples (bottles). Often one of these is selected to perform the more extensive tests.
In most cases, the PVT-report contains a derived well stream composition. A well stream
composition can also often be derived --- through mathematical recombination ---- from the
results of a separator test for which gas and liquid compositions are available together with an
indication of gas-oil ratio (GOR).
This base well stream composition is to be used as the starting point of the characterization. By
considering the presence of various types of components (light-heavy) and through an estimate
of the GOR, the fluid type must be asserted and compared to corresponding statements and
GOR values in the PVT report.
A crude but fit for purpose estimate of GOR can be performed in Hysys via a single flash to
ambient conditions.
The base composition will contain different ingredients
• Light hydrocarbons (reported as identified components)
• Heavy hydrocarbons (reported as carbon number fractions)
• Plus fraction (with average molecular weight and specific gravity)
• Inert components: nitrogen
• Sour components: CO2, H2S.
• Water. (Often, the amount of water is not specified, but in simulations it is assumed that
the well stream is saturated at reservoir conditions, and from this an estimate of the water
cut can be obtained).
It should be kept in mind that the base composition is usually derived from a recombination of
a gas and a liquid in a separator test. The gas composition is obtained as mole fractions,
whereas the liquid composition is usually obtained as weight fractions. In order to put them on
a single base, weight fractions have to be converted to mole fractions, for which the molecular
weights of the components are needed. These molecular weights are often obtained from
a correlation. It is important to investigate how exactly this was done in the PVT report.
Moreover, gas and liquid compositions have had to be recombined using a value for GOR. This
value is not necessarily completely fixed or reliable. In the characterization procedure, it may be
used as a variable --- within bounds --- allowing additional flexibility.
GS.06.53139 21 RESTRICTED

So instead of a single base composition, one may (preferably) work with two base compositions,
for separator liquid and gas. These are introduced in Hysys as separate streams, to be
combined --- using a mixer unit operation --- in a ratio representative of the GOR.

Figure 4: Representation of base composition in HYSYS

This leads to a representation of the base composition in HYSYS, as shown in Figure 4. The
stream labelled base_gas is obtained from the PVT report as the gas produced in the separator
test. The base_liquid is created using the C7PLUS unit operation. Through this operation, the
liquid composition can be entered as a combination of defined components and a C7+ fraction.
The two streams are combined using a mixer unit operation producing the stream labelled
well_stream.
This way the base stream is created in Hysys. In some cases only the (overall) composition for
the well stream is available, in which case this must be used as such.
In this initial stage, within the C7PLUS unit operation, default values and options must be used
as much as possible. These defaults are:
• Operation mode: C7+ non-standard components
• Base number of hypos: 10
• First and second distribution parameters 1 and 10.
The following data must be entered
• Type of heavy fraction (C7+, C8+, etc). To be deduced from the PVT-report. This
specification fixes the values of the lowest component MW and SG. An option is available
(type of heavy fraction = “other”) to adjust the latter values for a specific application.
• Average molecular weight of the C7+ fraction. This must be taken from the report either
directly (if available) or through computation (for example, by lumping a part of the
component slate)
• Specific gravity of the C7+ fraction. This must be taken from the report either directly
(if available) or through computation.
GS.06.53139 22 RESTRICTED

• Mole fractions of the non-C7+ components. These are referred to a light ends, but this
term should be taken literally.
• Mole fraction of the C7+ fraction in the stream.
With these data entered, the C7PLUS algorithm can be run. The hypothetical components
generated then need to be installed. Finally, flow rates of the base_gas and base_liquid must be
entered according to the recombination ratio inferred from the PVT report.
The result of this is a well stream with which the initial calculations -- without any tuning --- can
be done. The first calculation to be performed is getting the phase envelope, available as a utility
in Hysys.

6.2 Step 2: Inventory and selection of data

In order to select data from the PVT report on which to base the characterization, the following
questions must be considered

• How well does a particular set of data represent the field?

• What is the application? What are, for example, the conditions of the main separators in
the process?

• Is the data reliable?

It should be noted that the requirements for surface process engineering are different from those
of reservoir engineering. Reservoir engineering calculations are done at reservoir conditions, so
at pressures and temperatures that can be much higher than those encountered in the surface
processing. For the latter, separation test data are of particular importance, especially if the
conditions (pressure and temperature) are close to those of the separators used in the field.
Note, of course, that these will not be fully known if the project is still in the design phase.
We assume that we are dealing with surface engineering. The following types of data need to be
considered, roughly in order of importance

• Compositional of gas and liquid compositions leading to base well composition (see
previous subsection)

• Single stage or multi-stage separation test data. The most important data from these test
to be used are: first stage GOR; total GOR; stock tank density

• Saturation conditions: bubble or (retrograde) dew point: temperature, pressure and

density. Note that a saturation point is often included as a special point of a phase
behaviour experiment, such as constant composition expansion (CCE).

• Phase behaviour experiments: CCE, CVD, DL.

• Special data concerning the presence of particular components: BTEX, H2S, Hg, etc.
GS.06.53139 23 RESTRICTED

6.3 Step 3: Validation of the data

The procedures and potential pitfalls associated with PVT sampling and analyses are beyond
the scope of this document. The user is referred to [3].
A number of relatively straightforward numerical checks may be carried out to help establish the
validity of the reported data. These should be used to supplement validation checks carried out
by the contract laboratory as part of their normal procedures.
It should be noted that the overall validity of results obtained from PVT laboratory measurements
will depend to a large degree on whether or not the samples were representative of the reservoir
fluid. It is imperative therefore that every practical effort be made to obtain representative
samples through proper well conditioning and sampling.
The validation checks described below are aimed at establishing the consistency of the
measured data and are unlikely to detect unrepresentative sampling.
Before any experimental PVT data are used for design or study purposes, it is necessary to
ensure that there are no errors or major inconsistencies that would render any subsequent work
useless. Two such means of data validation are described below:

Buckley plot (or Campbell diagram). For hydrocarbon gas and liquid phase in equilibrium, there
is a linear relationship between the log of the individual component K-values and their respective
critical temperatures squared, see Figure C-8 (in Appendix-C). This technique is described by
Campbell [7]. Note that as components become less paraffinic in nature, the greater will be the
deviation from linearity. Thus, it is common for the components heavier than C5 to show such
deviations.
For the light components, any significant deviations from the linear relationship indicate possible
non equilibrium separation, suspect analyses or numerical errors in the data reporting. Because
it is a log scale any variation of log K of more than 0.1 is significant.

Mass balance diagram. The mass balance diagram is based on the following general flash
equation describing the individual component material balances around a flash separation stage:

Fzi = Lxi + Vyi Equation 3

where F, L and V (=F-L) are the molar flow rates of feed, flashed liquid and flashed vapour
respectively and zi , xi and yi are the mole fractions of component i in the feed, flashed liquid
and flashed vapour respectively. This equation can be rearranged to

yi  1  xi  1
= 1 −   +
zi  β  zi  β
Equation 4

with β = V / F . This should when plotted result in a straight line for which the slope and constant
add up to unity, see Figure C-8 (in Appendix-C).
GS.06.53139 24 RESTRICTED

Note that the well fluid composition reported in PVT reports are normally obtained from a
mathematical recombination of the test separator gas and liquid compositions in a mole ratio
corresponding with the measured separator GOR, i.e. the well fluid composition is calculated by
a component mass balance. In such cases, deviations on a mass balance diagram normally
indicate arithmetic errors in the data recombination.

6.4 Step 4: Selection of thermodynamic method

In fluid characterization, selection of a thermodynamic model boils down to the choice of an
appropriate equation of state --- for the basic phase equilibrium calculations --- and associated
options for parameters and properties such as liquid density and enthalpy.
Specific calculation options for at least density are always needed. It should be emphasized that
to obtain a proper characterization, the model should predict density fairly accurately (within 1%).
This accuracy is not obtained with the base equation of state model.
Non-technical considerations include
• is the work based on a contract with restrictions regarding the tool and the model?
• which program(s) will be employed to carry out simulations later on? Obviously, the
persons who are going to work with the results later on need to have access to the model
• The model used in the simulation(s) should be equivalent to that used in the
characterization
The C7PLUS procedure can in principle be combined with different equations of state as
described before in Section 4.
In addition, one needs to take into account the application that will be simulated later on, to avoid
unnecessary conversions. The following issues may be relevant
• presence of water, CO2 and H2S
• decompression (amount of liquid and gas produced)
• separation (high pressure, low pressure, cold separator, three phase)
• dehydration (glycol dehydration and regeneration)
• treating (removal of unwanted components, such as H2S, CO2, mercury)
• inhibition (ethylene glycol or methanol to avoid gas hydrates)
• dew pointing (water and hydrocarbon specifications on product streams)
• aromaticity
• pressure and temperature range

6.4.1 Hysys methods

Peng-Robinson. This model is recommended for general hydrocarbon processing. The default
options are:
• Phase equilibrium and enthalpy are based on the Peng-Robinson (1978) equation of
state (PR78).
• Density is computed from a correlation (smooth liquid density option).
GS.06.53139 25 RESTRICTED

• Nonzero but temperature independent binary interaction parameters (BIPs) are applied in
the a parameter. Values are retrieved from a databank.
• For hydrocarbon-hydrocarbon pairs, BIPs are calculated from a generalized expression.
These settings are fit for purpose for most applications. Note that HYSYS was designed with the
PR equation of state in mind with special treatment for systems containing H2, He, N2, CO2, H2S,
H2O, methanol and glycols (MEG, TEG) to allow simulation of common process units.
Alternatives.
To model certain particular phenomena, processes and units, variations or alternatives are
available. The most important being
• Kabadi Danner: recommended in HYSYS to compute water content of hydrocarbons
streams. Note that this model cannot be used for systems containing polar
substances other than water, e.g methanol, glycols

6.4.2 Shell methods (HYSPPTS).

Shell proprietary methods are available through the HYSPPTS extension. Two equation of state
models are relevant here: SMIRK and CPA.
Shell modified improved Redlich-Kwong (SMIRK).
• Phase equilibrium is based on the SMIRK equation --- based on the Redlich-Kwong base
expression --- in which both a and b are temperature dependent.
• Enthalpy and density are calculated from the SMIRK equation itself.
• Binary parameters (BIPs) may depend on temperature and composition. Default values
are retrieved as point values from the Shell databank or --- for certain combinations ---
computed from generalized correlations
• For hydrocarbon-hydrocarbon pairs, BIPs are zero.
This model is adequate for general hydrocarbon processing and also handles many polar-
nonpolar interactions well, such as water-hydrocarbon.
Cubic Plus Association (CPA).
• Phase equilibrium is based on the Soave-Redlich-Kwong equation to which a term is
added to account for association interactions (hydrogen bonding) in systems containing
water, methanol, glycols.
• Enthalpy is calculated with the Lee-Kesler method (implemented in the Shell code)
• Density is calculated with the SMIRK equation of state
• Binary parameters (BIPs) may depend on temperature. Default values are retrieved as
point values from the Shell/Pepper databank or --- for certain combinations of
components --- computed from generalized correlations
• For hydrocarbon-hydrocarbon pairs, BIPs are calculated from a generalized expression.
This model is recommended for special applications involving systems containing, besides
hydrocarbons and water, methanol or glycols.
GS.06.53139 26 RESTRICTED

6.5 Step 5: Simulation of the experimental data

The next step is to build a Hysys case representing the selected experiments. The feed well
stream is that created earlier in step 2.
Separator test. An example is shown in Figure 5, where a four-stage separation test is
represented as a number of separation vessels in series. It is convenient to add energy streams
for each of the stages and set pressure drops for each separator vessel to unspecified (missing).
The conditions (pressure and temperature) of each of the stages can then be entered as
conditions on the liquid product streams (L1, L2, etc). The last stage corresponds to the standard
conditions to which all reported GOR values refer.
Note: Energy streams can be easily attached to a separator in the corresponding drop-down menu of the dialog box in Hysys.
However, this menu is missing in Hysys 2004.1 due to a program bug. Fortunately, there is another way of attaching an energy
stream. On the PFD click Ctrl and keep it pressed, move the mouse over the separator (that will show the inlet and outlet nozzles).
Move the mouse to point to the red nozzle, click and drag...that will create a new energy stream attached to the separator

Normally, the Hysys case will converge without problem.

Figure 5: Four stage separation test represented in HYSYS.

To be able to compare with measured results, the various properties reported in the
measurements have to be calculated from the simulation results. It is convenient to use a Hysys
spreadsheet for this. (It is best to add an optimiser unit operation, and use the related Hysys
spreadsheet, to allow easy extension to optimisation later on.)
For the separation test depicted in Figure 5, the properties are calculated as follows
• Stage GOR. This is computed as the ratio of the standard gas flow (Sm3/h) --- of the
stage in question --- and the actual volume flow of the tank liquid (m3/h). This produces
the GOR in Sm3/Sm3. A unit conversion may be required depending on the system of
units employed in the PVT report. Standard conditions employed should be specified in
the PVT report.
GS.06.53139 27 RESTRICTED

• Liquid density. This is reported a stream property (mass density) that can be transferred
to the Hysys spreadsheet for all the relevant liquid streams.
• Other properties that may have been measured can be built in a similar way. Precise
definitions are usually given in the PVT report and these should of course be followed.
Saturation points. A saturation point corresponds to a set of conditions somewhere on the
phase envelope: a bubble point (gas is about to form) or ad dew point (liquid is about to form). In
Hysys, the procedure is as follows
• Clone the well stream composition using the balance unit operation, transferring the mole
flows c.q. fractions. The output of this operation is a stream S with the same composition
as the well stream, but otherwise detached from the flow sheet.
• For a bubble point, set the temperature of S equal to the experimental value and set its
vapour fraction to zero.
• For a retrograde dew point, set the temperature of S equal to the experimental value and
set its vapour fraction to minus one (-1). If the vapour fraction is set to one, then the
normal, low-pressure, dew point is obtained.
Constant composition expansion. A CCE experiment is a phase behaviour study on a stream
with a fixed composition. An example is shown in Figure 6 where a CCE experiment is
represented as a series of separator vessels with feed equal to the combination of the product
streams of each previous stage, that is the total well stream.
As before, it is convenient to add energy streams for each of the stages and set pressure drops
for each separator vessel to unspecified (missing). The conditions (pressure and temperature) of
each of the stages can then be entered as conditions on the liquid product streams (for an oil
system) or gas product streams (for a gas stream). The last stage corresponds to the standard
conditions employed in the experiment.
Via a balance unit operation, a clone of the well stream saturated at the temperature of the CCE
is created. The pressure at which the sample is just saturated is one of the points reported for
a CCE test, and quantities reported for other stages normally use this particular stage as
reference (see below).

Figure 6: Constant composition experiment represented in HYSYS.

GS.06.53139 28 RESTRICTED

As before, it is convenient to use (or extend) the Hysys spreadsheet to include the properties
measured in the CCE test. These properties include:
• Relative volume. This is obtained for each stage by dividing the total volume flow of the
two feed streams combined by the volume flow of the stream labelled saturated.
• Liquid volume (for condensate systems) or gas volume (for oil systems). This is obtained,
for each stage, as the total volume flow of the stream in question. Often, reported values
refer to the ratio of this volume flow to the total volume flow at stage conditions, or at
saturation conditions. Then, the appropriate conversion must be performed.
• Liquid density. This is reported a stream property (mass density) that can be transferred
to the Hysys spreadsheet for all the relevant liquid streams.
• For other quantities, if considered relevant, the definition must be checked and the
corresponding calculation added to the Hysys spreadsheet.
Differential liberation. In a differential liberation experiment, the total amount of gas evolving at
each stage --- which is at a lower pressure than the previous stage --- is removed from the
system. As shown in Figure 7, the set up can be represented as a series of separator vessels,
where each feed is taken as the liquid product stream of the previous stage. (Note that for the
first few stages, the pressure may be higher than the bubble point pressure, so that the gas
streams do not carry any flow).
As before, via a balance unit operation, a clone of the well stream saturated at the temperature
of the DL experiment is created. The pressure at which the sample is just saturated is one of the
points reported for a DL test, and quantities reported for other stages normally use this particular
stage as reference (see below).

Figure 7: Differential liberation experiment represented in HYSYS.

As before, it is convenient to use (or extend) the Hysys spreadsheet to include the properties
measured in the CCE test. These properties normally include:
• Oil volume factor. This is obtained as the ratio of the actual volume flow of the liquid
product stream at the given stage and the actual volume flow of the last stage (the
residual oil). With reference to Figure 7: Bo ,i = Li / LSTD
GS.06.53139 29 RESTRICTED

• Solution gas oil ratio. This is obtained as the total amount of gas (measured as standard
gas flow) evolved from all stages downstream the given stage divided by the actual
volume flow of the last stage (the residual oil).

With reference to Figure 7

 Last 
Rs ,i =  ∑ Gk  / LSTD
 k =i +1 
• Liquid density
• For other quantities, if considered relevant, the definition must be checked and the
corresponding calculation added to the Hysys spreadsheet.
Constant volume depletion (CVD). In a constant volume depletion experiment, after each
pressure reduction, the original volume of the system is restored through the removal of just the
right amount of gas,

The set up can be represented as a series of separator vessels, where each feed is taken from
the previous stage, subtracting a quantity of gas such that the volume flow is constant (isochoric
flash). The set up for one stage is shown in Figure 8. The removal of part of the gas is
accomplished through the use of a tee splitter and a mixer in series, coupled to an adjuster. The
adjuster controls the stream flow ratio applied in the tee splitter, such that the actual volume flow
of product stream (F1) matches the reference value (actual volume flow of the stream labelled
saturated).

Figure 8: One stage of a constant volume depletion experiment (CVD) represented in HYSYS

6.6 Step 6: Base performance

Once a suitable Hysys case has been set up, a base performance calculation can be performed.
At this stage, no tuning or matching is done, just a calculation using the base well fluid
composition.
GS.06.53139 30 RESTRICTED

Phase envelope. The first calculation to perform is the vapour-liquid phase envelope. In Hysys,
this is available as a utility. The shape and location of the phase envelope in the TP-plane
should give a confirmation of the type of well fluid and the sort of issues that may be expected
during the fluid characterization. Any experimental saturation points and separator conditions
can be overlaid (by transferring the data in table form to Excel).
Principal target quantities. The most important quantities to focus at are:
• Saturation point pressure or temperature
• First stage gas oil ratio and total GOR.
• Stock tank liquid density.
Values for these should be calculated in a Hysys spreadsheet and compared to the experimental
value, using a relative deviation in percent, defined for each quantity Q as

 Q calc 
ε (Q) = 100 exp − 1 Equation 5
Q 

Note that if Q stands for a temperature, an absolute scale is required for this to makes sense
(Kelvin or Rankine). Example results are given in Table 2 (see also Example-2 in Section 8)

Table 2: Fluid characterisation – Measured data versus simulated data

Parameter Value Data Calc Exp % dev
C7+ Fraction 0.29 Bubble point T[°C] 105.0 105.0 0.00
C7+ MW 195.62 Bubble point P[kPa] 25,997 23,950 8.55
C7+ SPGR 0.84 <empty>
C7+ First Distr Param 1.0 GOR1 [sm3/m3] 199.5 182.5 9.30
C7+ Second Distr Param 10.0 GOR2 [sm3/m3] 12.18 12.54 -2.88
C7+ Number of Hypos 10 GOR total [sm3/m3] 211.7 195.1 8.52
C7+ Lowest MW 78.11 <empty>
C7+ Lowest SPGR 0.66 Stock tank density [kg/m3] 825.6 815.0 1.30

6.7 Step 7. Sensitivities

From the base case, it may be useful to obtain an estimate for the sensitivity of target variables
wit respect to free input variables. Sensitivities are derivatives, scaled such that a meaningful
comparison between different sensitivities can be made. The definition of the sensitivity of target
variable y with respect to input variable x is defined as

x dy
Sens( y, x) ≡ Equation 6
y dx
GS.06.53139 31 RESTRICTED

This may be phrased as the percentage change that the target value undergoes upon changing
the input variable by 1%. Table 3 gives the sensitivities -- obtained using the derivative utility in
Hysys -- for a typical black oil (see also Example-2 in Section 8)

Table 3: Fluid characterisation – Sensitivity of target data (y) to variations in input data (x)

Sensitivities (x/y * dy/dx)

x => C7+ mol weight C7+ specific gravity

Saturation pressure -0.26 0.65

First stage GOR -0.98 1.118

Stock tank liquid mass density 0.03 1.07

The table shows the sensitivities of the principal target variables (saturation pressure, first stage
GOR and tank liquid density) with respect to the main variables characterizing the C7+ fraction.
An extensive overview of these sensitivities for different cases (gas wells, gas/condensate wells,
oil wells) can be found in Appendix-B.

6.8 Step 8. Tuning

In Hysys, an optimiser is available with which target quantities can be matched via tuning of
selected parameters. This can be done in a very general way. The following steps may be
distinguished
• Build a Hysys flow sheet
• Start the optimiser unit operation; a part of this is the optimiser spreadsheet
• Connect selected flow sheet variables (from streams, unit operations, and so on) to the
optimiser spreadsheet; some variables are target variables, others are tuning parameters
• Define a merit function in the optimiser spreadsheet (for example, the sum of squares of
deviations from experimental values)
• Select in the optimiser unit operation which parameters to tune, corresponding starting
values and boundaries
• Select options (concerning the algorithm, merit function, and so on) of the optimiser and
run the optimiser
In principle, any flow sheet variable that can be accessed by the user in a unit operation or
stream can be connected to the optimiser. The Shell C7PLUS unit operation is included.
In fluid characterization, the principle target quantities are those that were discussed before:
saturation pressure, liquid density, gas oil ratios. The principle tuning parameters are: input gas
to liquid ratio, C7+ average mole weight; C7+ specific gravity.
GS.06.53139 32 RESTRICTED

Currently, quantities defined in the base environment --- related to the thermodynamic model ---
cannot be connected to the optimiser. So binary interaction parameters cannot be tuned in this
way. We expect that this shortcoming will be removed in the future.
For detailed instructions on how to use the optimiser, we refer to the Hysys manuals and the
SPPTS tutorial that comes with Hysys.
Recommended procedures and tolerances for data matching
When adjusting parameters to tune a heavy-end characterisation, it should be remembered that
certain of the variables relate to laboratory-measured data, while others are essentially
correlating parameters.
The average molecular weight and SG of the heavy fraction are associated with measured
values but cannot be directly measured. In presenting these data, some laboratories use
correlations to calculate the molecular weight and SG of the heavy fraction and these data
should not be treated as a measurement unless specifically stated in the PVT report.
Where the heavy fraction SG is not given in the PVT report, it must be obtained by a trial and
error procedure through matching to the measured properties such as the stock tank liquid
density, which has a measurement accuracy of less than 1%.
The accuracy of molecular weight measurements is considerably worse than those for SG and
figures given in a PVT report may only be accurate to within 10 - 15%.
Molecular weight measurements on condensates may be even less accurate. It is very likely
therefore that adjustments to the average molecular weight value used in C7PLUS will be
required in order to achieve an acceptable match with the measured data.
The two component distribution parameters, while representing real system characteristics,
would not normally have measured values. Adjustment of these parameters is therefore
somewhat more arbitrary and should be based on sensitivity trend data.
For systems having left-skewed component distributions, the peak concentration normally occurs
at a carbon number of C7/C8. When characterising heavier residual fractions, such as C12+,
a value of 1.0 should therefore be used for the first distribution parameter.
The values of the minimum molecular weight and SG are essentially governed by the lowest
carbon number of the plus fraction being characterised. Large adjustments to these parameters
would therefore be unrealistic.
The order in which the program variables should be adjusted is as follows:
1. C7+ average specific gravity, SG (check agreement between predicted and measured
stock tank liquid density if available)
2. Average molecular weight, MW (adjustments should be within the experimental
measurement
3. First distribution parameter (value should be 1.0 for fractions heavier than C8+)
4. Second distribution parameter
5. Minimum C7+ molecular weight and SG (these values are governed by the lowest carbon
number of the plus fraction - large changes are unrealistic)
6. Number of components (unless there is good reason to deviate, a minimum of
10 components should be used)
GS.06.53139 33 RESTRICTED

The following recommendations on matching tolerances are given for general guidance. The
required degree of matching will depend on the purpose for which the data will be used and each
case should be assessed individually.
Matching Tolerances for gas and gas condensates
Dew Point. Measurement accuracies for dew point determinations are very system dependent
but typically lie in the range 2 - 5%. An acceptable match on dew point pressure would therefore
be within this range. To increase the predicted dew point temperature, increase the average
molecular weight of the heavy fraction, increase the average specific gravity and/or decrease the
value of the 1st. distribution parameter.
Retrograde liquid condensation. Agreement to within 10% between measured and predicted
liquid condensation is considered acceptable. To increase the predicted total liquid dropout,
increase the average molecular weight of the heavy fraction. To increase the liquid dropout in
the first stage, decrease the average SG of the heavy fraction or decrease the value of the
1st. distribution parameter.
Stock tank liquid density. Agreement within 2% between measured and predicted stock tank
densities is considered acceptable. To increase the predicted stock tank liquid density, increase
the average SG of the heavy fraction.
Matching tolerances for crude oils
In general, discrepancies of 20% or more between simulated and measured data would indicate
erroneous measurements; normally much better agreement could be obtained as indicated
below:
GORs. The GOR measurement for a field separator should be accurate to within ca 10%. An
acceptable match between measured and predicted values for a first stage separator GOR is
about 10% although better agreement should be possible. For the second and third stages in
a multistage flash, agreement within 30% is considered acceptable. GOR values measured in
the laboratory should be significantly more accurate, typically within 5%. Further to this:
• To increase the predicted GORs of all stages, decrease the average molecular weight of
the heavy fraction.
• To increase the first stage GOR only, increase the average SG of the heavy fraction.

Stock tank liquid density

Agreement within 2% between measured and predicted stock tank densities is considered
acceptable. To increase the predicted stock tank liquid density, increase the average SG of the
heavy fraction.

Bubble point
Crude oil bubble points can be measured to within an accuracy of 2% and agreement within
these limits would therefore constitute a good match. However, the SRK and Peng-Robinson
equations of state tend to under-predict bubble point pressures for mixtures containing heavy
components. As a result, it may not be possible to achieve a good match on bubble point.
The characterisation should therefore be tuned to measured data other than bubble points
whenever possible. To increase the predicted bubble point pressure, increase the average
SG and/or decrease the average molecular weight of the heavy fraction.
GS.06.53139 34 RESTRICTED

7. Example Cases
7.1 Case-1
This case was taken from the previous guide for heavy end characterisation [2], where another
process simulation program (PRO/II) was used in the calculations. Data of the fluid (black oil
type) are given in Table 4.

Table 4: Composition and PVT data of fluid in example case-1

Amount Molecular Specific P Dewpoint T
Component
[Mol%] weight gravity [bar] [degC]
CO2 1.1015 30 164
Nitrogen 3.3115 50 164
Methane 91.2221 80 158
Ethane 3.3576
Propane 0.5923 T P CGR
i-Butane 0.1103 [degC] [bar] [m3/Sm3]
n-Butane 0.1273 L1/V1 20 70 14.5
i-Pentane 0.0511 L2/V1 0 30 3.2
n-Pentane 0.0421 LIQ/V1 15.5 1.013 15.0
n-Hexane 0.0611
Benzene 0.0231 Density
[kg/m3]
C7+ 0.2270 130 0.75 Stock tank oil 0.766

Using the light end composition given and the amount of the C7+ fraction, we need to match the
dew point temperatures, condensate to gas ratios (CGR) and stock tank oil densities. For the
definition of CGR applied we refer to the diagram in Figure 9

Figure 9: HYSYS process flow diagram for example case-1

GS.06.53139 35 RESTRICTED

This is also the diagram representing the case in Hysys. The PR equation of state is used with
hydrocarbon-hydrocarbon (HC-HC) binary interaction coefficients set to zero. The C7PLUS unit
operation is used to enter the compositional data and the initial values C7PLUS parameters:
average mol weight 130; specific gravity 0.75; first distribution parameter (DIST1) 1.0; second
distribution parameter (DIST2) 20. These and other parameters are connected to the optimizer
spreadsheet, in order to calculate the quantities to match and built an objective function (sum of
squares of deviations). The results are shown in Figure 10 as screen images of HYSYS
optimizer spreadsheet.

Performance based on initial values: FOBJ=75.2

Performance after optimization: FOBJ=0.61

Figure 10: HYSYS optimiser spreadsheets for example case-1

The ‘raw’ quantities retrieved from the flow sheet are in column A. From top to bottom there are:
three dew point temperatures; standard gas flow V1; liquid flows of streams L1, L2 and LIQ; the
mass densities of these streams; C7PLUS parameters MW, SG, number of hypos, DIST1,
DIST2. The quantities to be matched are calculated in column C and compared to experimental
values in column D. The value of the objective function is in cell E8. Deviations between
measured and calculated values are in column H.
GS.06.53139 36 RESTRICTED

7.2 Case-2
Below are given data for a black oil, consisting of a separator test (with the set up of Figure 11
and a constant composition expansion (CCE) test. In the latter, the (recombined) fluid was
introduced in a cell and at constant temperature, the pressure was decreased and volumes
measured. Relative volume is defined as system volume divided by system volume at saturation
(at the bubble point for this case)

V1

Well Stream
Test V2
Separator

Stock Tank
L1
L2

Figure 11: Test rig. Conditions: test separator, 30°C, 120 bara; tank 15°C, 1.013 bara.
GS.06.53139 37 RESTRICTED

Table 5: Separator test data.

Sample V1 Sample V2 Sample L2 Well fluid

Component
Mol% Mol% Mol% Mol %
C1 85.44 47.61 0.28 53.75
C2 6.95 16.21 0.63 5.10
C3 4.21 19.09 2.89 4.36
IC4 0.98 5.46 2.14 1.58
NC4 1.11 6.41 3.79 2.28
IC5 0.31 1.82 2.91 1.30
NC5 0.21 1.17 2.56 1.08
C6 0.11 0.56 4.35 1.63
C7+ 0.25 1.25 80.39 28.66
N2 0.10 0.01 0.00 0.06
CO2 0.30 0.36 0.00 0.2
Data
C7+ MW 195.62
C7+ SG 0.839
GOR V1/L2 V2/L2 (V1+V2)/L2

(sm3/m3) 182.536 12.537 195.074

Table 6: Constant composition expansion study at 105°C

Pressure (bara) Relative Volume v/v% gas

350 0.96 0
300 0.97 0
250 0.99 0
239.5 1.0 0 (bubble point)
200 1.12 14.5
150 1.39 33.9
100 1.86 54.0
50 3.25 77.1
20 8.23 90.3
5 34.35 92.1
GS.06.53139 38 RESTRICTED

Table 7: HYSYS spreadsheets for example case-2

Base: straight calculation from the data.
Parameter Value Data Calc Exp % dev
C7+ Fraction 0.29 Sat temp [°C] 105.0 105.0 0.00
C7+ MW 195.62 Sat press [kPa] 25,997 23,950 8.55
C7+ SPGR 0.84 <empty>
C7+ First Distr Param 1.0 GOR1 [sm3/m3] 199.5 182.5 9.30
C7+ Second Distr Param 10.0 GOR2 [sm3/m3] 12.18 12.54 -2.88
C7+ Number of Hypos 10 GOR total [sm3/m3] 211.7 195.1 8.52
C7+ Lowest MW 78.11 <empty>
C7+ Lowest SPGR 0.66 ST density [kg/m3] 825.6 815.0 1.30

Sensitivities (x/y * dy/dx)

x
y
C7+MW C7+SG
Sat press -0.26 0.65
GOR1 -0.98 1.18
ST Density 0.03 1.07

Step 1. Fit C7+SPGR to stock tank density (manually).

Parameter Value Data Calc Exp % dev
C7+ Fraction 0.29 Sat temp [°C] 105.0 105.0 0.00
C7+ MW 195.62 Sat press [kPa] 25,380 23,950 5.97
C7+ SPGR 0.83 <empty>
C7+ First Distr Param 1.0 GOR1 [sm3/m3] 197.5 182.5 8.21
C7+ Second Distr Param 10.0 GOR2 [sm3/m3] 12.27 12.54 -2.11
C7+ Number of Hypos 10 GOR total [sm3/m3] 209.8 195.1 7.54
C7+ Lowest MW 78.11 <empty>
C7+ Lowest SPGR 0.66 ST density [kg/m3] 817.6 815.0 0.32

Step 2. Fit C7+MW to GOR1 and bubble point pressure (manually).

Parameter Value Data Calc Exp % dev
C7+ Fraction 0.29 Sat temp [°C] 105.0 105.0 0.00
C7+ MW 213.00 Sat press [kPa] 24,912 23,950 4.02
C7+ SPGR 0.83 <empty>
C7+ First Distr Param 1.0 GOR1 [sm3/m3] 182.9 182.5 0.19
C7+ Second Distr Param 10.0 GOR2 [sm3/m3] 11.64 12.54 -7.17
C7+ Number of Hypos 10 GOR total [sm3/m3] 194.5 195.1 -0.28
C7+ Lowest MW 78.11 <empty>
C7+ Lowest SPGR 0.66 ST density [kg/m3] 819.0 815.0 0.49

To work out this case, a simple simulation needs to be set up for the configuration of Figure 11
where the well stream is generated using a C7PLUS unit operation (similar to Figure 4). We
have selected the Peng-Robinson equation of state with smooth liquid density option (default)
In a Hysys spreadsheet, the various target quantities can be calculated from properties retrieved
from the simulation. GOR for example is the ratio of the gas stream standard volume flow to the
actual volume flow of liquid stream L2.
Since a well stream composition is available, including C7+ properties, this can be introduced
directly into the simulation and a straight calculation (operation mode 1) leads to the base results
GS.06.53139 39 RESTRICTED

(see Table 7, upper part). The bubble point pressure and first stage GOR are about 9% too high
and the stock tank density ca 2% too high.
From the derivatives (or sensitivities, see Equation 6) we observe that the C7+ specific gravity
has a strong influence on all target properties, whereas the C7+ average mole weight does not
influence the stock tank density very much. This allows matching the stock tank liquid density
first --- to within 1% ---- by tuning the C7+ specific gravity. In a second step, the C7+ average
mole is adjusted to match bubble point pressure and GOR.
The adjustment of SPGR was within 1%, whereas the C7+ mole weight needed to be increased
by almost 10%. This is allowed given typical experimental accuracies for these quantities.
We achieved that the GOR of the first stage is reproduced within 1% and the saturation pressure
within 5%. It is not possible to improve both simultaneously using the two principle variables.
However, as can also be seen in Figure 12 from the results for the CCE experiment, the match is
satisfactory. Further tuning would make much sense. A better match may be possible, but the
model parameters may become unphysical.

CCE at 105 degC

Simulation Saturation pressure calc.
Exptl Saturation pressure exptl.
100
Volume % gas

10

1
0 5000 10000 15000 20000 25000 30000
Pressure [kPa]

Figure 12: Reproduction of CCE data, gas phase fraction in volume %.

GS.06.53139 40 RESTRICTED

8. Using C7PLUS in the HYSYS Process Simulation Program

Availability and instructions for use.
In order to be able to use the C7PLUS procedure the Shell thermodynamic package HYSPPTS
must be installed. Instructions for how to invoke and use the C7PLUS procedure within Hysys
can be found in the HYSPPTS tutorial that comes with it, which (for version 3.3) can be found in
the folder:

C:\Program Files\Hyprotech\HYSPPTS 3.3 (Build 51)\HYSPPTS\Documentation

C7PLUS unit operation in Hysys

C7PLUS is one of the unit operations available in Hysys. Specifications can be entered by the
user via a menu containing several Tabs.

On the “Design” Tab

shown in the Figure
on the right-hand-
side, one of the four
Characterization
Modes can be
selected to
characterize the
heavy end of the
connected stream
(typically a well
stream or separator
liquid stream).
GS.06.53139 41 RESTRICTED

C7+Parameters Tab
MODE-1:
C7+ non-standard
components
The primary and
secondary
parameters can be
entered as
described in
Section 5.1
(or Section A.1 in
Appendix A)

C7+Parameters Tab
MODE-2:
C7+ standard
components
Similar parameter
window as in
Mode-1, but with
one additional
parameter (Spacing)
to control the
mapping of
components.

The primary and

secondary
parameters can be
entered as
described in
Section 5.1, 5.2
(or Section A.2 in
Appendix A)
GS.06.53139 42 RESTRICTED

C7+Parameters Tab
MODE-3
C7+ flexible grid
components
Similar parameter
window same as in
Mode-1, but with five
additional
parameters to
control the mapping
of components.

The primary and

secondary
parameters can be
entered as
described in
Section 5.1, 5.3
(or Section A.3 in
Appendix A)

C7+Parameters Tab
MODE-4
Single CN-fraction
correlation
Similar parameter
window same as in
Mode-1, but with five
additional
parameters to
control the mapping
of components.

The primary and

secondary
parameters can be
entered as
described in
Section 5.4
(or Section A.4 in
Appendix A)
GS.06.53139 43 RESTRICTED

“Composition” Tab
shown in the Figure
on the right-hand-
side is the same for
all modes of
characterization.
The mole fraction of
the. C7+ fraction can
be specified together
with the composition
of the light
components in the
fluid (given in blue
font)

The calculated
composition of the
created hypos is
also shown on this
menu.

“Tabular” Tab
shown in the Figure
on the right-hand-
side
The base properties
of the created hypos
are listed

Finally, by pressing the Install” button the hypos are installed on the component list in the Hysys
base environment after which the new fluid composition is available and process simulation work
can continue.
GS.06.53139 44 RESTRICTED

References

[1] EP 88-2515, Sutton, J.N., Langenberg, A., and Marshall, J.D. A Guide for the Heavy End
Characterisation of Hydrocarbon Streams, Using the C7PLUS Program; November 1988.
[2] EP 93-0065, B. Steenson, Heavy-end characterisation of hydrocarbon streams using the
C7PLUS program, July 1994.
[3] EP 92-0980, B.E. Steenson, Guidelines for Manual Sampling and Analysis of Hydrocarbon
Fluids, October 1992.
[4] AMGR.92.220, S. Schreuder and E. Hendriks, Complete description of the oil fraction
characterization method Frachar, 1992
[4] DEP 20.00.10.10-Gen "Basic Data and Phase Behaviour Methods", April 2003
[5] AMGR.85.192; De Dood, J. & Heijink, P. "Characterisation of C7 Plus Fractions for Physical
Property Calculations: 1. Development of EPSPLIT"; February 1986.
[6] Katz, D.L. & Firoozabadi,A. "Predicting Phase Behaviour of Condensate/Crude-Oil Systems
Using Methane Interaction Coefficients" Journal of Petroleum Technology - Nov. 1978.
[7] Campbell, J.M. "Gas Conditioning and Processing", Volume 1 Chap.6.
[8] Firoozabadi A, Thermodynamics of Hydrocarbon Reservoirs, McGraw-Hill Co. (1999)
GS.06.53139 45 RESTRICTED

Appendix A. Mathematical Description of the C7PLUS Procedure

A.1 Base procedure (operation modes 1, 2 and 3)

Input data
The input data contain the following items

M+ Average molecular weight of plus fraction Equation 7

ρ+ Specific gravity of plus fraction
ML Lowest component molecular weight of plus fraction
ρL Lowest component specific gravity of plus fraction
Np Number of pseudo components in plus fraction
α First distribution parameter
Q Second distribution parameter

What is computed?
The procedure will result in an internal composition of the plus fraction, defined by a set of mole
fractions and primary component properties

zj Mole fraction of component j in plus fraction Equation 8

Mj Molecular weight of component j in plus fraction
ρj Specific gravity of component j in plus fraction

These results should be consistent with the input. In other words, the average mole weight and
the specific gravity of the plus fraction as a whole --- as specified on input --- should correspond
to the values calculated from the composition and the component properties

N+ Equation 9
M+ = ∑ z jM j Average molecular weight of plus fraction
j =1

M+ N+
M
= ∑zj j Average molar volume of plus fraction
ρ+ j =1 ρj
GS.06.53139 46 RESTRICTED

The procedure is based on two assumptions. The first concerns the precise shape (functional
form) of the internal distribution, which depends on the first distribution parameter. The second is
the relation between component mole weight and component specific gravity within the plus
fraction, which depends on the second distribution parameter. These two assumptions are
sufficient to compute the internal composition and primary component properties.

Internal composition of the plus fraction

The internal composition is assumed to be of the form of a Schultz distribution (also known as
Gamma-distribution), which may be written in terms of the continuous variable molecular weight
M as

α -1  M −M L  Equation 10
1  M − M L  − β

F (M ) =   e 
βΓ(α )  β 

Where α is the first distribution parameter, the Gamma function value Γ(α ) is just a number
such that the distribution is normalized (integrates to unity)

∞ Equation 11
∫ML
F ( M )dM = 1

and β is a scale parameter, which can be computed from the average molecular weight of the
plus fraction (specified on input) since

∞ Equation 12
M + = ∫ MF ( M )dM
ML

which can be worked out as

α -1
(M − M L + M L )  M − M L  Equation 13
 M −M L 
∞ −  
M+ = ∫   e  β 
dM = M L + αβ
M Γ(α )
L
 β 

so that
GS.06.53139 47 RESTRICTED

M+ − ML Equation 14
β=
α

This continuous distribution is not applied directly. Rather, discrete mole fractions are defined,
each corresponding to a range of molecular weights:

µ j +1 Equation 15
zj = ∫ F ( M )dM
µj

The numbers µ j designate consecutive intervals on the molecular mass axis. The lowest of them
[
must be less or equal to M L . The average molecular weight corresponding to range µ j , µ j +1 , ]
in other words the molecular weight of the pseudo-component j equals

µ j +1 Equation 16
∫ µj
MF ( M )dM
Mj =
zj

Note that this implies that the average molecular weight of the plus fraction is recovered from the
discrete mole fractions and component properties --- as should be the case:

N+ Equation 17
∞
M + = ∫ MF ( M )dM = ∑ z j M j
ML
j =1

The values µ j are yet to be specified. The lowest of them is chosen to lie just below the smallest
molecular weight

µ1 = M L − 10 −6 Equation 18

whereas the higher ones are obtained as stretched intervals --- the size of these intervals
increase linearly on a logarithmic scale
GS.06.53139 48 RESTRICTED

µ j = C j −1µ1 Equation 19

The largest value µ N + is at the start of the rightmost interval. It is fixed by demanding that the
heaviest pseudo-component has a mole fraction of 0.01

∞ Equation 20
z N+ = ∫ F ( M )dM = 10 − 2
µ N+

The proportionality factor C is related to the span as follows

1 Equation 21
 µN  N + −1
C =  + 
 µ1 

The equations are solved as follows

• β is computed directly from Equation 14 based on user input. (At this point, the
distribution F (M ) is fixed, but the interval markers µ j must still be found.)

• z N + is obtained by numerically solving Equation 20

• C is computed from Equation 21

• The set µ j is obtained from Equation 19

• The mole fractions z j are computed through numerical integration (Equation 15)

• The component molecular weights are M j are computed through numerical integration
as well (Equation 16)

At this point, the mole fractions and corresponding molecular weights of all pseudo-components
in the plus fraction have been determined. The next step is to find the specific gravities of all
pseudo-components. This is done based on the molecular weights already determined and the
second distribution parameter.
GS.06.53139 49 RESTRICTED

Densities of the pseudo-components in the plus fraction.

The relation between molecular weight and density (specific gravity) for the pseudo-components
is assumed to follow a single curve that may be represented by a power law behaviour (just
a correlation)

ρ j = ρ L + a (M j − M L )
b Equation 22

where a and b are parameters. These are fixed by a imposing a condition on the density of the
heaviest pseudo-component together with the requirement that the density of the plus fraction as
a whole corresponds to the input value. The first condition is

 1   1  Equation 23
M H  - 1  = M +  - 1  − Q
 ρH   ρ+ 

where we used the subscript H to denote the heaviest pseudo-component. The parameter Q is
a measure of the aromaticity of the fraction. This relation was inspired by studying the way the
parameter

1  Equation 24
M  -1 
ρ 
 

behaves experimentally as a function of mass M for a number of homologous series (normal

paraffins, naphtenes, mono-aromatics, di-aromatics, and so on) and within crudes. The second
condition expresses the fact that the molar volume should be equal to the molar average of the
component values

M+ N+
Mj Equation 25
= ∑ zj
ρ+ j =1 ρj

The equations are solved in an iterative cycle, with the parameter b as the principal unknown, as
follows (note that the set of molecular weights and mole fractions is already known)

• The parameter b is given a starting value

• The density of heaviest pseudo-component ρH is determined from Equation 23
GS.06.53139 50 RESTRICTED

• The parameter a is determined through application of Equation 22 to the heaviest

pseudo-component
• Values of the densities of all the pseudo-components are computed using Equation 22
• Equation 25 is checked, and if not satisfied the parameter b is adjusted such that the
discrepancy decreases. The cycle is repeated until the deviation between the two sides
of this equation is in absolute value below a small tolerance

The net result of this is a set of component density values consistent with the input and
reproducing the correct overall values. So at this stage we have a set op pseudo-components
with mole fractions, molecular weights and densities (specific gravities). In order to be able to do
calculations with them, other properties have to be derived for them, such that their behaviour
can be predicted by a thermodynamic method. The thermodynamic method is based on an
equation of state, available in the process simulation, which can be one of the vendor's choices
or a Shell proprietary equation of state (if available in the process simulation program). If a Shell
equation of state is used (SMIRK or CPA), then the FRACHAR method is applied for the
calculation of the required additional properties.

A.2 Mapping to grid: the standard components (operation mode 2 )

Within C7PLUS, a fixed set of so-called standard components are defined which, if the
corresponding option is selected are used to represent the fraction. Each standard component
has a fixed molecular weight mk and molar volume vk . Each original pseudo-component is
replaced by four of the standard components --- the ones that are closest to it in terms of mol
weight and molar volume --- with corresponding amounts. The group of four standard
components will have the same average molecular weight and molecular volume as the original
pseudo-component j, in formula

Equation 26
∑ξ
j
kj mk = M j

∑ξ k
kj k v = Vj

∑ξ k
kj = 1

The contribution of original pseudo-component j to the mole fraction of standard component k is

then z j ξ kj .
GS.06.53139 51 RESTRICTED

Table A-1.
Molecular Specific Molecular Specific Molecular Specific
Name mass gravity Name mass gravity Name mass gravity
CP 70.14 0.7505 CP 70.14 0.7505 NC5 72.15 0.6312
BNZN 78.11 0.8846 CH 84.16 0.7834 NC6 86.18 0.6640
TOLU 92.14 0.8719 MCH 98.19 0.7740 NC7 100.21 0.6881
EBZN 106.17 0.8718 ECH 112.22 0.7922 NC8 114.23 0.7069
PBZN 120.20 0.8666 BCYP 126.24 0.7978 NC9 128.26 0.7217
NPHT 128.17 1.0310 BCH 140.27 0.8032 NC10 142.29 0.7341
11B 142.20 1.0244 11N 154.30 0.8076 NC11 156.31 0.7443
1ENP 156.23 1.0120 12A 162.28 0.8617 NC12 170.34 0.7526
13B 170.26 0.9915 13A 176.30 0.8609 NC14 198.39 0.7667
X180 180.00 1.1 15A 204.36 0.8591 NC16 226.45 0.7773
X210 210.00 1.1 17A 232.41 0.8588 17N 238.43 0.8233
X240 240.00 1.1 19A 260.46 0.8582 19N 266.48 0.8262
X300 300.00 1.1 23B 310.49 0.9177 24A 330.56 0.8548
X350 350.00 1.1 28B 380.62 0.8985 29A 400.69 0.8536
X410 410.00 1.1 X430 430.00 0.9247 33B 450.75 0.8855
X470 470.00 1.1 X490 490.00 0.9333 38B 520.87 0.8763
X530 530.00 1.1 X550 550.00 0.9402 X570 570.00 0.9120
X580 580.00 1.1 X600 600.00 0.9449 X620 620.00 0.9185
X640 640.00 1.1 X660 660.00 0.9496 X680 680.00 0.9255
X690 690.00 1.0 X710 710.00 0.9530 X730 730.00 0.9299
X740 740.00 1.1 X760 760.00 0.9560 X780 780.00 0.9341
X800 800.00 1.1 X820 820.00 0.9591 X840 840.00 0.9385

For historical reasons, many of the standard components correspond to library components
present in the PRO/II database. In order to cover the full range of molecular weights and specific
gravity, several pseudo components have been added. Hence these pseudo components are
standards within the context of this C7PLUS method. They are organised in three sets of
22 components each (see Table A-1). The standard components are n-paraffins (NC5 - NC16),
Naphthenes (CP, CH, MCH, ECH, BYCP, BCH, 11N, 17N, 19N), mono-Aromatics (BNZN,
TOLU, EBZN, PBZN, 12A - 29A) and di-aromatics (NPHT, 11B, 1ENP, 13 - 38B) and pseudo
components (X180 – X840).

A.3 Mapping to flexible grid of components (operation mode 3)

Although the principles are sound, some of the aspects of the mapping to grid cause problems
within Hysys. To overcome these, an alternative method is available. Here follows
a mathematical description.
The grid components in this method are strictly hypothetical components, forming a fixed set.
(This set can be changed, however, by the user through the use of input parameters). In the
molar mass-volume diagram they are in a region bounded by four straight lines

MS ≤ M ≤ ME Equation 27
a L + bL M ≤ V ≤ a H + bH M
GS.06.53139 52 RESTRICTED

Default values of the parameters are

M S = 70 ; M E = 800 Equation 28

The parameters of the lower volume line a L and bL are such that it goes through the points

( M ,V ) = {(70,80); (1000,770)} Equation 29

and those of the higher volume lines aH and bH are such that it goes through the points

( M ,V ) = {(60,101); (1000,1200)} Equation 30

The latter line is very close to the curve representing normal alkanes. Both the Firoozabadi
standard set and the original standard set in the C7PLUS method lie in the range thus
designated.
The grid components are defined as having parameters corresponding to intersections of
straight lines in this range. A set of N M molar mass values is defined first

k −1 Equation 31
 M  N M −1
M k = M S  E  ; (k = 1, L , N M )
 MS 

For each of these values, the corresponding volume bounds are

VLk = aL + bL M k ; VHk = aH + bH M k Equation 32

and in the corresponding interval, NV volume values are defined

j −1 Equation 33
Vkj = VLk + (VHk − VLk ) ; ( j = 1, L , NV )
NV − 1
GS.06.53139 53 RESTRICTED

With the current default values NM =16 and NV =4, this leads to a set of 64 standard components
(see Figure A-1).

1000
[m3/kmol

800

600
Molar volume

400

200

0
0 200 400 600 800
Molar mass [kg/kmol]

Figure A-1: Flexible grid. Each component corresponds to a point

The mapping is done as follows. Each pseudo-component obtained in the previous step must
have its parameters corresponding to a point lying inside a triangle of nearest neighbouring grid
points. The mole amount of the original component is then distributed over these three points
according to the lever rule, that is in such a way that the original point becomes the centre of
gravity of the triangle.
For each separate original hypo, the mapping is performed. For the given hypo, first the highest
lower mass and the lowest upper mass, between which the hypos mass must lie, are found. This
leaves eight standard components, but there is only one square in the MV-plane within which the
hypo will lie. This square is readily found based by comparing the volume of the hypo to the
volumes computed at the boundaries of the squares (for the same mass). With one square left
there are still four candidate triangles, only two of which actually include the hypo. Of these, the
one yielding the shortest average hypo-vertex distance is selected. By these simple steps, the
best triangle containing the hypo is determined. Through application of the lever rule, the mole
amount of the hypo is distributed over the three vertices, and the corresponding mole amounts
being assigned the respective three standard components.
GS.06.53139 54 RESTRICTED

A.4 Single hydrocarbon number fraction method: mathematical description

(operation mode 4).
In order to provide more flexibility in HYSYS, but based on the same general principles, we have
developed a separate procedure, which may be used as an alternative. Here we give
a mathematical description.
The procedure is based on a fixed curve in the volume mass space

V = f mid ( M ) Equation 34

which is based on the standard set of hypothetical components proposed by Firozabaadi and
represents at a typical relation between density and volume found in real crudes and as such is
consistent with the basic relationships applied in the original Shell C7PLUS method.
A set of masses is defined first, between (user defined) bounds, which may be spaced linearly

 k −1  Equation 35
M k = M S +  (M E - M S ) ; (k = 1, L , N M )
 NM −1

or logarithmically, as follows

k −1 Equation 36
 M  N M −1
M k = M S  E  ; (k = 1, L , N M )
 MS 

For each mass, two pseudo-components are defined, one with a lower molar volume and one
with a higher molar volume

Vk+ = f mid ( M k )(1 + δ + ) ; Vk− = f mid ( M k )(1 − δ − ) Equation 37

where δ + and δ − are parameters having default values of 0.05 and 0.1 respectively. If the
number of masses, the type of spacing and these parameters are fixed, then the properties of all
pseudo-components generated will be fixed and the set can be used as standard set which can
be used in the characterization of different fluids within the context of, say, a single project.
The internal C7+ composition is assumed to decay exponentially with molar mass, controlled by
a decay parameter b . The mole fractions may initially increase, and thus go through
GS.06.53139 55 RESTRICTED

a maximum at some intermediate mass. This is controlled by a separate parameter, γ . At one

mass, the subdivision over the high and low-density component controlled by a parameter ε .
The formula for the mole fraction reads

 γk  k −1 Equation 38
z k± = 1
(1 ± ε ) 1 − γ + b
2
 µ 0 (b) µ1 (b) 

In this formula, ε and γ are user defined input parameters. The function µ 0 (b) and
µ1 (b) represents sums of the type

NM Equation 39
µ q (b) = ∑ k q b k −1 ; (q = 1 resp. 2)
k =1

which can be expressed in closed form. The expression for the mole fractions satisfies the
requirement of normalization that these numbers should add up to unity. Parameter b is fixed
through the (user defined input) value of the average molar mass, which amounts to the
following condition (which does not contain parameter ε ):

Equation 40
∑∑ z
k ±
±
k Mk = M+

This equation for b is solved numerically using a bisection procedure. Note that not for all input
will this equation have a solution, but for physically reasonable input it should. Acceptable values
of b lie in the interval [0,1] and the existence of a solution can be checked at the start. Finally,
the parameter ε is fixed through the (user defined input) value of the specific gravity of the
petroleum fraction

ρ+ Equation 41
∑∑ z V
k ±
± ±
k k = V+ =
M+

This condition directly leads to a closed expression for ε . If the value found is in absolute value
below unity, then the density can be matched; otherwise it cannot. For higher value for the δ +
and/or δ − , ε will be smaller in absolute value. This freedom may be used, but the properties
of the resulting pseudo-components should lie between physical bounds. For example, the
density of a pseudo-component should never lie below that of the normal paraffin of the same
mass. This is a responsibility of the user. Default values and error checks are available that
ensure that these bounds will not be violated.
GS.06.53139 56 RESTRICTED

Appendix B. Sensitivity of simulated data to the C7PLUS parameters

For the purposes of developing sensitivity data, the C7PLUS variables have been divided into
two categories:

Primary Variables:

Average MW (molecular weight) of the heavy fraction

Average SG (specific gravity) of the heavy fraction

1st distribution parameter

2nd distribution parameter

and

Secondary variables:

Number of components used in heavy-end breakdown

Minimum MW used in heavy-end breakdown

Minimum SG used in heavy-end breakdown

In general, simulated data are more sensitive to the primary program variables, particularly the
average molecular weight and SG of the heavy fraction. In tuning a heavy-end characterisation
to measured data, it is the primary variables, which should be adjusted in preference to the
secondary variables. When using the Hysys OPTIMISER to automatically match PVT data, it is
only possible to vary the primary variables. The secondary variables must be set or left at their
default values. Using the defaults for the secondary variables will achieve an adequate match in
most cases.
The sensitivity of simulated data to the individual program variables will be dependent upon the
type of fluid being characterised and in the following three sections, the sensitivities of the main
categories of well fluid (gas, gas/condensate and crude oil) are addressed. For ease of
reference, these sensitivities are also illustrated graphically in Figs. C-9 to C-11 (in Appendix C).
Note that the sensitivity data for all three types of well fluid as presented in the latter Figs were
generated by varying each C7PLUS variable individually whilst maintaining the values of the
remaining variables at their default values. When more than one variable is adjusted
concurrently, it is likely that the cumulative effect on the simulated data will differ from the
summation of the individual effects. The sensitivity diagrams should therefore be used for
general guidance only.

B.1 Gases - Typical Liquid Content 0 - 50 m3/106 Sm3 (10 bbl/MMSCF)

FigureC-9 (in Appendix C) shows a typical low temperature gas treatment process and the
corresponding sensitivity of the simulation results to the C7+ characterisation.
GS.06.53139 57 RESTRICTED

It can be seen that this process is particularly sensitive to the average molecular weight of the
heavy fraction and also to the minimum molecular weight used in the breakdown.
Since the stabilised liquid comprises essentially C7+ components, its calculated SG shows a
direct relationship with the average SG of the C7+ fraction specified. The SG is insensitive to the
remaining variables since the program always generates a breakdown with an average SG,
which matches the specified value.
For the particular "once-through'' gas processing system (i.e. no recycles) used in this example,
the simulated data are insensitive to the number of components used providing 4 or more
components are used in the breakdown. However, care should be exercised when choosing the
number of components since the sensitivity is very system-dependent.

B.2 Gas/Condensates - Typical Liquid Content 50 - 1500 m3/106m3

(10 -300 bbl/MMSCF)
For a typical gas/condensate, the sensitivities of simulated data to the C7+ characterisation are
illustrated in FigureC-10 (in Appendix C).
In general, they show similar trends to those for the gas processing system although for this
system, the secondary program variables have less impact. The values of the two component
distribution parameters also have less effect on the simulated data and thus tuning of the
characterisation to the measured data must be carried out by adjustment of the average
molecular weight and SG of the heavy fraction.

B.3 Oils - Typical Liquid Content 1500+ m3/106m3 or GOR < 600 m3/m3
A typical three-stage oil separation process is shown in FigureC-11 (in Appendix C), together
with the associated sensitivity data.
With the exception of the average molecular weight and SG, paradoxically the values of the
program variables have little effect on the simulated data, due to the relatively high proportion of
C7+ material present. Unlike gas systems whose behaviour is sensitive to the characterisation of
the small amount of heavy-end material present, the behaviour of oil systems will be more
dependent upon the concentrations of light components (C7-) present in the system, as given in
the PVT report.
GS.06.53139 58 RESTRICTED

Appendix C. Figures
Figures taken from the previous guide [2] and referenced in the main text and in Appendix B are
reproduced here.

Figure C-1
GS.06.53139 59 RESTRICTED

Figure C-2
GS.06.53139 60 RESTRICTED

Figure C-3
GS.06.53139 61 RESTRICTED

Figure C-4
GS.06.53139 62 RESTRICTED

Figure C-5
GS.06.53139 63 RESTRICTED

Figure C-6
GS.06.53139 64 RESTRICTED

Figure C-7
GS.06.53139 65 RESTRICTED

Figure C-8
GS.06.53139 66 RESTRICTED

Figure C-9a
GS.06.53139 67 RESTRICTED

Figure C-9b
GS.06.53139 68 RESTRICTED

Figure C-10a
GS.06.53139 69 RESTRICTED

Figure C-10b
GS.06.53139 70 RESTRICTED

Figure C-11a
GS.06.53139 71 RESTRICTED

Figure C-11b
GS.06.53139 72 RESTRICTED

Appendix D. Phase Behaviour of Systems Showing Liquid-Liquid

Separation

The well-known shape of the phase envelope of a hydrocarbon fluid changes when a second
liquid phase forms at lower temperatures. This is typical for fluids containing substantial amounts
of H2S, which forms a separate H2S-rich liquid phase. However, liquid-liquid separation may take
place also in hydrocarbon fluids when both light and heavy hydrocarbons are present in
appreciable amounts along with an insufficient amount of intermediates to keep both types in
a single liquid.
The phenomenon of liquid-liquid separation in hydrocarbon mixtures is well known, particularly
for “simple” binary mixtures when the size difference between the light and heavy component
becomes too large. For instance, according to experimental data methane already phase
separates with n-hexane in a narrow PT-range close to –70°C and 50 bar. When intermediate
alkanes (i.e. ethane up to pentanes) are added to this binary then liquid-demixing disappears.
Basically the intermediate alkanes mitigate the differences between methane and n-hexane,
which avoids the formation of a second liquid phase.
As an illustration of this phenomenon, model predictions (using Shell/CPA) for a binary mixture
of methane and n-octane are presented in Figure D-1. The results are in qualitative agreement
with experimental data (not shown here). As can be seen in the figure, the phase boundary
curve behaves normal down to about –70°C, below which the saturation pressure increases
dramatically due to liquid-liquid separation. In case of multi-component fluids, this behaviour may
sometimes be predicted at much higher temperatures close to normal operating conditions.
Often this can be attributed to a poor fluid characterization and/or the use of an inadequate set of
binary interaction parameters in equation of state.

Phase boundary critical points

500

400
Pressure [bar]

300

200

100

0
-200 -150 -100 -50 0 50 100 150 200
Temperature [C]

Figure D-1: Phase behaviour of binary mixture of methane and n-octane (90/10 mol/mol)
GS.06.53139 73 RESTRICTED

Bibliographic Information

This report has been classified as Restricted and is not subject to US Export Control regulations.

Report Number : GS.06.53139

Title : Guide for Fluid Characterization using C7PLUS method in HYSYS
Author(s) : E.M. Hendriks GSUF
H. Meijer GSUF
Reviewed by : C. John and M. Doonan GSUD
Approved by : T.M.M. Verheggen GSUF
Content Owner : M.F. Post GSUF
Issue Date : December 2006
Activity Code : 54006680
Sponsor : Shell Exploration and Production
Electronic file : GS.06.53139.pdf
Issuing Company : Shell Global Solutions International BV, Amsterdam
P.O. Box 38000, 1030 BN Amsterdam, The Netherlands.
Tel: +31 20 630 9111
Established at The Hague, Amsterdam Office, Badhuisweg 3,
1031 CM Amsterdam
Commercial Register, Amsterdam 33276928
GS.06.53139 74 RESTRICTED

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