NORSK Field Development & Technology MANUAL

HYDRO Reservoir Technology PVT ANALYSIS

Chapter 1 About the Manual Rev. 0.6

Page 1
November 1998

1. ABOUT THE MANUAL

1.1 Introduction
1.1.1 Objectives
The objective with this manual is to help reservoir engineers to plan, define,
initiate, follow up and quality-control fluid samples and PVT analyses. In
addition, guidelines are given to assemble, compare, and apply PVT data for
input to reservoir calculations, e.g. fluid characterization, "quick-look" material
balance calculations, black-oil and compositional reservoir simulation, well test
analysis, process simulation, etc.

1.1.2 How to Use the Manual

Engineers with little or no experience in fluid sampling, PVT analysis, and
equation of state (EOS) simulation, should read this manual carefully. The main
body of the manual may not include all the general background material
required. However, selected PVT references are enclosed in the manual.

The experienced engineer familiar with PVT may use this manual as a
reference on the following subjects:

Fluid Sampling and Laboratory Analyses

Chapters 2 and 3 assist in how to design, initiate, follow up, and quality- control
fluid samples and PVT analysis of laboratory data. Chapter 3 summarizes the
sampling procedures used to collect fluids and the experimental methods used to
measure fluid properties. Procedures and recommendations related to initiating
fluid sampling and PVT analyses are presented in Chapter 2. We urge the
engineers to use the order forms included for fluid sampling, compositional
analyses, and PVT studies.

PVT Requirements/Oil and Gas Correlations

Chapter 4 summarizes PVT requirements and correlations. This chapter is
useful as a reference for engineers working with prospect evaluation, where
measured PVT data are often unavailable and must be calculated from
correlations. Engineers who already use certain PVT correlations (e.g. on a
spreadsheet) may find useful the discussions related to each correlation.

Example Calculations: Correlations and EOS Simulation

Perhaps the most important contribution of this manual are the example
calculations in Chapter 5. The examples are based on several different fluid
systems from the Visund field: Brent North II oil, gas and water samples,
Statfjord undersaturated oil samples, and Lunde condensate samples.

Oil and gas PVT properties for Brent North are calculated from correlations in
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Sections 5.2 and 5.3. Section 5.4 gives a short discussion of the steps involved
in using an equation of state model, and how the program PVTx (or a similar
program) handles the various steps in an EOS characterization. Example
calculations using an EOS model are presented in Sections 5.5-5.8, including
PVTx input files. These examples include EOS predictions, CN+
characterization using TBP data, regression, pseudoization, generation of
modified BO parameters, slim-tube simulations, and compositional gradients.

1.2 Other Norsk Hydro Manuals Related to PVT

1.2.1 Well Test Manual
Production Technology F&T has generated an internal manual on well test
planning and operations. The manual includes procedures and description of
tools used for fluid sampling, and this manual is recommended for engineers
ordering and planning fluid sampling.

1.2.2 Reservoir Simulation Manual

Reservoir Technology F&T has recently completed a reservoir simulation
manual including a short description of the PVT input required for Eclipse 100.

The ECLIPSE 200 options, e.g. Solvent- (Todd-Longstaff), GI-, and Polymer-
options have recently been described in a report which also specifies the required
PVT input.

1.2.3 Manual for Laboratory PVT Analysis

A manual for laboratory PVT analysis exists at the Fluid Laboratory Department
at the U&P Research Centre in Bergen. This manual gives detailed procedures
for performing various PVT experiments and compositional analyses. Standard
methods for measuring physical properties, and the accuracy of measured data
are also included.

1.3 PVT Manual Revisions

This manual is not yet fully complete. Special PVT experiments like swelling,
multi-contact gas injection and slim-tube experiments are yet to be described.

A library of programs related to fluid analysis and EOS simulation will later
be organized and described in this manual. Also, as new methods and tools
become available, descriptions of these will be added to the manual.
NORSK Field Development & Technology MANUAL
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2. INITIATING A PVT STUDY

2.1 Ordering a PVT Study

2.1.1 What PVT Sampling Do I Need?
This section summarizes which fluid sampling methods can be recommended
for a given type of reservoir fluid. For more details see Section 3.2 and Tables
3.1 and 3.2. Composition and physical properties typical for each type of
reservoir fluid are presented in Table 3.3.

The following table summarizes reservoir fluid types, the approximate range of
GOR for each fluid type, and the recommended sampling method(s) for each
fluid type.

Reservoir Fluid Type GOR Recommended

3 3 a
Sm /Sm Sampling Method
b
Black Oil <150 BHS, SEP, WHS
b
Volatile Oil >150 BHS, SEP, WHS
Near-Critical Oil 400-600 SEP
Rich Gas Condensate <1000 SEP
c
Gas Condensate >2000 SEP, IKS
c
Wet Gas >10000 SEP, IKS
c
Dry Gas >100000 SEP, IKS

Notes
a. BHS : Bottom Hole Sampling
WHS : Well Head Sampling
SEP : Separator sampling
IKS : Isokinetic Sampling

b. Recommended sampling method for a reservoir oil depends primarily on reservoir pressure, pR,
relative to saturation pressure, psat; for more details see Table 3.2 and Section 3.2.
In general, the following recommendations are made:

pR=psat: SEP; pR>psat: BHS; pR>>psat: WHS

WHS sampling requires single-phase fluid at the wellhead.

c. Isokinetic sampling should be considered when significant carry-over of separator liquid into the
gas stream is suspected (lean gas condensates at high rates).
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2.1.2 Summary of Available PVT Studies

This section summarizes the standard PVT studies that are available at PVT
laboratories (Norsk Hydro in-house and commercial labs).

An overview of the standard PVT experiments is given on the following pages.

The summary tables focus on the objectives of each experiment, measured and
calculated data resulting from the experiment (non-standard data, with added
cost, are noted in brackets []), and finally, the cost and time required to perform
an experiment are given. For a detailed description of each experiment, see
Section 3.4.

2.1.3 What PVT Studies Do I Need?

This section defines the standard PVT experiments that are recommended for a given type of
reservoir fluid. Which experiment to perform is to some extent dependent on the development
phase of the well/field. When the well is an appraisal well, the fluid sampling and PVT program
may be less extensive.

Reservoir Fluid BHS/SEP TBP DLE CCE CVD SST MST

Type Comp.

Black Oil • m • • N • •

Volatile Oil • m • • N • •
Near-Critical Oil • m m • • • •
Rich Gas Cond. • m N • • • m
Gas Condensate • m N • • • m
Wet Gas • m N • N • N

Dry Gas • N N • N • N

Water m N N m N m N

Note: • standard experiment m can be performed N not performed

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Bottomhole Sample Composition

Objectives Obtain molar composition of a reservoir fluid collected by bottomhole
sampling. See also single-stage separator test.
Measured Data zi, (xi)sc, (yi)sc, GOR, (ρo)sc, γg, Mg, Mo, MC6-C10+, γC6-C10+
Consistency ⋅ Bubblepoint of BHS at "rig" temperature.
Checks ⋅ Compare bubblepoints of BH samples taken at same time.
⋅ Compare bubblepoint at TR with bottomhole flowing pressure(s)
before/during sampling.
⋅ Watson characterization factor for C7+.
Cost 7 kNOK
Duration 1 day

Recombined Separator Sample Composition

Objectives Obtain the recombined molar composition of a reservoir fluid collected
by separator sampling.
Measured Data zi, (xi)sp, (yi)sp, GOR (Rsp), ρo, γg, Mg, Mo, MC6-C10+, γC6-C10+
Consistency ⋅ Hoffman et al. (Kp-F) plot.
Checks ⋅ Quantify effect of (1) separator GOR, (2) M7+, and (3) liquid
carryover on recombined composition.
⋅ Watson characterization factor for C7+ (from M7+ and γ7+).
Cost 30 kNOK
Duration 3 days

True Boiling Point Analyses (TBP)

Objectives Obtain mole, mass and volume fractions and physical properties for
distillation cuts of a stock-tank oil or condensate.
a
Measured Data xi, wi, Vi, Mi, γi [PNA distribution]
Consistency ⋅ Fit weight (or mole) fraction and molecular weight data using
Check gamma distribution function (CHAR program). Eventually adjust
residue molecular weight.
⋅ Watson characterization factor for C7+ (from M7+ and γ7+).
Cost 60 kNOK (to C20+)
Duration 10 days

a. An extended TBP analysis is sometimes requested by the process department. This type of analysis requires a
minimum 5 liter sample. Additional data for each distillation cut include: viscosity, pour point, freezing point,
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refractive index, and enthalpy.

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Single-Stage Separator Test (SST)

Objectives Determine recombined or bottomhole reservoir fluid composition.
May also be used in converting DLE data from residual to stock-tank
basis (not usual).
Measured Data Bo, Rs, Bg, ρo, Zg, Mg, Mo, zi, (yi)sc, (xi)sc
Consistency ⋅ Compare wellstream composition with other wellstream
Check compositions based on separator samples.
⋅ Watson characterization factor for C7+ (from M7+ and γ7+).
Cost 15 kNOK
Duration 1-2 days

Multistage Separator Test (MST)

Objectives Converting DLE from residual basis to stock-tank basis.
Also (historically) to determine the separator conditions that maximize
stock-tank oil production (now obsolete; not recommended for this
use).
Measured Data Bo, Rs, Bg, ρo, Zg, Mg, Mo, yi [(xi)each stage]
Consistency ⋅ Calculate reservoir fluid density using FVF, GOR, and specific
Check gravity data; i.e. bulk material balance.
⋅ Component material balance when both oil and gas compositions
are measured.
⋅ Watson characterization factor for C7+ (from M7+ and γ 7+).
Cost 20-30 kNOK
Duration 5 days
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Constant Volume Depletion (CVD):

Objectives Provides volumetric and compositional data for gas condensate and
volatile oil reservoirs producing by pressure depletion.
Measured Data psat, Vro, Gp, Zg, g, yi, MgN+, γ gN+ [(xi)last stage]
Consistency ⋅ Component and bulk material balance (see Whitson and Torp,
Check 1983).
⋅ K-value (Kp-F) plots based on material balance results.
⋅ Compare relative oil volume data with CCE relative oil volume
data.
⋅ Plot data versus pressure to identify erroneous data (data not
following physically acceptable trends).
Cost 65 kNOK
Duration 10 days

Constant Composition Expansions (CCE) - Gas Condensates

Objectives Determine dewpoint pressure and volumetric properties at reservoir
temperature (and eventually at other lower temperatures).
Measured Data pd, Vro, Vrt, Zg, g, Bgw
Consistency ⋅ Compare reported Z-factors with values calculated from
Check composition and the Standing-Katz chart (p ≥pd).
⋅ Plot data versus pressure to identify erroneous data (data not
following physically acceptable trends).
Cost 20 kNOK
Duration 3 days
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Constant Composition Expansions (CCE) - Oils

Objectives Determine bubblepoint pressure and volumetric properties at reservoir
temperature and eventually at lower temperature.
Measured Data pb, Vrt, ρo, co, Y [Vro, o]

Consistency ⋅ Make undersaturated oil relative volume plot to determine

Check compressibility relation co=A/p; A=constant.
⋅ Plot data versus pressure to identify erroneous data (data not
following physically acceptable trends).
Cost 10 kNOK (TR) ; 5 kNOK (Tsc)
Duration 1 days

Differential Liberation Expansion (DLE):

Objectives Approximate the depletion process of a reservoir oil, and thereby
provide suitable PVT data for calculating depletion reservoir
performance.
a
Measured Data Bod, Rsd, Bgw, ρo, Zg, g, γ g, ρg [ o, yi, xi]
Consistency ⋅ Component and bulk material balance.
Check ⋅ Compare reported Z-factors with values calculated from
composition and the Standing-Katz chart (p ≥pd).
⋅ Plot data versus pressure to identify erroneous data (data not
following physically acceptable trends).
⋅ Plot differential Bod and Rsd data relative to bubblepoint oil volume
instead of residual oil volume using the variables Bod/Bodb and
(Rsdb-Rsd)/Bodb.
Cost 40 kNOK
Duration 8 days

a. Oil viscosity should always be ordered. Equilibrium gas compositions (through C7+ or C10+) should also be ordered
3 3
for oils with a solution GOR>100-150 Sm /Sm .
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2.1.4 Contact & Cooperation with Other Engineering Groups

When ordering PVT sampling and analyses, Reservoir Technology R&T
cooperates with Production Technology and Process Technology to collect
samples for analyses performed by these departments.

Fluid analyses performed or purchased by other departments may include:

Production Technology:
• Wax Point, Hydrate and Asphaltene Analyses (large separator samples
required)
• Formation Water/Brine Analyses

Process Technology:
• TBP-Analyses with high-temperature cuts (minimum 5 liter sample)
• CCEs specified at temperatures lower than reservoir temperature for
process simulation (also ordered by Reservoir Technology and used by
Production Technology in well hydraulics)

Production Geology:
• Formation water/brine resistivity for petrophysical analyses
• Geochemical analyses of collected fluids (natural tracers, Strontium-
isotope analyses, etc.)

Most of these special studies require large samples of separator or tank oil.

Design and planning of fluid sampling in cooperation with the department

responsible for well testing is important. Well test design and sample
preparations that may affect sampling should be discussed and included in plans
before sampling is performed.

Handling and transportation of the sample bottles after sampling should also be
discussed. Wax-, hydrate- and asphaltene analyses may be adversely affected if
o
the temperature of the sample bottles drop below about 30 C (even for a short
period).

2.1.5 Forms for Ordering Standard PVT Studies

Special forms have been generated for planning and ordering PVT samples and
analyses. Use of these forms (which are divided into three parts) is
recommended. The three parts are:

Part I describes fluid sampling (formations, conditions, methods) and

quality control of the samples collected.

Part II describes compositional analyses of the samples collected. Some

guidelines for quality control of compositional analyses are also discussed.
Part III specifies which PVT experiments should be performed, and
recommended design of the experiments (number of pressure steps, which
properties to measure, etc.).
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The laboratory chosen to perform the PVT analyses should present a quality
control of Part I before continuing to Parts II and III. This will ensure that
compositional analyses and PVT experiments to be performed are based on the
sample(s) considered most representative for the actual formation(s). The
purchaser should also require a preliminary report of Part II results before
continuing with Part III.

It is also important that the reservoir-, production-, and process engineers all
take part in filling out the forms, and eventually approve the plans for sampling
and analyses by signing the forms (page 1).

2.1.6 Ordering Special PVT Studies

Special PVT studies like Swelling Experiments, Multi-Contact Gas Injection
Experiments and Slimtube Experiments should be designed and ordered in
cooperation with PVT specialists. These experiments are considered important
for evaluation of EOR methods such as miscible and immiscible gas injection,
and WAG (water-alternating gas).

2.1.7 Following Up an Ongoing PVT Study

The order form discussed in Section 2.1.5 includes a few hints regarding follow
up of an ongoing PVT study. Some suggestions are:

• Stay in contact with the PVT laboratory during all phases of the study.

• Remind the PVT laboratory to respond back after quality control of sample
bottles, to ensure that the PVT study will be continued based on the best
samples.

• Remind the PVT laboratory to respond back after the compositional analyses
have been performed and quality checked. The PVT laboratory should ask
for your permission before they initiate the PVT experiments (i.e. they
should not start before the compositional analyses have been approved).

• Ask the PVT laboratory for all measured data; sometimes even "raw-data"
may be needed to check questionable reported data.
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2.2.2 Sampling Companies

Companies dealing with fluid sampling in the North Sea are listed below:

Company Sampling Methods Comments

Schlumberger RFT, MDT, BHS, SEP Used most for RFT, MDT
ELS BHS, RFT Single phase BHS
Western Atlas RFT, BHS, SEP Associated CoreLab
Petrotech BHS, SEP, IKS Single phase BHS
Altinex, NH BHS Petrotech is operator
Exal BHS, SEP ELS operator in Norway
Oilphase BHS Single phase BHS
(Petrotech is operator)

2.2.3 PVT Laboratories (external)

Company Available PVT Comments

Experiments

GECO Prakla Standard PVT ISO 9002 certification ongoing

Core Laboratories Standard PVT ISO 9002 certified
Aberdeen Swelling
Slimtube
Wax and Asphaltene
EXPRO Standard PVT ISO 9002 certified in 1994
Swelling
Slimtube
Wax and Asphaltene
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2.3 NOMENCLATURE
Abbreviations
BHS Bottomhole Sampling
BO Black Oil
CCE Constant Compositional Experiment
CVD Constant Volume Depletion
DLE Differential Liberation Experiment
FVF Formation volume factor
GC Gas Chromatography
GOR Gas-Oil Ratio
IKS Isokinetic Sampling
MST Multistage Separator Test
OGR Oil-Gas Ratio
RFT Repeat Formation Test
SEP Seperator Sample or Sampling
SST Single-stage Seperator Test
TBP True Boiling Point Analysis
WHS Wellhead Sampling

Symbols
3 3
Bg Dry Gas FVF from flash, m /Sm
3 3
Bgd Dry Gas FVF from DLE, CVD, m /Sm
3 3
Bgw Wet Gas FVF, m /Sm
3 3
Bo Oil FVF from seperator flash, m /Sm
3 3
Bod Differential oil volume factor from DLE, m /residual m
-1
co Isothermal oil compressibility, bar
Fi Hoffmann et al. Characterization Factor
3 3
GOR Gas Oil Ratio, Sm /Sm
Gp Cumulative mole percent (wet) gas produced in CVD experiment,
relative to initial moles at dewpoint
Ki Equilibrium constant, yi/xi
1/3
Kw Watson Characterization Factor [Kw≡Tb /γ]
Mg Molecular weight of gas, kg/kmol
MgN+ Molecular weight of the CN+ fraction in gas, kg/kmol
Mi Molecular weight of component i, kg/kmol
Mo Molecular weight of oil, kg/kmol
pb Bubblepoint pressure, bar
pd Dewpoint pressure, bar
pR Reservoir pressure, bar
psat Saturation pressure, bar
psp Separator pressure, bar
3 3
Rs Solution GOR from seperator flash, Sm /Sm
3 3
Rsd Differential solution GOR from DLE, Sm /residual m
3 3
Rsp Separator GOR, Sm /sep.m
rs Solution OGR from seperator flash of a gas condensate (rs=1/GOR),
3 3
Sm /Sm
TR Reservoir temperature, °C or K
Tsp Seperator temperature, °C or K
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Vi Volume fraction of component i at standard conditions

Vro Relative oil volume, relative to either total volume or volume at
saturation pressure (depends on the laboratory)
Vrt Total (gas-plus-oil) volume relative to volume at saturation pressure
wi Weight fraction
xi Oil molar composition
xir Residual oil molar composition
Y Function used in smoothing two-phase (gas-oil) volumetric data
below the bubblepoint during a constant compositional experiment
yi Gas molar composition
zi Recombined wellstream (reservoir) molar composition
Zg Deviation or Z-factor for gas
g Gas viscosity, mPa⋅s
m Cell Mixture Viscosity, mPa⋅s
o Oil viscosity, mPa⋅s
3
ρo Oil density, kg/m
go Gas-oil interfacial tension, mN/m
γg Specific gravity of gas (air=1)
γgN+ Specific gravity of the CN+ fraction in gas, water=1
γi Specific gravity of component i (water=1)
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Curtis H. Whitson (PERA a/s) November 1998

3. FLUID SAMPLING AND ANALYSIS OF

LABORATORY DATA

3.1 Introduction
3.1.1 Important PVT Data
Oil and gas samples are taken to evaluate the properties of produced fluids at
reservoir conditions, in the production tubing, and in pipeline transportation.
The key PVT (pressure-volume-temperature) properties to be determined for a
reservoir fluid include:

• Original reservoir composition(s)

• Saturation pressure at reservoir temperature
• Oil and gas densities
• Oil and gas viscosities
• Gas solubility in reservoir oil
• Liquid (NGL/condensate) content of reservoir gas
• Shrinkage (volume) factors of oil and gas from reservoir to surface
conditions
• Equilibrium phase compositions

Standard experimental procedures are used for measuring these properties,

including expansion and depletion studies, and multistage separator tests.

Reservoir fluid samples can also be used in gas injection studies, where oil
recovery by vaporization, condensation, and developed miscibility are
quantified. Slimtube tests and multicontact gas injection PVT studies are
typically used for this purpose.

Less traditional PVT analyses include:

• Analysis of produced water, including salinity and brine composition

• Wax and asphaltene analysis
• Hydrates and emulsions

This chapter summarizes the sampling procedures used to collect fluids, and
the experimental methods used to measure fluid properties. A summary of PVT
data is given in Table 3-1.

3.2 Sampling Methods

3.2.1 Type of Sampling
1
The API gives recommended practices for sampling oil and gas wells.
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Furthermore, Norsk Hydro has a chapter on Sampling Procedures in their Well

2
Testing Manual . Several sampling methods can be used to collect reservoir
fluids, including

• RFT Sampling
• Bottomhole sampling
• Separator sampling
• Wellhead sampling

The choice of method depends primarily on (1) whether the reservoir fluid is an
oil or gas, and (2) whether the reservoir fluid is saturated (or nearly saturated) at
reservoir conditions. The second condition is determined by whether the well
produces single phase fluid into the wellbore at the flowing bottomhole pressure.

Table 3-2 gives a Schlumberger-produced look-up table for determining

sample requirements for various situations in the testing of oil and gas
condensate reservoirs.

3.2.2 Representative Samples

Before field development starts, the primary goal of sampling is to obtain
"representative" samples of the fluid or fluids found in the reservoir at initial
conditions. It may be difficult to obtain a representative sample because of two-
phase flow effects near the wellbore. This occurs when a well is produced with
a flowing bottomhole pressures below the saturation pressure of the reservoir
a
fluid(s).

Misleading fluid samples may also be obtained if gas coning or oil coning
occurs.

The best (most representative) samples are usually obtained when the
reservoir fluid is single phase at the point of sampling, be it bottomhole or at the
surface. Even this condition, however, may not ensure representative sampling
(see section 3.2.5).

Because reservoir fluid composition can vary areally, between fault blocks,
and as a function of depth, we are actually interested in obtaining a sample of
reservoir fluid that is representative of the volume being drained by the well
during the test.

Unfortunately, the concept of a "representative" sample is usually

a
If a significant positive skin effect exists, then the region near the wellbore that actually is
below the saturation pressure may be insignificant (i.e. consisting of a volume that will practically
not effect produced fluid sampling). The well testing engineer should quantify the pressure drop
due to damage skin (if it exists) at the rate when the well experiences the lowest wellbore flowing
pressure. In fact, they should provide an adjusted flowing wellbore pressure plot versus time
during sampling that shows the effect of positive skin. The adjusted flowing pressure is probably
better to use in evaluating if wellbore conditions were in fact condusive to sampling.
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A sample that correctly reflects the composition of reservoir fluid at the

depth or depths being tested.

If we suspect or know that a sample is not "representative" (according to this

definition), then we tend to do nothing with the sample. Or we question the
validity of the PVT analysis done on the "unrepresentative" sample, and
consequently don't include the measured data when developing our EOS fluid
characterization.

In general, we should not use this definition of "representivity." First of all,

it is a definition that costs our industry in terms of wasted money and time, and
lost opportunity. Some points to keep in mind are:

Any fluid sample that produces from a reservoir is automatically

representative of that reservoir. After all, the sample is produced from the
reservoir!

The final EOS fluid characterization of the reservoir fluid(s) should be

required to match all (accurate) PVT measurements of all samples produced
from the reservoir, independent of whether the samples are representative of
insitu compositions.

Accuracy of PVT Data ≠ Representivity of Sample

Accurate PVT measurements can be made on both representative and

unrepresentative samples. Inaccurate PVT measurements can also be made
on both types of samples; bad PVT data should be ignored.

Furthermore, an EOS fluid characterization is used to predict compositional

changes during depletion which represent a much greater variation than the
compositional differences shown by "representative" and "unrepresentative"
samples.

Another misconception in "representative" fluid sampling of gas condensates

is that it is difficult to obtain insitu-representative samples in saturated gas
condensate reservoirs (with underlying oil). The exact opposite is true! We can
readily show that if a gas condensate is initially saturated and in contact with an
underlying oil zone, then a near-perfect insitu-representative sample can be
obtained (at the gas-oil contact). Independent of whether the reservoir gas and
reservoir oil samples collected are insitu-representative.

3.2.3 Define the Fluid Type

For a new discovery it is important that the fluid type and saturation conditions
can be estimated based on somewhat limited production data. Such data might
include producing gas-oil ratio, stock-tank oil and separator gas gravity,
reservoir temperature, and initial reservoir pressure. Produced wellstream
composition may also be available.
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Correlations such as presented by Standing and Glasø (section 4.4) can be

used to estimate bubblepoint pressure with an accuracy of 5 to 10%. When
composition is available, an equation of state can be used to predict the
saturation pressure (bubblepoint or dewpoint) with about the same accuracy.
Better predictions can usually be expected for oils, but with accurate
composition and C7+ properties, dewpoint predictions of gas condensates also
can be expected.

Figure 3-1 shows a typical pressure-temperature diagram for a reservoir

fluid. The phase envelope defines the locus of bubblepoints and dewpoints
joined at the critical point. A reservoir with temperature less than the critical
point is defined as an oil reservoir. A reservoir with temperature between the
critical temperature and the cricondentherm is defined as a gas condensate
reservoir. If reservoir temperature is higher than the cricondentherm then the
reservoir is defined as a gas reservoir.

Further qualtitative fluid definitions are sometimes used. For example, oil
reservoirs are classified in two categories: black-oil resevoirs and volatile oil
reservoirs (determined according to their initial solution GOR and STO gravity;
3 3 3 3
approximately, black-oil: Rs<150 Sm /Sm and volatile oil: Rs>150 Sm /Sm ).

Gas reservoirs are sometimes classified as wet gas reservoirs (producing

some liquid at surface conditions) or dry gas reservoirs (neglible surface liquid
production). Furthermore, gas condensate reservoirs are sometimes grouped into
3 3
the categories lean gas condensate reservoirs (GOR>2000 Sm /Sm ) and rich
3 3
gas condensate reservoirs (GOR<1000 Sm /Sm ).

Returning to Figure 3-1, a resevoir fluid is a single phase at conditions

outside the phase envelope. Within the phase envelope, two phases (gas and oil)
exist. Any time two phases coexist locally (e.g. gas and oil within a pore), each
phase separately is in a saturated state; the oil is at its bubblepoint and the gas is
at its dewpoint. This fundamental concept is instrumental in understanding
a
reservoir phase behavior.

Initially a reservoir will always be at a pressure and temperature that is one

or outside the phase envelope. During production and subsequent pressure
b
reduction in the reservoir, the system may enter the two-phase region.
a
Likewise, the concept of saturated phases applies to water and hydrocarbon phases in local
equilibrium. For example, in an oil-water system system, both phases are saturated - with respect
to each other. Even though the oil is highly undersaturated with respect to a gas phase, the oil is
still saturated - with respect to water; likewise, water is saturated with components in the oil phase.

b
After the reservoir enters the two-phase region, differential amounts of reservoir gas and oil
are produced, according to relative permeability and viscosity ratios of the two phases.
Subsequently, the remaining reservoir fluid does not have the same composition, and its phase
envelope will therefore change from the original phase envelope. It is therefore of limited use to
design reservoir behavior during depletion based on the original p-T diagram.
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In practice there are three types of fluid systems in a given geological

formation with vertical hydrodynamic communication. As shown in Figure 3-1,
these are:

• Undersaturated System with Uniform Composition

• Saturated System with Uniform Composition

• Saturated and/or Undersaturated System with Compositional Gradient

A primary objective of fluid analyses in new discoveries is to establish the type

of fluid system. However, without production from several intervals and/or
several wells, it will be difficult to establish the classification with any great
certainty.

Ula is an example of an undersaturated oil reservoir with relatively uniform

composition. Sleipner is an example of an undersaturated gas condensate
reservoir with relatively uniform composition. Troll is a saturated reservoir with
fairly uniform composition in the gas cap and in the oil.

Oseberg is an example of a saturated/undersaturated reservoir with

significant compositional variation with depth (particularly in the oil). Another
exmaple is the Statfjord formation in the Statfjord field.

Eldfisk and Ekofisk fields are examples of undersaturated oil reservoirs with
3
some compositional variation with depth. Interestingly, the variation of
composition (bubblepoint) with depth is not the same in the two main geological
formations (Ekofisk and Tor).

The Statfjord formation in the Brent field is perhaps the most unusual fluid
4
type. The reservoir is undersaturated throughout, but the composition varies
from a somewhat volatile oil at the bottom to a gas condensate at the top. At
some depth a transition from bubblepoint to dewpoint occurs - but without a gas-
oil contact! The point of transition is marked by a mixture with critical
temperature equal to reservoir temperature (at that depth); at the transition,
reservoir pressure is higher than the saturation (critical) pressure of the mixture
(see Figure 3-1).

3.2.4 Conditioning a Well Before Sampling

A well should normally be "conditioned" before sampling, particularly for gas
condensate and saturated oil wells. First the well is produced long enough to
clean up all chemicals that were used during the well completion. Next, the rate
is stepwise decreased until the flowing bottomhole pressure is larger than the
estimated saturation pressure (if possible).

The final flow rate must be large enough to maintain a stable producing
GOR and wellhead pressure, even if the flowing bottomhole pressure is less than
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the saturation pressure. Also, the final flow rate should be maintained long
enough to ensure that the producing GOR is more-or-less constant.
A constant producing GOR does not necessarily indicate that the produced
wellstream is "representative" of the original reservoir fluid. In fact, it may not
be possible to obtain a truly representative sample for reservoir oil and gas
condensate systems initially in a saturated state.

Sample containers are usually shipped by boat to land, and thereafter by air
or ground transport to the PVT laboratory. As requested by the field operator,
compositional analysis and standard PVT experiments are performed on the
samples at a PVT laboratory.

3.2.5 RFT Sampling

Repeat Formation Tester (RFT) sampling (open wellbore sampling) is probably
the least accurate of all methods of sampling, mostly because of the limited
volume of sampling. However, RFT samples should be valid under the
following conditions:

• Undersaturated oil
• High Permeability
• Water-based mud used when drilling

If oil-based mud is used during drilling then the samples can only be used for
approximate compositional analysis. The hydrocarbon components found in the
oil-based mud must be backed out of (subtracted from) the overall composition.

The greatest advantage of RFT sampling is that the fluid is defined for a
precise depth. Many reservoirs exhibit compositional variation with depth.
Accurate RFT samples can help establish this variation, typically a task that is
very difficult.

3.2.6 Bottomhole Sampling

Undersaturated oils are usually sampled with bottomhole containers lowered into
the wellbore on a wireline (Figure 3-3, Figure 3-1). The bottomhole sample is
taken while the well is flowing at a relatively low rate. The flowing bottomhole
pressure should always be higher than the estimated bubblepoint pressure of the
reservoir oil.

Bottomhole oil samples can also be taken when a well is shutin. The
flowing bottomhole pressure prior to shutin should be higher than the
bubblepoint pressure.

The typical procedure for bottomhole sampling includes:

• Install sample container in the production tubing

• Make pressure gradient measurements going into the hole
• Position sampler at the specified depth
• Produce the well at a low, stable rate (following conditioning)
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• Sample during the flow test (dynamic sample) or after shuting in the well
(static sample)
Traditional bottomhole samplers are often transferred to a sample container
while still on the drilling rig. (Norsk Hydro tries to practice transfer on land
when possible.) The procedure for this transfer includes:

• Measure the opening pressure of the BH sampler

o
• Heat the BH sampler to about 80 C
• Mix the sample by agitation/rotation
• Transfer to sample container

The saturation pressure of the sample is measured in the sample container at the
prevailing temperature.

To ensure that representative samples have been obtained, at least two (and
preferably three) BH samples should have the same bubblepoint pressure at
ambient temperature, within 3 to 4%.

3.2.7 Wellhead Sampling

If a produced oil is single phase at the wellhead then a sample can be taken
upstream to the choke. Several wellhead sampling methods can be used:

• Fill a membrane sampler by displacing the backpressure fluid (ethylene

glycol)
• Fill a piston cylinder sampler
• Fill an open cylinder containing mercury (sometimes not allowed
offshore, e.g. in Norway)

Successful wellhead samples should be very accurate if the temperature is above

the wax appearance point (WAP). Usually wellhead samples can only be taken
from high-pressure, deep wells that are highly undersaturated (e.g. Embla). In
general, wellhead (or bottomhole) samples are preferred for asphaltene studies.

3.2.8 Separator Sampling

Separator sampling is used for gas condensates and saturated oils. Separator
samples are also taken for gas injection studies requiring large sample volumes,
and for special studies involving analysis of asphaltene precipitation, wax
(paraffin) point, emulsions, hydrates, and corrosion.

The method relies on sampling separately the gas and oil leaving the primary
separator (Figure 3-1). The samples should be taken simultaneously, filling the
sample containers at a constant rate of about 1 liter/minute. The 20 liter gas
3
bottles are initially evacuated. The separator oil (about 600 cm ) can be
collected in a membrane bottle by displacing ethylene glycol, a piston cylinder,
or a mercury-filled container (not allowed offshore Norway). A good rule-of-
thumb is that it takes about one-half hour to collect a set of separator samples.

Criteria for valid separator sampling include:

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• Stable separator pressure and temperature, liquid level, and flow rates.
Excessive carryover (due to high rates) should be avoided.

• Critical flow through the choke, requiring that separator pressure is less
than 1/2 of the wellhead flowing pressure. Sometimes this criterion
cannot be achieved, and strictly speaking it is not necessary if separator
conditions are stable.

Separator gas and separator oil rates are measured during the sampling to
determine the ratio with which to recombine the separator samples. The
recombined mixture should yield an overall fluid representing the wellstream
that entered the separator. This wellstream hopefully represents the reservoir
fluid. Measured separator gas rates are corrected in the laboratory using standard
orifice equations.

Separator gas rate is about 3 to 10% accurate (Daniel mixer), and the liquid
rate should be 2 to 5% accurate using a rotameter. Carryover of separator oil in
the gas stream may be a problem for high-rate gas condensate wells (particularly
lean condensate wells). As much as 30-40% of the separator oil (condensate)
may be carried over in the gas stream of a lean condensate producing into a
standard 20-foot separator. The separator gas sampler may or may not capture
the carried-over liquid. Irregardless, the potential error in calculated wellstream
composition may be significant for large carryover (low separator efficiency).

Three types of separator sampling can then be requested:

• Standard sampling
• Isokinetic sampling
• Mini-laboratory (Thorton) sampling

Standard separator sampling should almost always be collected for gas

condensate and saturated oils.

If carryover is suspected, isokinetic samples can be taken to quantify the

separator efficiency, and thereby establish the neccesary corrections to make a
valid recombination. A more expensive alternative is the Thorton sampling
technique for gas condensates.

3.2.9 Isokinetic Sampling

Isokinetic sampling may be recommended for lean gas condensates with
documented low separator efficiency, characterized by significant carryover of
separator oil into the separator gas stream. The method is based on sampling the
separator gas twice:

• First, a sample of the oil-free gas is taken by sampling in the same

direction as gas flows.
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• Second, a sample of the separator gas containing the entrained

(carryover) separator oil is taken by sampling against the direction of gas
flow at a properly controlled sampling rate (isokinetically).

Comparing the two sample compositions, carryover or separator efficiency can

be quantified. 1 shows the isokinetic sampling equipment.

3.2.10 Mini-Laboratory (Thorton) Sampling

A mixing block is placed in a vertical 2.3" flowline, upstream from a 5/64"
sample line lodged perpendicular to flow. The sampling assembly is located
downstream to the choke and upstream to the separator (Figure 3-1). A mini
laboratory separator is used to analyze the wellstream sample by conducting a
controlled multistage separation, with compositions and separator GORs
measured directly, and wellstream recombination calculated onsite.

The mini-laboratory sampling approach is expensive and therefore not

usually recommended. Careful separator sampling, eventually with isokinetic
sample control of liquid carryover, should usually be sufficient for most gas
condensate reservoirs.

3.2.11 Sample Treatment at the PVT Laboratory

When the samples arrive at the PVT laboratory the samples must be checked for
quality and possible leakage. Several methods can be used to check sample
consistency. It is important to establish which samples should be used for the
PVT study, mainly based on these consistency checks.

Bottomhole and wellhead oil samples are brought to the same temperature
that was used to determine the bubblepoint on the wellsite. The bubblepoint is
determined for each sample, and if the bubblepoints from the laboratory and the
wellsite check within 1% for a given sample then it is considered valid.

Several problems may cause lab and wellsite bubblepoints to deviate. If the
3 3
oil is somewhat volatile (GOR>150 Sm /Sm ) then it may be difficult to
measure the bubblepoint graphically using a pressure-volume plot. This is a
typical problem for high bubblepoint oils (pb>250 bar). Another problem is that
equilibrium may not have been reached at each pressure when measurements
were conducted on the wellsite. Finally, the pressure gauges may have been
improperly calibrated.

Separator samples also can be checked for leakage (look in the sample box!).
The oil sample is checked by measuring the bubblepoint at separator
temperature. If the measured bubblepoint is within about 1-2% of the separator
pressure then the oil sample is considered valid.

The pressure in the gas sample bottle is checked against the separator
pressure. Note that the opening pressure at room temperature may be larger than
separator pressure because the sample container may have been colder than
room tempearature when filled at the separator. The basic control relation for
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checking opening pressure of gas samples is

Topening
popening = psp (3-1)
Tsp
where pressures and temperatures are given in absolute units. It may be difficult
to establish the proper "Tsp" in this equation, as the actual temperature may be
affected by the atmospheric conditions, as well as temperature reduction during
the "flashing" of gas into the sample bottle.

3.3 Compositional Analysis and Quality Control

PVT studies are usually based on one or more samples taken during a production
test. Bottomhole samples can be obtained by wireline using a high-pressure
container, either during the production test or during a shutin period. Separator
samples may also be taken during a production test.

This section discusses how wellstream compositions are determined. The

standard approach consists of first separating the high-pressure sample into low-
pressure gas and oil samples which are each analyzed using gas chromatography
(GC). The overall mixture composition is obtained by mathematically
recombining the separated gas and oil compositions.

The standard components quantified in petroleum reservoir fluids include

• Non-Hydrocarbons N2 CO2 H2S

• Hydrocarbons C1 C2 C3 iC4 nC4 iC5 nC5 C6s C7+

(or C7 C8 C9 C10+)

Table 3-2 lists example compositions of the main fluid types, together with
relevant reservoir and surface properties. Figure 3-1 illustrates the classification
of fluid types based on composition in the form of a simple ternary diagram.
Also shown is the classification based on producing (initial) gas-oil ratio and oil-
gas ratio.

3.3.1 Gas Chromatography

Compositional measurements are made using gas chromatography and
sometimes true boiling point (TBP) distillation. Gas chromatography measures
the weight (mass) fraction of individual components in a mixture. TBP analysis
gives additional information about the amount and properties of heavier
components (heptanes and heavier, C7+).

Gas chromatography is based on selective separation of components as

5
temperature is increased in a capillary tube (Figure 3-1) . The sample is injected
to the GC, followed by a carrier gas such as helium or nitrogen. As temperature
increases, the lighter components separate and move together with the carrier gas
to a flaming ion detector (FID).
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Instead of a carrier gas, a carrier liquid or supercritical fluid can be used to

transport separated components. These methods are referred to as liquid
chromatography and supercritical fluid chromatography, respectively.

The FID signal for a component is shown as a peak on the chromatographic

line (Figure 3-1). The relative mass of a component is given by the area under
the peak, divided by the total area created by all components in the mixture.
Note that FID only responds to organic compounds. A particular component can
be identified by the time (temperature) when its peak appears. For example, the
methane peak appears before the ethane peak, which occurs before the propane
peak, and so on.

A thermal capacity detector (TCD) may be used in some chromatographs.

This dector measures the difference in thermal capacity between the pure carrier
gas and the carrier gas mixed with the component being detected. The
difference in thermal capacity is a function of the number of molecules of the
component. In contrast to the FID, which measures relative mass of each
component, the TCD measures relative moles of each component. Also, the
TCD can be used for both hydrocarbon and nonhydrocarbon compounds.

Norsk Hydro uses TCD for non-hydrocarbons, and FID for hydrocarbons.

Accurate quantitative GC analysis depends on reproducible retention times,

and known dector response for the range of components being analyzed. Several
sources of error in GC analysis are given below:

• Improper handling of the sample before injection

• Method used for injection
• Decomposition of sample during analysis
• Bad chromatographic system; tailing or overuse of the system
• Variation in detector response
• Calibration errors
• Error in response area measurements (integration)

3.3.2 Natural Gas Analysis

A packed column with TCD is used to separate nonhydrocarbon (inorganic)
components such as nitrogen, carbon dioxide, and hydrogen sulphide, as well as
methane and ethane. Chromatographic separation using FID in a capillary
column is used for components methane through decane.

An external standard and response factor are used to quantify the analysis
more precisely. The response factor for FID includes (implicitly) the molecular
weight to convert from mass to mole fraction. Finally, the FID and TCD
analyses are combined using ethane analyses to "bridge" the combination of the
two analyses, where normalization with a volume correction is used.

3.3.3 Oil/Condensate GC Analysis

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A capillary column with FID is used to analyse atmospheric oil and condensate
samples. The analysis can be carried out to carbon numbers 30 or greater, but an
internal standard such as squaline is usually needed to ensure accurate
quantitative conversion of response areas to mass fractions. Figure 3-1 shows a
typical oil chromatogram (of a stock-tank condensate).

Simulated distillation (SIMDIS) by GC analysis may also be used. SIMDIS

is usually conducted with a 30-50 m capillary column using Helium as the
o o
carrying gas with a diluted sample (1:100), temperatures from 50 -280 C at
o
4 C/min.

Conversion from mass fraction to mole fraction requires molecular weights

of all components. Because molecular weights are not measured, and for a given
carbon number the molecular weight may vary by 5 or 10 molecular weight units
(depending on the type of hydrocarbons found in the particular carbon number),
conversion to mole fractions is only approximate.

Many laboratories use paraffin molecular weights (given by the relation

Mi=14i+2) to convert GC mass fractions to mole fractions. The molecular
6
weights given by Katz and Firoozabadi for carbon numbers up to C45 are
probably more accurate for stock tank oils and condensates (Charts 3 and 4 in
7
the Fluid Properties Data Book) .

3.3.4 True Boiling Point (TBP) Analysis

True boiling point distillation may supplement traditional GC analysis of oil and
condensate samples. TBP distillation separates an oil into cuts or fractions
according to the range of boiling points used for separation. Figure 3-1 defines
typical refined petroleum products in terms of carbon number fractions. Figure
3-1 illustrates the range of carbon number fractions containing various
hydrocarbon compounds (e.g. n-alkanes).
6
The recommended standard uses normal boiling points of paraffins to
separate individual carbon number fractions. To avoid decomposition
("cracking") of the oil during distillation, vacuum is applied in four stages to
reduce the distillation temperatures for heavier components:

• Atmospheric (1013.0 mbar)

• 100 torr (133.0 mbar)
• 10 torr (13.0 mbar)
• 2 torr (2.6 mbar)

The distillation usually proceeds from C7 (or C9) to about C25, plus a residue
(~C26+). Figure 3-1 shows a TBP distillation apparatus recommended in ASTM
8
D-2892.

The mass, volume, molecular weight, and density (specific gravity) of each
distilled fraction is measured directly. Table 3-4 gives results of TBP distillation
o o
of stock-tank oil. Reported densities are at a temperature of 15 C (60 F) and
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atmospheric pressure. Some of the heavier fractions may have a higher pour
o o
point than 15 C (i.e the fraction is not fluid at 15 C), and the measured density is
made at a higher temperature (Table 3-5). This density is then corrected to the
reported value using standard thermal correction tables.

Because the separation of components in a given distillation cut is only

approximate, some overlap is observed. For example, the C12 cut may contain
10% C11 compounds, 85% C12 compounds, and 5% C13 compounds. The
overlap worsens at lower distillation pressures because the difference in
distillation temperatures is reduced between cuts. Table 3-6 and Figure 3-1
show the overlap for an example TBP distillation.

The overlap can be corrected to yield an "ideal" distillation curve (Table 3-

7). The resulting ideal distillation curve should be quite similar to the simulated
distillation curve, as shown in Figure 3-1.

One advantage with TBP analysis is that measured molecular weights are
available for converting from mass to mole fraction. Molecular weights are
measured using a cryoscopic method (freezing point depression), a method that
is sensitive to error and probably reliable at best to about ±2 to 5%. Measured
molecular weights are compared with GC-based calculated molecular weights in
Table 3-5.

Table 3-8 summaries the GC/TBP analysis of the example stock-tank oil,
where results are provided through C10+.
6
Average boiling points are taken from the tables of Katz and Firoozabadi.
With these boiling points and with measured specific gravities the critical
properties and acentric factors of the fractions can be estimated from
correlations. Critical properties are needed in PVT calculations with an equation
of state (EOS). Reservoir, pipeflow, and process simulations may also require
EOS calculations.

It is recommended that at least one TBP analysis be measured for each

reservoir fluid in a given field. As an extreme example, a field such as Visund
might require up to four TBP studies:

• (1) gas cap and (2) equilibrium oil samples in the Brent formation
• (3) gas condensate in the Statfjord formation
• (4) near-critical oil in the Lunde formation

Note that it may be difficult to use several TBP analyses to come up with a
single EOS characterization for reservoirs with multiple fluids (e.g.
compositional variation or gas cap/oil). The examples in sections 5.5.2 and
5.6.2 discuss the use of TBP data in EOS fluid characterization.

Mass fractions measured from TBP analysis should be reasonably close to

mass fractions determined from simulated distillation. However, SIMDIS does
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not provide properties of the individual fractions (molecular weight and density).
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3.3.5 Bottomhole Sample Composition

Table 3-8 shows the reported wellstream composition of a reservoir oil, where
C6, C7, C8, C9, and C10+ specific gravities and molecular weights are also
reported. In the example report, composition is given both as mole and weight
percent, though many laboratories only report molar composition.
Experimentally, the composition of a bottomhole sample is determined by
(Figure 3-3, Figure 3-1):

• Flashing the sample to atmospheric conditions.

• Measuring the quantities of surface gas and oil.
• Determining the normalized weight fractions of surface samples by gas
chromatography.
• Measuring molecular weight and specific gravity of the surface oil.
• Converting weight fractions to normalized mole fractions.
• Recombining mathematically to the wellstream composition.

The most probable source of error in wellstream composition of a

bottomhole sample is the surface oil molecular weight which usually is accurate
within 5 to 10%. TBP data, if available, can be used to check surface oil
molecular weight.

3.3.6 Recombined Sample Composition

Table 3-10 presents the separator oil and gas compositional analyses of a gas
condensate fluid, together with recombined wellstream composition. The
separator oil composition is obtained using the same procedure as for
bottomhole oil samples. This involves bringing the separator oil to standard
conditions, measuring properties and compositions of the resulting surface oil
and gas, and recombining these compositions to give the separator oil
composition which is reported as shown in Table 3-10.

The separator gas sample is introduced directly into a gas chromatograph.

Weight fractions are converted to mole fractions using appropriate molecular
weights. C7+ molecular weight is back-calculated using measured separator gas
specific gravity.

The separator oil and gas compositions can be checked for consistency using
9 10
the Hoffman et al. K-value method and Standing's low-pressure K-value
equations (section 3.4.10).

Table 3-12 gives a summary of equations used to correct test separator gas-
oil ratio for use in recombination.

3.4 PVT Experiments

3.4.1 Multistage Separator Test
The multistage separator test is conducted on oil samples primarily to provide a
basis for converting differential liberation data from a residual oil to a stock-tank
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oil basis (see section 3.4.4).

Occasionally, several separator tests are conducted to determine the separator

conditions that maximize stock-tank oil production. Usually two or three stages
of separation are used, with the last stage being at atmospheric pressure and
near-ambient temperature (15 to 25°C). The multistage separator test can also
be conducted for rich gas condensate fluids.

Figure 3-1 illustrates schematically how the separator test is performed.

Initially the reservoir sample is brought to saturation conditions and the volume
is measured. The sample is then brought to the pressure and temperature of the
first-stage separator. All of the gas is removed and the oil volume at the
separator stage is noted, together with the volume, number of moles, and specific
gravity of the removed gas. If requested, the composition of gas samples can be
measured.

The oil remaining after gas removal is brought to the conditions of the next
separator stage. The gas is again removed and quantified by moles and specific
gravity. Oil volume is noted, and the process is repeated until stock-tank
conditions are reached. The final oil volume and specific gravity are measured
o
at 15.5 C and one atmosphere.

Table 3-13 gives results from a three-stage separator test. Gas removed at
each stage is quantified as standard gas volume per volume of stock-tank oil.
Sometimes an additional column of data is reported, giving standard gas volume
per volume of separator oil; note, you can not add GORs reported relative to
separator oil volumes.

3.4.2 Constant Composition Expansion - Oils

For an oil sample the constant composition expansion (CCE) experiment is used
to determine the bubblepoint pressure, the undersaturated oil density and
isothermal oil compressibility, and the two-phase volumetric behavior at
pressures below the bubblepoint. Table 3-14 presents data from an example
CCE experiment for a reservoir oil.

The procedure for the CCE experiment is shown in Figure 3-1. A PVT cell
is filled with a known mass of reservoir fluid and brought to reservoir
temperature. Temperature is held constant during the experiment. The sample
is initially brought to a condition somewhat above the initial reservoir pressure,
ensuring that the fluid is single phase. As the pressure is lowered, oil volume
expands and is recorded.

The fluid is agitated at each pressure by rotating the cell. This avoids the
phenomenon of supersaturation or metastable equilibrium where a mixture
remains as a single phase, even though it should split into two phases.
Sometimes supersaturation occurs 3 to 7 bar below the actual bubblepoint
pressure. By agitating the mixture at each new pressure, the condition of
supersaturation is avoided and the bubblepoint can be determined more
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accurately.

Just below the bubblepoint the total volume will increase more rapidly
because gas evolves from the oil. This yields a higher system compressibility.
Visually, gas can be seen at the top of the cell (if a visual cell is used). The total
volume is recorded after the two-phase mixture is brought to equilibrium.
Pressure is lowered in steps of 1 to 15 bar, where equilibrium is obtained at each
pressure. When the lowest pressure is reached, total volume is 3 to 5 times
larger than the original bubblepoint volume.

The recorded cell volumes are plotted versus pressure, and the resulting
curve should be similar to one of the curves shown in Figure 3-1. For a "black
oil" the discontinuity in volume at the bubblepoint is sharp. The bubblepoint
pressure and bubblepoint volume are easily read from the intersection of the
pressure-volume trends from the single-phase and the two-phase regions.

Volatile oils do not exhibit the same clear discontinuity in volumetric

behavior at the bubblepoint pressure (Figure 3-1). Instead, the p-V curve is
practically continuous in the region of the bubblepoint because undersaturated
oil compressibility is similar to the effective two-phase compressibility just
below the bubblepoint. This makes it difficult to determine the bubblepoint of
a
volatile oils using a pressure-volume plot. Instead, a windowed cell is used for
visual observation of the first bubble of gas at the bubbleopint. Liquid shrinkage
below the bubblepoint can also be measured in a visual cell during the constant
composition expansion.

Reported data from commercial laboratories usually include bubblepoint

pressure, bubblepoint density or specific volume, and isothermal compressibility
of the undersaturated oil at pressures above the bubblepoint. The oil's thermal
expansion may also be reported, indicated by the ratio of undersaturated oil
volume at a specific pressure and reservoir temperature to the oil volume at the
same pressure and a lower temperature.

Total volume below the bubblepoint can be correlated by the Y function,

defined as
(pb /p) - 1 (p b /p) - 1
Y≡ = (3-2)
V rt - 1 (V t / V b) - 1

where p and pb are given in absolute pressure units. Plotting Y versus pressure
should yield a straight line, as shown in Figure 3-1. The linear trend can be used
to smooth total volume data at pressures below the bubblepoint.

a
Reported bubblepoint pressures measured at the wellsite on bottomhole samples of volatile
oils are obviously subject to large inaccuracy because a pressure-volume plot is used. This should
be kept in mind when comparing laboratory-measured bubblepoint with wellsite-determined
bubblepoint in the selection (rejection) of valid samples.
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3.4.3 Constant Composition Expansion - Gas Condensates

The CCE experiment for a gas condensate reports the total relative volume,
defined as the volume of the gas or gas-plus-oil mixture divided by the dewpoint
a
volume. Z-factors are also reported, at the dewpoint pressure and above. Table
3-15 and Figure 3-1 gives example CCE data for a gas condensate.

Wet-gas FVF (or its inverse) is reported at the dewpoint and/or initial
reservoir pressure. These values represent the gas equivalent or wet-gas volume
at standard conditions produced from one volume of reservoir gas.

Most CCE experiments are conducted in a visual cell for gas condensates.
Relative oil (condensate) volumes are reported at pressures below the dewpoint,
where relative oil volume is usually defined as the oil volume divided by the
total volume of gas-plus-oil; in some reports, however, relative oil volume is
defined as the oil volume divided by the dewpoint volume (Norsk Hydro
practice).

3.4.4 Differential Liberation Expansion

The differential liberation expansion (DLE) experiment is designed to
approximate the depletion process of an oil reservoir, and thereby provide
suitable PVT data for calculating reservoir performance. Figure 3-1 illustrates
the laboratory procedure of a DLE experiment. Figure 3-1 through Figure 3-1
and Table 3-16 through Table 3-19 give DLE data for an oil sample.

A blind cell is filled with an oil sample which is brought to a single phase at
reservoir temperature. Pressure is decreased until the fluid reaches its
bubblepoint, where the oil volume is recorded; knowing the initial mass of the
sample, the bubblepoint density can be calculated.

The pressure is decreased below the bubblepoint and the cell is agitated until
equilibrium is reached. All gas is removed at constant pressure, and the volume,
moles, and specific gravity of the removed gas are measured. Sometimes gas
compositions are also measured. The remaining oil volume is also recorded.
This procedure is repeated 10 to 15 times at decreasing pressures, and finally at
atmospheric pressure.

The final oil is cooled, where the resulting "residual" oil volume and specific
gravity are measured (or calculated) at 15.5°C. Residual oil composition may
b
also be reported.
a
If Z-factors are also reported below the dewpoint then they represent ficticious, non-physical
quantities that should not be used.

b
None of the data reported for the residual oil should be used as data in doing an EOS fluid
characterization. The reason is simply that the process used in the lab from the next-to-last stage to
atmospheric pressure (and reservoir temperature) is not a single flash as simulated by an EOS. The
last-stage depletion process may be conducted differently by various laboratories; usually it is a
bleeding process, or bleeding/flash/bleeding process.
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Based on measured data, other properties are calculated, including

differential solution gas-oil ratio (Rsd), differential oil FVF (Bod), oil density, and
gas Z-factor.

3.4.5 Converting from Differential to Stock-Tank Basis

Traditionally the most important step in the application of oil PVT data for
reservoir calculations is the conversion of differential solution gas-oil ratio (Rsd)
and differential oil FVF (Bod) to a stock-tank oil basis. For engineering
calculations, volume factors Rs and Bo are used to relate reservoir oil volumes to
produced surface volumes.

Differential properties Rsd and Bod reported in the DLE report are relative to
residual oil volume, i.e., the oil volume at the end of the DLE experiment,
corrected from reservoir to standard temperature. The equations traditionally
used to convert differential volume factors to a stock-tank basis are:
Bob )
R s = R sb - (R sdb - R sd )( (3-3)
Bodb

Bob )
Bo = Bod ( (3-4)
Bodb
where Bob and Rsb are the bubblepoint oil FVF and solution GOR, respectively,
from a multistage separator flash. Rsdb and Bodb are differential volume factors at
the bubblepoint pressure. The term (Bob/Bodb) is used to eliminate the residual
oil volume from the Rsd and Bod data. Note that the conversion from differential
to "flash" data depends on the separator conditions because Bob and Rsb depend
on separator conditions.

The conversions given by Eqs. (3-3) and (3-4) are only approximate. Figure
3-1 shows the conversion of differential Bod to flash Bo for the example oil with
differential data reported in Table 3-16 through Table 3-19.
11
A more accurate method was suggested by Dodson et al. Their method
requires that some of the equilibrium oil be taken at each stage of a depletion
experiment (DLE, CCE, or CVD (see section 3.4.6)) and flashed through a
multistage separator. The multistage separation gives Rs and Bo directly. This
laboratory procedure is costly and time-consuming, and therefore never used.
However, the method is readily simulated with an equation of state model
12 13
(Whitson and Torp ; Coats ).

Figure 3-1 shows oil volume factors and solution GORs calculated using the
standard conversion given by Eqs. (3-3) and (3-4), compared with the Dodson
method (Whitson and Torp procedure) using an EOS. The oil is slightly
volatile, and it is seen that the approximate conversion gives approximately the
same results as using the more rigorous Dodson method.

Figure 3-1 shows a similar comparison for a highly (near-critical) volatile

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oil. The difference in both oil volume factor and solution GOR is significant,
and clearly the traditional conversion of DLE data can not be used for this type
of fluid.

It should be realized that even when dealing with a slightly volatile oil
3 3
(GOR>125 Sm /Sm ), a modified black-oil (MBO) PVT formulation should be
used in reservoir calculations (material balance and simulation). The MBO
formulation is compared with the traditional black-oil formulation in Figure 3-1.
The main difference is that the MBO treatment accounts for the ability of
reservoir gas to volatilize intermediate and heavier components that produce a
suface condensate when produced.

The ratio of surface condensate produced from reservoir gas to surface gas
produced from reservoir gas is the solution oil-gas ratio RV (sometimes written
rs). The gas FVF also must be adjusted from the traditional definition to account
for the reservoir gas that becomes condensate at the surface (i.e. that the moles
of reservoir gas does not equal the moles of surface gas, as is assumed in the
traditional definition of gas FVF). The resulting gas FVF is called "dry" gas
FVF, with symbol Bgd.

3.4.6 Constant Volume Depletion

The constant volume depletion (CVD) experiment is designed to provide
volumetric and compositional data for gas condensate (and volatile oil)
reservoirs producing by pressure depletion. The stepwise procedure of a CVD
experiment is shown schematically in Figure 3-1. Table 3-19 and Table 3-21
give CVD data for an example gas condensate fluid.

The CVD experiment provides data that can be used directly in reservoir
engineer calculations, including:

• Reservoir material balance giving recovery of total wellstream (wet gas

recovery) versus average reservoir pressure.

• Produced wellstream composition and surface products (sales gas,

condensate, and NGLs) versus reservoir pressure.

• Average oil saturation in the reservoir (liquid dropout and

revaporization) that occurs during pressure depletion.

For most gas condensate reservoirs producing by depletion, the recoveries and
oil saturations versus pressure from the CVD analysis closely approximate actual
a
field performance. If other recovery mechanisms such as water drive and gas

a
The basic assumption is that hydrocarbons condensed in the reservoir, on the whole (i.e.
neglecting local saturation effects near the wellbore), do not flow in significant amounts to
production wells. The reason is simply that the relative mobility of oil is much smaller than the
reservoir gas mobility.
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cycling are considered, the basic data required for reservoir engineering are still
taken mainly from a CVD report.

3.4.7 PVT Data Accuracy

The accuracy of PVT measurements is difficult to quantify. Norsk Hydro has,
however, studied the problem and Table 3-22 gives guidelines for measurement
accuracies of most PVT data.

3.4.8 PVT Consistency Checks

The quality of PVT data may vary from poor to excellent. It may not be
obvious, however, when inaccurate data are reported. Several methods can be
used to determine the quality of reported PVT data. The recommended
consistency checks given below should be used for PVT data that will be used in
reservoir studies, or in the development of an equation of state characterization.

3.4.9 Watson Characterization Factor

The C7+ molecular weight is highly susceptible to error, with an accuracy
ranging from 2 to 10%. Specific gravity of C7+, on the other hand, should be
accurate within a fraction of a percent.
14
The characterization factor Kw was introduced by Watson to qualitatively
describe the relative paraffinicity of a petroleum product. Kw is defined as
K w = T b / γ , where Tb is the normal boiling point in R and γ is the specific
1/ 3 o

gravity relative to water.

Stock-tank oils and condensates contain many hundreds of hydrocarbon

compounds. Because STO consists mainly of the C7+ material, the
characterization or "paraffinicity" of a reservoir fluid can be described by the
Watson characterization factor of the C7+ fraction.

The following table gives the range of the Watson characterization factor for
pure compounds in the three main hydrocarbon families, and for stock-tank
oils/condensates.

Hydrocarbon Pure Stock-Tank Oil/

Type Compound Condensate (C7+)
Paraffin 12-14 12-12.5
Napthene 10-12
Aromatic 8-10 11-11.5

15
Whitson gives an approximate relation for Kw that can be used for
heptanes-plus,
γ 7+
0.15178 -0.84573
K w 7+ = 4.5579 M7+ (3-5)

Austad et al. show that for a given formation in a reservoir, Kw7+ should be very
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constant, even during depletion and even if the STO gravity varies initially
(Figure 3-1).

Based on this observation, it is recommended that Kw7+ be calculated for

each new PVT sample in a field/reservoir. A plot of M7+ versus γ7+ can be
updated with each new sample, where a line of constant Kw7+ is drawn for the
field average. Deviation of ±0.03 in Kw7+ is acceptable. Larger deviations in
Kw7+ from the field/reservoir average may (probably) indicate an error in the
measured M7+.

If larger errors in M7+ are found, then potential errors in reported molar
composition should be checked.

3.4.10 Hoffman et al. Kp-F Plot

The consistency of separator gas and oil compositions can be checked using a
9
diagnostic plot proposed by Hoffman, Crump, and Hocott. They show that K-
values (on a log scale) plotted versus a component factor Fi (on a linear scale)
should result in a straight-line relationship.

To apply this method to separator samples, the K-values are calculated first
from separator gas and oil compositions, Ki=yi/xi where yi=separator gas molar
composition and xi=separator oil molar composition.

The Hoffman characterization factor Fi is given by

Fi = bi (1 / Tbi - 1 / Tsp) (3-6)

o
where Tbi is the normal boiling point in R, Tsp is the separator temperature in
o
R, and bi is a component constant given formally by
log(pci / psc)
bi = (3-7)
1 / T bi - 1 / Tci
where pci is critical pressure in psia, psc is standard pressure in psia, and Tci is
o
critical temperature in R.
10
Standing gives modified values of bi and Tbi to be used with the Hoffman
et al. method, as shown in Table 3-23. Standing also gives the expected slope
and intercept of the line as a function of pressure and temperature for typical
separator conditions,
log K i psp = a + c Fi (3-8)

where
a = 1.20 + 4.5 × 10-4 psp + 15.0 × 10-8 psp
2

(3-9)
c = 0.89 - 1.7 × 10- 4 psp - 3.5 × 10-8 psp
2

with psp given in psia.

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According to Standing, the correlations for a and c are valid up to pressures

o
of 70 bar and temperatures from 5 to 95 C.

A plot of measured separator K-values using this method should not deviate
significantly from the Standing straight line. Heptanes plus, nonhydrocarbons,
and components with small amounts (<0.5 mol-%) in either the separator oil or
gas sample may deviate from the straight line without causing concern.
However, if the key hydrocarbons methane through hexane show significant
deviation from the straight line, the compositional analysis should be used with
scrutiny.

Figure 3-1 shows a Kp-F plot for the separator sample given earlier (Table3-
10).

3.4.11 Correcting GOR for Liquid Carryover

The reported separator GOR (Rsp) may be in error for several reasons:

• Incorrect separator oil rate

• Incorrect separator gas rate
• Carryover of separator oil in separator gas stream
• Gas in the oil line
• Incorrect measurement of the "meter factor"
• Combination of the above

It is probably reasonable to say that reported GOR has an accuracy of 5 to 15%,

with even greater errors possible for lean gas condensates producing at high
rates.

The recombined wellstream zi composition is calculated from

zi = Fgsp yi + (1 - Fgsp ) xi (3-10)
where Fgsp is the total mole fraction of total wellstream that leaves the separator
a
in the gas stream,
-1
 ρosp 
Fgsp = 1 + 23.68
(3-11)
 M osp R sp 
3
where ρosp is the separator oil density in kg/m , Mosp is the separator oil
3 3
molecular weight (kg/kmol), and Rsp is separator gas-oil ratio in Sm /sep. m .

If the GC analyses are done properly, both separator oil composition xi and
separator gas composition yi should be correct, even if carryover is a problem.

a
When carryover occurs, Fgsp calculated using test GOR will also include the entrained liquid
that is carried over in the gas stream leaving the separator. This is because the measured gas rate
includes the amount (moles) of carryover.
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The traditional method of sampling gas (downstream) will minimize the amount
of carryover that enters the gas sample container. Also, if the gas sample is
brought to separator conditions before charging the chromatograph, only
equilibrium gas will be removed for analysis, and the carryover separator oil will
remain in the sample container.
We can usually assume with reasonable accuracy that the separator gas and
oil compositions, as reported, can be used for recombination if the Hoffman et
al. plot is acceptable. To obtain a valid wellstream composition from Eq. (3-10),
however, the recombination GOR may need to be corrected (for one of several
reasons).

If carryover exists then the separator gas rate reflects both the amount
(moles) of separator gas ng plus the moles of carryover separator oil ÿno, the
total being expressed as a standard gas volume (Figure 3-1). The separator oil
rate reflects the total separator oil rate no less the moles of separator oil carryover
(i.e. n *o = n o − ∆n o ). In terms of an overall molar balance,

n = ng + no
(3-12)
= n g + (n *o + ∆ n o)
and in terms of a component molar balance,
zi n = yi n g + x i n o
= y i n g + x i ∆ n o + x i n *o (3-13)
= y i (n g + ∆ n o) + x i n *o
*

where yi and xi are standard separator samples (i.e. true equilibrium phase)
compositions (assuming downstream sampling of the separator gas collects little
if any of the carryover separator oil). An isokinetic gas sample, on the other
hand, represents the separator gas plus carryover separator oil y*i .

Defining the separator oil carryover osp as

∆ no
δosp ≡ (3-14)
no
the effect of carryover on wellstream composition is calculated by first
correcting the test gas mole fraction (Fgsp)test calculated from the test GOR. The
corrected gas mole fraction reflects the true fraction of the total wellstream that
is separator gas (ng/n),
ng n
(Fgsp )corr = = g
ng + no n
(3-15)
(F ) - δosp
= gsp test
1 - δosp

Furthermore, the measured test separator GOR (Rsp)test can be corrected for
carryover to yield the true separator GOR,
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1 /( Fgsp )test - 1
(R sp )corr = (R sp )true = (R sp )test (3-16)
1 /(Fgsp )corr - 1

Table 3-12 and section 4.3.2 discuss the corrections to reported wellsite
separator test GOR. The corrections result in a test GOR (Rsp)test that is then
used in Eq. (3-11) to determine (Fgsp)test (referred to in the equations above).
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3.5 References
1. API Recommended Practice for Sampling Petroleum Reservoir Fluids,
American Petroleum Institute (1966) 44.

2. "Well Testing Manual," Norsk Hydro.

3. Belery, P. and da Silva, F.V.: "Gravity and Thermal Diffusion in

Hydrocarbon Reservoirs," paper presented at the Third Chalk Research
Program, Copenhagen (1990).

4. Bath, P.G.H., van der Burgh, J., and Ypma, J.G.J.: "Enhanced Oil Recovery
in the North Sea," 11th World Petroleum Congress (1983).

5. Freyss, H., et al.: "PVT Analysis for the Oil Reservoirs," The Technical
Review (Schlumberger) (1989) 37, No. 1, 4-15.

6. Katez, D.L., and Firoozabadi, A.: "Predicting Phase Behavior of

Condensate/Crude-Oil Systems Using Methane Interaction Coefficients,"
JPT (Nov. 1978) 1649-1655; Trans., AIME, 265.

7. Whitson, C.H.: Petroleum Engineering Fluid Properties Data Book,

Trondheim, Norway (1994).

8. "Distillation of Crude Petroleum (15-Theoritical Plate Column): Designation

D2892-84, "Annual Book of ASTM Standards, (1984) 821-860.

9. Hoffmann, A.E., Crump, J.S., and Hocott, C.R.: "Equilibrium Constants for
a Gas-Condensate System," Trans., AIME (1953) 198, 1-10.

10. Standing, M.B.: "A Set of Equations for Computing Equilibrium Ratios of a
Crude Oil/Natural Gas System at Pressures Below 1,000 psia," JPT (Sept.
1979) 1193-1195.

11. Dodson, C.R., Goodwill, D., and Mayer, E.H.: "Application of Laboratory
PVT Data to Reservoir Engineering Problems," Trans., AIME (1953) 198,
287-298.

12. Whitson, C.H. and Torp, S.B.: "Evaluating Constant Volume Depletion
Data," JPT (March 1983) 610-620; Trans., AIME, 275.

13. Coats, K.H.: "Simulation of Gas Condensate Reservoir Performance," JPT

(Oct. 1985) 1870-1886.

14. Watson, K.M., Nelson, E.F., and Murphy, G.B.: "Characterization of

Petroleum Fractions," Ind. Eng. Chem. (1935) 27, 1460-1464.

15. Whitson, C.H.: "Characterizing Hydrocarbon Plus Fractions," SPEJ (Aug.

1983) 683-694; Trans., AIME, 275.
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Table 3-1

Gas
Laboratory Analysis Oils Condensates

Standard
Bottomhole Sample Composition

Recombined Separataor Composition 

C7+ TBP Distillation  
C7+ Simulated Distillation (SIMDIS)  
Constant Composition Expansion


Multistage Surface Separation

Differential Liberation
N
Constant Volume Depletion 

Special
Multicontact Gas Injection  
Wax Point Determination  
Asphaltene Precipitation  
Slimtube Analysis (MMP/MME)  
Water Analysis  
Salinity, salt composition, solution gas ratio Rsw and solution
gas composition, water FVF Bw, density

Standard
 Can Be Performed
N Not Performed
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Table 3-2
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Table 3-3

Near-
Component/ Dry Wet Gas Critical Volatile Black
Properties Gas Gas Condensate Oil Oil Oil
CO2 0.10 1.41 2.37 1.30 0.93 0.02
N2 2.07 0.25 0.31 0.56 0.21 0.34
C1 86.12 92.46 73.19 69.44 58.77 34.62
C2 5.91 3.18 7.80 7.88 7.57 4.11
C3 3.58 1.01 3.55 4.26 4.09 1.01
iC4 1.72 0.28 0.71 0.89 0.91 0.76
nC4 0.24 1.45 2.14 2.09 0.49
iC5 0.50 0.13 0.64 0.90 0.77 0.43
nC5 0.08 0.68 1.13 1.15 0.21
C6s 0.14 1.09 1.46 1.75 1.61
C7+ 0.82 8.21 10.04 21.76 56.40
M7+ 130 184 219 228 274
γ7+ 0.763 0.816 0.839 0.858 0.920
Kw7+ 12.00 11.95 11.98 11.83 11.47
GOR, Sm3/Sm3 ∞ 18,700 970 650 265 53
OGR, Sm3/Sm3 0 0.000053 0.00103 0.00154
γo 0.751 0.784 0.802 0.835 0.910
γ API 57 49 45 38 24
g 0.61 0.70 0.71 0.70 0.63
psat, bara 236 452 484 374 194
Bsat, m3/Sm3 0.0051 0.0039 2.78 1.73 1.16
ρsat, kg/m
3
154 428 492 612 823
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Table 3-4

CUT AET (C) PRESSURE CORR. MOLE- DEN-SITY CUMUL. CUNUL. CUMUL.
No. (mbar) WEIGHT WEIGHT VOLUME% WEIGHT% MOLE%

6 69.2 1013.0 2.0678 74.0 637.3 2.82 2.10 6.80

7 98.9 1013.0 2.8579 91.9 737.7 6.19 5.00 14.40
8 126.1 1013.0 4.1783 105.0 761.4 10.96 9.24 24.10
9 151.3 1013.0 3.1564 119.6 767.0 14.54 12.45 30.60
10 174.6 1013.0 3.3304 135.5 781.2 18.24 15.83 36.60
11 196.4 1013.0 3.2152 152.1 788.8 21.79 19.09 41.80
12 217.3 133.0 2.6398 166.8 814.6 24.60 21.77 45.60
13 236.1 133.0 3.2922 177.6 821.6 28.09 25.11 50.20
14 253.9 133.0 3.2779 192.0 831.5 31.51 28.44 54.30
13 271.1 133.0 3.4858 205.4 839.0 35.13 31.98 58.50
16 287.3 133.0 3.1219 218.9 845.0 38.34 35.15 62.00
17 303.0 133.0 3.3203 238.1 841.9 41.77 38.52 65.40
18 317.0 13.3 2.0351 249.8 857.2 43.83 40.58 67.40
19 331.0 13.0 2.4673 260.7 856.8 46.33 43.09 69.70
20 344.0 13.0 3.1851 267.7 854.9 49.57 46.32 72.60
21 357.0 13.0 2.9337 281.8 868.5 52.51 49.30 75.20
22 369.0 13.0 1.8715 298.4 869.4 54.38 51.20 76.70
23 381.0 13.0 2.2685 311.4 870.5 56.65 53.50 78.5
24 392.0 13.0 2.6268 326.2 873.6 59.26 56.17 80.40
25 402.0 13.0 2.2631 347.5 876.7 61.51 58.46 82.00
26 413.0 2.6 2.8756 362.8 887.6 64.32 61.38 84.00
27 423.0 2.6 2.7514 368.5 891.1 67.01 64.18 85.00
28 432.0 2.60 1.6452 383.1 896.2 68.60 65.85 86.00
RESIDUE 33.6463 630.0 931.6 100.00 100.00 99.00
SUM 98.5136 241.0 856.4

+ DENSITY MOLE WEIGHT% MOLE% VOLUME%

FRACTION WEIGHT
C7+ 853.50 252.30 97.90 93.16 97.18
C1O+ 868.00 303.10 87.55 69.35 85.46
C15+ 885.30 377.00 71.56 45.58 68.49
C20+ 898.50 452.20 56.91 30.22 53.67
C25+ 911.60 540.40 43.83 19.48 40.74
C29+ 921.60 627.60 34.15 13.07 31.40
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Table 3-5

Cut Dens. Dens. Dens. Dens. MW MW Carb.

15.0C 30.0C 35.0C 50.0C cryo. gc nr.
C7- *637.3 * *
C7 *737.7 * *
C8 *761.4 * *
C9 *767.0 * *
C10 781.2 135.5 141.0 9.9
C11 788.8 152.1 155.5 11.0
C12 814.6 166.8 170.8 12.0
C13 821.6 177.6 182.9 12.9
C14 831.5 192.0 196.5 13.9
C15 839.0 205.4 210.3 14.9
C16 845.0 218.9 224.6 15.9
C17 841.9 238.1 239.0 16.9
C18 857.2 249.8 252.5 17.9
C19 856.8 260.7 261.5 18.5
C20 854.9 267.7 274.7 19.5
C21 868.5 281.8 290.2 20.6
C22 859.2 298.4 304.0 21.6
C23 860.5 311.4 315.5 22.4
C24 863.4 326.2 329.9 23.4
C25 866.5 347.5 345.8 24.6
C26 873.8 362.8 363.0 25.8
C27 877.4 368.5 378.1 26.9
C28 872.4 383.1 393.2 27.9
C28+ 909.1 630.0
NORSK Field Development & Technology MANUAL
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Curtis H. Whitson (PERA a/s) November 1998

Table 3-6

CUT NO. CORR. MOLE- DENSITY N-2 N-i N N+1 N+2

WEIGHT WEIGHT

6 2.0678 74.0 637.3 0.0 0.0 100.0 0.0 0.0

7 2.8579 91.9 737.7 0.0 0.0 100.0 0.0 0.0
8 4.1783 105.0 761.4 0.0 0.0 100.0 0.0 0.0
9 3.1564 119.6 767.0 0.0 0.0 100.0 0.0 0.0
10 3.3304 135.5 781.2 0.1 14.3 75.5 10.1 0.0
11 3.2152 152.1 788.8 0.2 11.3 78.4 10.2 0.0
12 2.6398 166.8 814.6 0.1 7.6 77.0 15.3 0.0
13 3.2922 177.6 821.6 0.2 17.7 69.7 12.4 0.0
14 3.2779 192.0 831.5 0.2 19.3 69.2 11.3 0.0
15 3.4858 205.4 839.0 0.3 20.2 68.8 10.8 0.0
16 3.1219 218.9 845.0 0.2 18.8 69.7 11.3 0.0
17 3.3203 238.1 841.9 0.2 15.9 72.1 11.8 0.0
18 2.0351 249.8 857.2 0.3 17.4 72.7 9.6 0.0
19 2.4673 260.7 856.8 1.9 41.2 56.6 0.4 0.0
20 3.1851 267.7 854.9 5.2 43.3 47.3 4.2 0.0
21 2.9337 281.8 868.5 4.8 35.2 53.9 6.1 0.0
22 1.8715 298.4 869.4 3.7 35.7 58.1 2.5 0.0
23 2.2685 311.4 870.5 6.2 47.0 46.3 0.6 0.0
24 2.6268 326.2 873.6 5.9 44.5 49.7 0.0 0.0
25 2.2631 347.5 876.7 2.6 37.8 59.6 0.0 0.0
26 2.8756 362.8 887.6 1.5 31.4 52.0 15.0 0.0
27 2.7514 368.5 891.1 3.3 23.3 57.0 14.2 2.2
28 1.6452 383.1 896.2 3.1 19.3 55.5 22.1 0.0
RESIDU 33.6463 630.0 931.6 0.0 0.0 100.0 0.0 0.0
E
SUM 98.5136 241.0 856.4
NORSK Field Development & Technology MANUAL
HYDRO Reservoir Technology PVT ANALYSIS

Chapter 3 Fluid Sampling & Laboratory Data Rev. 0.6

Page 33
Curtis H. Whitson (PERA a/s) November 1998

Table 3-7

FRACTION WEIGHT% VOLUME% CUMUL.

VOLUME%

C7- 2.10 2.82 2.82

C7 2.90 3.37 6.19
C8 4.25 4.77 10.96
C9 3.69 4.12 15.08
C10 2.92 3.20 18.28
C11 3.11 3.38 21.66
C12 2.99 3.15 24.81
C13 3.39 3.53 28.34
C14 3.44 3.54 31.88
C16 3.41 3.48 35.36
C16 3.13 3.17 38.53
C17 3.19 3.25 41.78
C18 3.10 3.10 44.87
C19 3.16 3.15 48.03
C20 2.66 2.66 50.69
C21 2.56 2.52 53.22
C22 2.52 2.49 55.70
C23 2.36 2.32 58.02
C24 2.25 2.21 60.23
C25 2.38 2.32 62.55
C26 2.22 2.14 64.69
C27 2.35 2.26 66.95
C28 1.32 1.27 68.22
RESIDUE 34.58 31.78 100.00
SUM 100.00 100.00
NORSK Field Development & Technology MANUAL
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Chapter 3 Fluid Sampling & Laboratory Data Rev. 0.6

Page 34
Curtis H. Whitson (PERA a/s) November 1998

Table 3-8

WELL 34/8-1
DATE 01-AUG-86

WEIGHT OF OIL (g) 98.5136

DENSITY (kg/m3) 847.24
MOLEWEIGHT (STO) 240.12
LOSS (%) 0.553

COMPOSITION OF LIGHT END.

GROUP WEIGHT% DENSITY MOLE WEIGHT MOLE%

N2 0.000 260.0000 28.0000 0.000

C02 0.000 420.0000 44.0000 0.000
Cl 0.002 260.0000 16.0000 0.030
C2 0.009 358.0000 30.0700 0.072
C3 0.067 507.6000 44.0970 0.365
iso-C5 0.050 563.3000 58.1240 0.206
n-C4 0.209 584.7000 58.1240 0.863
neo-C5 0.005 596.7000 72.1510 0.017
iso-C5 0.222 624.6000 72.1510 0.738
n-C5 0.406 630.9000 72.1510 1.350
C6 1.129 665.9611 85.4676 3.169
C7 2.901 737.7272 91.8668 7.576
C8 4.245 761.3593 104.9967 9.700
C9 3.687 767.0172 119.5922 7.397
C10+ 87.067 867.1056 304.8689 68.518
SUM 99.999 847.24 240.12 100
NORSK Field Development & Technology MANUAL
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Chapter 3 Fluid Sampling & Laboratory Data Rev. 0.6

Page 35
Curtis H. Whitson (PERA a/s) November 1998
Table 3-9

Component Wt % mol % mol wt.

Nitrogen 0.10 0.29

Carbon dioxide 0.59 1.05
Methane 12.58 61.07
Ethane 1.77 4.58
Propane 1.79 3.16
iso-Butane 0.41 0.55
n-Butane 1.07 1.43
iso-Pentane 0.52 0.57
n-Pentane 0.72 0.78
Hexanes 1.16 1.07 84.50
P 1.06 0.96
N 0.10 0.11
A 0.00 0.00
Heptanes 2.00 1.72 90.70
P 0.00 0.67
N 0.90 0.81
A 0.24 0.24
Octanes 2.89 2.14 105.00
P 1.17 0.80
N 1.19 0.90
A 0.53 0.44
Nonanes 2.21 1.45 118.50
P 1.08 0.65
N 0.42 0.28
A 0.71 0.52
Decanes plus 72.19 20.14 279

SUM 100.00 100.00

Average molecular weight: 77.90
zi - mol % Mi ρi zi Mi zi Mi / ρ=i
C7 1.72 90.7 0.74 156.0 210.0
C8 2.14 105.0 0.76 224.7 296.0
C9 1.45 118.5 0.78 171.8 220.9
Cl0+ 20.14 279.0 0.88 5619.1 6407.1
Sum / Aver. 25.45 242.5 0.87 6171.6 7134.0
Kw7+= 11.85
 NORSK Field Development & Technology MANUAL
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Chapter 3 Fluid Sampling & Laboratory Data Rev. 0.6

Page 36
Curtis H. Whitson (PERA a/s) November 1998
Table 3-10

RECOMBINED COMPOSITION
DATE 11/11-88
3 3
WELL 34/8-3 Rsp = 2638 / 1.157 = 2280 Sm / Sm
BOTTLE NO. A10996
TYPE OF DST2 * Pseudo?? = Lab recomb. Conditions ≠=sep. cond.
SAMPLE
TEMP. (C) 56.3
PRESSURE 50.3 field
(bara):
3 3
GOR (Sm3/Sm3) 2385 (pseudo) X 2638 Sm / Sm
OIL 721 Field
DENSITY (kg/m3): 754.1 (pseudo) X sep. oil 15 C
MOLEWEIGHT 115.50 CRYOSCOPY

GAS PHASE LIQUID PHASE RECOMBINED COMPOSITION

FRACTION WEIGHT% MOLE% WEIGHT% MOLE% DENSITY MOLEWG WEIGHT% MOLE%
N2 1.273 0.848 0.015 0.064 260.0 0.910 0.800
C02 2.906 1.232 0.155 0.407 420.0 2.111 1.181
Cl 76.952 89.496 2.259 16.263 260.0 55.379 84.988
C2 7.263 4.506 0.842 3.235 358.0 5.409 4.428
C3 4.908 2.076 1.403 3.674 507.6 3.895 2.174
ISO-C4 1.017 0.326 0.546 1.086 563.3 0.881 0.373
N-C4 2.226 0.714 1.647 3.273 584.7 2.059 0.872
NEO-C5 0.013 0.003 0.015 0.024 596.7 0.013 0.005
ISO-C5 0.744 0.192 1.166 1.867 624.6 0.866 0.295
N-C5 0.907 0.234 1.817 2.909 630.9 1.170 0.399
C-6 0.796 0.174 3.926 5.281 664.4 85.88 1.700 0.488
C-7 0.667 0.139 8.194 10.280 736.3 92.06 2.841 0.763
C-8 0.287 0.053 10.280 11.277 753.4 105.29 3.173 0.743
C-9 0.041 0.006 8.342 8.020 764.6 120.14 2.439 0.499
C-10+ 0.000 0.000 59.391 32.341 870.5 212.11 17.154 1.991
GAS PHASE LIQUID PHASE RECOM. COMPOSITION
WEIGHT-% C6+ 1.7917 90.13 27.3071
NOLE-% C6+ 0.3715 67.20 4.4850
MOLEWEIGHT 89.9680 154.92 149.8737
C6+
MOLEWEIGHT C1O+ 156.0000 212.11 212.1052
MEAN NOLEWEIGHT 18.6546 115.50 24.6159
MOLE-DISTRIBUTION 93.8429 6.16 100.0000
WEIGHT-DISTRIBUTION 71.1123 28.89 100.0000
GAS GRAVITY 0.6433
CRITICAL 205.2575
TEMP(K)
CRITICAL PRESS(bara) 46.4660 M7+ 160.8
Z-FACTOR 0.9179 ρ 7+ 829.6
DENSITY (kg/m3) 37.3054 346.4548
VISCOSITY (mpa*s) 0.0131
FRACTION GAS PHASE LIQUID PHASE RECOM. COMPOSITION
P N A P N A P N A
C6 97.10 2.90 98.50 1.50 98.00 2.00
C7 37.50 47.20 15.40 48.50 40.80 10.60 46.70 41.90 11.40
C8 32.50 43.70 23.70 48.20 35.80 16.00 47.20 36.30 16.50
C9 84.60 13.10 2.10 56.70 20.30 23.00 57.00 20.20 22.80
 NORSK Field Development & Technology MANUAL
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Chapter 3 Fluid Sampling & Laboratory Data Rev. 0.6

Page 37
Curtis H. Whitson (PERA a/s) November 1998

Table 3-11

DATE 11/11-88
WELL 34/8-3
BOTTLE NO. 23
TYPE OF SAMPLE KOND . DST2
TEMP. (C) 56.30
PRESSURE (bara): 50.30
GOR (Sm3/5m3) 44.40
OIL
DENSITY (kg/m3): 783.6 15 C
NOLEWEIGHT 146 CRYOSCOPY

GAS PHASE LIQUID PHASE RECOMBINED COMPOSITION

FRACTION WEIGHT% MOLE% WEIGHT% MOLE% DENSITY MOLEWG WEIGHT% MOLE%
N2 0.255 0.249 0.000 0.000 260.00 0.015 0.064
C02 2.560 1.588 0.000 0.000 420.00 0.155 0.408
Cl 37.202 63.308 0.003 0.027 260.00 2.259 16.268
C2 13.257 12.034 0.041 0.199 358.00 0.842 3.236
C3 17.650 10.924 0.354 1.172 507.60 1.403 3.675
ISO-C4 4.582 2.152 0.286 0.718 563.30 0.546 1.086
N-C4 10.522 4.941 1.074 2.698 584.70 1.647 3.274
NEO-C5 0.063 0.024 0.012 0.024 596.70 0.015 0.024
ISO-C5 3.397 1.285 1.022 2.068 624.60 1.166 1.867
N-C5 3.913 1.480 1.682 3.404 630.90 1.817 2.910
C-6 3.066 0.978 3.982 6.768 664.40 85.89 3.926 5.282
C-7 2.505 0.767 8.561 13.568 736.00 92.12 8.194 10.283
C-8 0.938 0.250 10.883 15.088 753.40 105.31 10.280 11.280
C-9 0.091 0.020 8.875 10.785 764.60 120.14 8.342 8.022
C-10+ 0.000 0.000 63.225 43.479 827.00 212.30 59.391 32.321
GAS PHASE LIQUID PHASE RECOM. COMPOSITION
WEIGHT-% C6+ 6.5996 9S.S3 90.1340
MOLE-% C6+ 2.0149 89.69 67.1880
MOLEWEIGHT C6+ 89.4029 155.50 154.9925
MOLEWEIGHT C10+ 156.0000 212.30 212.3037
MEAN MOLEWEIGHT 27.2958 146.00 115.5350
MOLE-DISTRIBUTION 25.6598 74.34 100.0000
WEIGHT-DISTRIBUTION 6.0620 93.94 100.0000
GAS GRAVITY 0.9412
CRITICAL TEMP(K) 256.3946
CRITICAL PRESS(bara) 45.4203
Z-FACTOR 0.8095
DENSITY (kg/m3) 61.8986 734.2313
VISCOSITY (mpa*s) 0.0125
FRACTION GAS PHASE LIQUID PHASE RECOM. COMPOSITION.
GAS
P N A P N A P N A
C6 97.0 3.0 98.5 1.5 98.5 1.5
C7 36.3 49.2 14.5 48.7 40.7 10.6 48.5 40.8 10.6
C8 30.7 55.2 14.1 48.3 35.7 16.0 48.2 35.8 16.0
C9 58.3 32.7 9.0 56.7 20.3 23.0 56.7 20.3 23.0
NORSK Field Development & Technology MANUAL
HYDRO Reservoir Technology PVT ANALYSIS

Chapter 3 Fluid Sampling & Laboratory Data Rev. 0.6

Page 38
Curtis H. Whitson (PERA a/s) November 1998

Table 3-12

TEST SEPARATOR GOR CORRECTION

FOR WELLSTREAM RECOMBINATION CALCULATIONS

( Zg )field ( γ g )field (psc )field

(R sp )lab = (R sp )field
( Zg )lab ( γ g )lab (psc )lab

1
Fgsp =
ρosp
1 + 23.68
M osp (R sp )lab

zi = Fgsp yi + (1 - Fgsp ) xi

(Rsp)field = separator gas-oil ratio based on rates calculated in the field,

3 3
Sm /sep.m

(Rsp)lab = corrected separator GOR at laboratory conditions, used to determine the

physical and mathematical recombination molar ratio Fgsp

(Zg)field = separator gas Z-factor used in field calculation of gas rate

(Zg)lab = laboratory (true) separator gas Z-factor determined in the laboratory at

conditions during gas metering

(γg)field = separator gas gravity used in field calculations of gas rate

(γg)lab = separator gas gravity based on measured composition or direct

measurement
3
(ρosp) = separator oil density at separator conditions during sampling, kg/m

(Mosp) = separator oil molecular weight

Fgsp = mole fraction of total wellstream leaving the separator in the gas stream

yi = laboratory measured separator gas molar composition

xi = laboratory measured separator oil molar composition

zi = wellstream molar composition

NORSK Field Development & Technology MANUAL
HYDRO Reservoir Technology PVT ANALYSIS

Chapter 3 Fluid Sampling & Laboratory Data Rev. 0.6

Page 39
Curtis H. Whitson (PERA a/s) November 1998

Table 3-13

THREE STAGE SEPARATOR TEST OF RESERVOIR FLUID TO

STOCK TANK CONDITIONS

Stage Pressure Temp. °C Evolved gas Rs Bo Density of st. Gas gravity

3 3 3 3 3 3 3
bar 3) Sm /m 3) Sm /m 4) m /m tank oil kg/m Air=1

424.5 1) 114.0 2) 221.8 1.640 0.659

1 70.0 50.0 183.6 38.2 1.140 0.628
2 30.0 50.0 20.1 18.1 1.104 0.662
3 atm 15.0 18.1 0.0 1.000 851.8 0.974
34.4 API

1 Bubble point pressure at reservoir temperature

2 Reservoir
temperature
3 3
3 Standard m gas per m stock tank oil
4 3 3
m liquid at indicated pressure and temperature per m stock tank oil
NORSK Field Development & Technology MANUAL
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Chapter 3 Fluid Sampling & Laboratory Data Rev. 0.6

Page 40
Curtis H. Whitson (PERA a/s) November 1998

Table 3-14

PRESSURE-VOLUME RELATION OF RESERVOIR FLUID

Pressure Relative Isothermal "Y"

volume V/Vbp compressibility
-1
bar

548.7 0.9737 1.78E-04

525.9 0.9781 1.91E-04
501.7 0.9824 2.05E-04
478.3 0.9874 2.19E-04
452.6 0.9934 2.34E-04
430.5 0.9985 2.46E-04
424.5 1.0000 2.50E-04
412.8 1.0063 4.520
391.4 1.0197 4.294
368.3 1.0363 4.200
338.6 1.0622 4.078
306.4 1.0977 3.944
276.1 1.1416 3.796
239.3 1.2149 3.602
202.7 1.3219 3.399
155.9 1.5512 3.126
116.4 1.9184 2.882
85.9 2.4620 2.696

Best fit V equation above boiling point

-4 -7 2
Vrel = 1.1617 - 5.120 X 10 p + 3.091 X 10 p

Best fit Y equation

-2
Y = 2.286 + 0.532 X 10 p
NORSK Field Development & Technology MANUAL
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Chapter 3 Fluid Sampling & Laboratory Data Rev. 0.6

Page 41
Curtis H. Whitson (PERA a/s) November 1998

Table 3-15

T = 112 °C
Pressure bara Relative Rel. (1) Volumetric (2) Compositional
volume liquid % Z-factor (3) Z-factor
532.42 0.909 1.2172 1.2171

511.54 0.924 1.1887 1.1927

491.25 0.940 1.1612 1.1693
470.57 0.958 1.1334 1.1459
451.48 0.976 1.1080 1.1247
435.89 0.992 1.0873 1.1076
432.39 0.998 1.0834 1.1038
430.39 0.999 1.0801 1.1017
Pd - 430.00 1.000 Trace 1.0788 1.1007
422.99 1.007 0.045 1.0707
416.50 1.015 0.218 1.0633
401.50 1.035 0.787 1.0448
381.61 1.065 1.606 1.0215
361.71 1.099 2.550 0.9994
341.51 1.139 3.460 0.9778
321.41 1.185 4.354 0.9574
301.51 1.239 5.507 0.9391
281.41 1.304 6.714 0.9225
261.50 1.380 7.528 0.9074
241.79 1.473 8.179 0.8951
221.79 1.587 8.848 0.8850
201.47 1.729 9.230 0.8761
181.46 1.909 9.701 0.8711
161.54 2.139 9.912 0.8688
141.43 2.443 10.076 0.8688
121.31 2.857 10.097 0.8715
101.69 3.433 9.972 0.8777
81.16 4.343 9.726 0.8863
63.14 5.656 9.395 0.8980

(1). Retrograde liquid deposit in volume % of sample

volume at dewpoint.

(2). Z = pV/nRT. Not corrected for liquid deposit

below the dewpoint.

(3). Z-factor from the recombined composition in

table 4 by the Dranchuc
correlation
 NORSK Field Development & Technology MANUAL
HYDRO Reservoir Technology PVT ANALYSIS

Chapter 3 Fluid Sampling & Laboratory Data Rev. 0.6

Page 42
Curtis H. Whitson (PERA a/s) November 1998

Table 3-16

DIFFERENTIAL LIBERATION OF RESERVOIR FLUID AT 114 °C

3 3
Pressure (bar) 3) Oil Formation 4) Solution Gas- 5) Gas Density of 2) Bt (m /Sm )
Volume Factor Oil Ratio Rs Formation saturated oil
3 3 3
Bo (Sm /Sm ) Volume Factor (kg/m )
3 3
Bg (m /Sm )
548.7 1.691 643.40
525.9 1.698 640.50
501.7 1.714 634.40
452.6 1.725 630.60
430.5 1.734 627.40
424.5 1.736 250.50 626.40 1) 1.736
391.3 1.650 217.10 3.76E-03 643.20 1.775
345.3 1.557 180.90 4.00E-03 662.50 1.835
300.7 1.484 151.20 4.43E-03 679.00 1.924
252.5 1.415 123.60 5.17E-03 696.40 2.071
203.1 1.354 98.30 6.28E-03 712.80 2.309
153.1 1.297 74.60 8.24E-03 729.50 2.747
101.8 1.242 51.50 1.256E-02 746.50 3.741
49.7 1.187 29.10 2.649E-02 764.80 7.050
14.2 1.140 12.60 9.664E-02 781.60 24.129
1.0 1.091 787.40

Density of residual oil at 15 °C: 859.0 kg/m3

3
1) Density at bubble point from single flash: 634.5 kg/m Bo, see fig. 8
2) Volume of oil and liberated gas at p and tivolume of residual oil Rs, see fig. 9
3 3
3) m liquid at indicated pressure per m residual oil Bg, see fig. 10
3 3
4) Standard m gas per m residual oil Density of saturated oil, see fig. 14
3 3
5) m gas at indicated pressure per m gas at standard condition
NORSK HYDRO A/S
Well: 34/8-3A DST1A
NORSK Field Development & Technology MANUAL
HYDRO Reservoir Technology PVT ANALYSIS

Chapter 3 Fluid Sampling & Laboratory Data Rev. 0.6

Page 43
Curtis H. Whitson (PERA a/s) November 1998

Table 3-17

DIFFERENTIAL LIBERATION OF RESERVOIR FLUID AT 114 °C

(Gas properties calculated from molecular composition)

Pressure (bar) 1) Gas Gas gravity Compressibility Molecular

viscosity (Air = 1) factor, Z wieght
(mPa/s)
391.3 0.0256 0.654 1.0697 18.94
345.3 0.0242 0.662 1.0238 19.18
300.7 0.0226 0.661 0.9844 19.16
252.5 0.0208 0.657 0.9488 19.02
203.1 0.0190 0.656 0.9234 19.00
153.1 0.0174 0.654 0.9135 18.94
101.9 0.0159 0.665 0.9196 19.27
49.7 0.0146 0.702 0.9463 20.33
14.2 0.0135 0.835 0.9763 24.18
1.0 - 2.069 - 59.93

1) For the calculation ref. page 46

Gas viscosity, see fig. 11
Gas gravity, see fig. 12
Compressibility factor, see fig. 13
 NORSK Field Development & Technology MANUAL
HYDRO Reservoir Technology PVT ANALYSIS

Chapter 3 Fluid Sampling & Laboratory Data Rev. 0.6

Page 44
Curtis H. Whitson (PERA a/s) November 1998

Table 3-18

DIFFERENTIAL LIBERATION OF RESERVOIR FLUID AT 114.0 °C

MOLECULAR COMPOSITION OF LIBERATED GASES weight % (wt.%) and mol%

Pressure/bar 391.3 345.3 300.7

Wt% mol % Mol. Wt% mol % Mol. Wt% mol Mol.
weight weight % weight
Nitrogen 0.91 0.61 0.99 0.68 0.89 0.61
Carbon dioxide 2.91 1.25 2.87 1.25 2.87 1.25
Methane 75.19 88.79 73.92 88.40 74.19 88.61
Ethane 7.45 4.69 7.26 4.64 7.28 4.64
Propane 5.67 2.44 5.84 2.54 5.57 2.42
iso-Butane 1.17 0.38 1.13 0.37 1.10 0.36
n-Butane 2.60 0.85 2.57 0.85 2.50 0.82
i so-Pentane 0.99 0.26 1.01 0.27 0.98 0.26
n-Pentane 1.18 0.31 1.28 0.34 1.22 0.32
Hexanes 1.07 0.24 84.2 1.42 0.32 84.3 1.35 0.31 84.3
Heptanes 0.71 0.15 90.3 1.30 0.27 90.8 1.34 0.28 91.1
Octanes 0.15 0.03 105.1 0.41 0.07 105.1 0.61 0.11 105.1
Nonanes 0.00 0.00 0.00 0.00 0.08 0.01 118.2
Decanes-plus 0.00 0.00 0.00 0.00 0.02 0.002 156
Sum 100.00 100.00 100.0 100.00 100.0 100.0
0 0 02
Average molwt. 18.94 19.18 19.16
NORSK Field Development & Technology MANUAL
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Chapter 3 Fluid Sampling & Laboratory Data Rev. 0.6

Page 45
Curtis H. Whitson (PERA a/s) November 1998

Table 3-19

VISCOSITY OF RESERVOIR
FLUID AT 114 °C

Pressure Viscosity
bar mPa.s
530.0 0.321
510.5 0.315
491.5 0.310
471.5 0.306
451.5 0.300
Pb 431.5 0.293
424.5 0.292
394.5 0.320
371.3 0.340
341.9 0.367
299.4 0.418
253.7 0.484
202.3 0.580
152.1 0.685
101.5 0.829
49.5 1.045
12.1 1.397
1.0 1.564
NORSK Field Development & Technology MANUAL
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Chapter 3 Fluid Sampling & Laboratory Data Rev. 0.6

Page 46
Curtis H. Whitson (PERA a/s) November 1998

Table 3-20

Depletion study of reservoir fluid at 112 °C

Pressure Retrograde Cumulative Z-factor, Z-factor

bara liquid deposit produced fluid volumetric compositional
vol % of mole % of Z=pV/nRT (D.P.R.)
dewpoint vol. initial fluid
Pd 430.0 0.00 0.00 1.080 1.102
407.7 0.67 2.71 1.103 1.074
372.2 2.43 7.07 1.033 1.033
321.6 4.86 14.72 0.979 0.982
271.7 6.75 24.42 0.943 0.942
220.8 7.82 36.06 0.912 0.913
170.3 8.22 49.13 0.908 0.903
121.2 8.04 62.63 0.917 0.907
62.3 7.40 79.16 0.953 0.943

Mass balance Initial fluid amount, moles : 4.513 *

:
- Residual fluid amount, moles : 0.835 **
= Produced fluid amount, moles : 3.678

Recovered fluid amount, moles: 3.572 ***

Recovery % : 3.572 / 3.678 * 100% : 97.12%

* Initial amount of fluid in the condensate cell at 112 °C and 430 bar.
** Residual fluid amount in the condensate cell at 112 °C and 62.3 bar.
*** Total recovery of gas and condensate at standard conditions.
NORSK Field Development & Technology MANUAL
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Table 3-21

Composition (mole %) of produced gas from depletion study at 112 °C

Pressure 407.7 372.2 321.6 271.7 220.8 170.3 121.2 62.3

bara
N2 0.819 0.817 0.845 0.799 0.867 0.867 0.811 0.836
CO2 1.212 1.210 1.260 1.250 1.242 1.250 1.198 1.262
C1 85.484 85.435 85.920 86.687 87.166 87.816 88.067 88.640
C2 4.499 4.494 4.483 4.491 4.490 4.494 4.357 4.603
C3 2.214 2.214 2.196 2.183 2.172 2.135 2.061 2.099
iso-C4 0.381 0.382 0.378 0.373 0.370 0.355 0.361 0.325
n-C4 0.887 0.892 0.879 0.863 0.854 0.810 0.859 0.729
neo-C5 0.004 0.004 0.004 0.004 0.004 0.004 0.004 0.003
iso-C5 0.298 0.301 0.295 0.286 0.282 0.258 0.308 0.235
n-C5 0.396 0.402 0.393 0.379 0.375 0.337 0.427 0.298
C6 0.468 0.482 0.470 0.439 0.435 0.373 0.493 0.292
C7 0.670 0.703 0.678 0.604 0.552 0.494 0.472 0.280
C8 0.606 0.654 0.620 0.526 0.423 0.365 0.289 0.176
C9 0.371 0.410 0.379 0.306 0.204 0.161 0.108 0.075
C10+ 1.692 1.599 1.198 0.809 0.563 0.282 0.186 0.144
Total 100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0

Moleweight 22.80 22.80 22.10 21.30 20.70 20.10 19.90 19.30

Gravity (air=1) 0.7857 0.7855 0.7629 0.7348 0.7143 0.6920 0.6866 0.6663
Viscosity (cP) 0.0317 0.0299 0.0265 0.0234 0.0206 0.0183 0.0165 0.0150

C7+ 3.339 3.366 2.875 2.245 1.742 1.302 1.055 0.675

NORSK Field Development & Technology MANUAL
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Table 3-22
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Table 3-23

K i psp = a + c Fi
o
Fi = bi (1/ Tbi - 1/ Tsp) ; T ( R)

bi Tbi
Component cycle-oR o
R
Nitrogen N2 470 109
Carbon Dioxide CO2 652 194
Hydrogen Sulfide H2S 1136 331
Methane C1 300 94
Ethane C2 1145 303
Propane C3 1799 416
i-Butane iC4 2037 471
n-Butane nC4 2153 491
i-Pentane iC5 2368 542
n-Pentane nC5 2480 557
Hexanes (lumped*) C6s 2738 610

n-Hexane nC6 2780 616

n-Heptane nC7 3068 669
n-Octane nC8 3335 718
n-Nonane nC9 3590 763
n-Decane nC10 3828 805
Heptanes-plus:

n7+ = 7.3 + 0.0075 Tsp(oF) + 0.0016 psp(psia)

b7+ = 1013 + 324 n7+ - 4.256(n7+)2

Tb7+ = 301 + 59.85 n7+ - 0.971(n7+)2

* Lumped hexanes include 25% 2-methyl pentane, 25% 3-methyl pentane, and 50% normal hexane.
NORSK Field Development & Technology MANUAL
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Table 3-24
NORSK Field Development & Technology MANUAL
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Figure 3-1
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Figure 3-2
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Figure 3-3
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Figure 3-4
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Figure 3-5
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Figure 3-6
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Figure 3-7
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Figure 3-8
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Figure 3-9
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Figure 3-10
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Figure 3-11
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Figure 3-12
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Figure 3-13
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Figure 3-14
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Figure 3-15
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Figure 3-16
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Figure 3-17
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Figure 3-18
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Figure 3-19
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Figure 3-20
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Figure 3-21
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Figure 3-22
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Figure 3-23
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Figure 3-24
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Figure 3-26
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Figure 3-27
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Figure 3-28
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Figure 3-27
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Figure 3-30
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Figure 3-27
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Figure 3-38
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Figure 3-39
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4. PVT REQUIREMENTS AND CORRELATIONS

4.1 Introduction
4.1.1 Where Do Measured PVT Data Come From?
In this chapter we look at how to use measured PVT data in reservoir
calculations. Measured PVT data may include:

• Production data from a well test, including separator GOR, stock-tank oil
and separator gas gravities (γo and γg), and reservoir temperature.

• Standard laboratory PVT analyses (see chapter 3), including

compositional analysis, constant composition expansion, a depletion
experiment, and perhaps a multistage separator test.

• Special laboratory PVT analyses such as multiple-contact gas injection

studies and slimtube displacements.

Production data will almost always be available from the initial discovery of a
reservoir. Standard laboratory tests may take one to six months to obtain.
Special PVT analyses may not be available for several years, as they are usually
ordered only after gas injection has been deemed a viable development strategy.

4.1.2 Why Do We Need PVT Data?

All reservoirs require black-oil PVT properties for volumetric calculations.
Most reservoirs will eventually be studied with a black-oil reservoir simulator.
Some reservoirs may also require compositional simulation. The following list
gives the primary applications of PVT data in reservoir calculations:

• Volumetric calculations of original gas and oil in place.

• Interpretation of well test and production data.

• Material balance calculations.

• Deliverability (inflow performance) calculations.

• Black-oil reservoir simulation of depletion, water injection, and some

gas injection processes.

• Compositional (EOS) reservoir simulation of gas condensate and volatile

oil systems, reservoirs with compositional variation, and gas injection
processes.
NORSK Field Development & Technology MANUAL
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• Compositional (EOS) process simulation

It is clear from this list that we must develop black-oil PVT properties for a
reservoir as early as possible. In particular we need as a function of pressure: (1)
volume factors Bo and Bg, and (2) solution gas-oil ratio Rs and/or oil-gas ratio rs.

The saturation pressure of a reservoir fluid must also be determined as soon

as possible. PVT properties are discontinous at the saturation pressure, and the
reservoir production performance may be significantly different above and
below the saturation pressure.

4.1.3 How do we get PVT Data?

PVT properties can be obtained from three primary sources:

• Empirical PVT correlations.

• Laboratory measurements.

• Equation of state fluid characterization.

Depending on the time since discovery, the type and size of the hydrocarbon
accumulation, and the type of reservoir model being used, any or all three of
these sources may be used to obtain the necessary PVT data.

Empirical correlations are useful in two situations. First, when the only
information available is data from production tests. Correlations can be used to
estimate the black-oil properties Bo, Bg, and Rs as a function of pressure. A
second application of correlations is to fit measured data from a given reservoir
or field, using the developed correlations to interpolate and extrapolate PVT
properties as a function of temperature and "composition" (e.g. STO gravity).

Laboratory measured PVT data can be used directly to determine black-oil

properties for low- and moderately-volatile reservoir oils. The properties so
derived (Bo, Bg, Rs, and sometimes rs) relate surface oil and gas volumes for a
specific set of separator conditions to volumes at reservoir conditions.

Laboratory measured PVT data can alternatively be used to tune an equation-

of-state PVT model, with the resulting PVT model (hopefully) being able to
generate more accurate black-oil properties for a wider range of reservoir
compositions and temperatures.

Equation of state models can be fairly accurate for predictions of depletion-

type processes, where the overall compositional effects are not large. Several
equations of state characterization methods are even what might be termed
"predictive," meaning that they predict saturation pressure, gas and oil densities
and volumes with reasonable accuracy, based only on fluid composition and
properties of the heaviest fraction (e.g. C7+).
Usually the predictions of laboratory PVT data are not sufficiently accurate
NORSK Field Development & Technology MANUAL
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and adjustments to the EOS model must be made. This process may be difficult,
even with automated nonlinear regression methods for modifying the EOS
model. Usually, however, a match of the experimental data can be obtained.
The resulting EOS model will then be valid for predicting depletion-type
processes.

A word of caution. For an EOS model to accurately predict PVT behavior of

systems with varying compositions, near-critical behavior, and developed
miscibility processes, special care must be taken when tuning the EOS model. It
is particularly important to include all available PVT data when tuning the EOS,
including multi-contact gas injection experiments (e.g. swelling tests) and
slimtube results if available.

4.1.4 Coming Up With PVT Data Can Be Difficult!

Many petroleum reservoirs recently discovered and currently being developed
have rather complicated PVT behavior. For example, it is not uncommon that
composition and PVT properties vary with depth, or that different geological
formations in the same field produce significantly different fluids.

A result of this more complicated PVT behavior is that a field (or even a
single geological formation) can not be described properly by a single set of
PVT properties. Composition can vary. Saturation pressure can vary. Stock-
tank oil gravity can vary. Producing GOR can vary. Reservoir temperature can
vary.

Particular care must be given to how PVT properties are developed for
reservoir modelling. Reservoir simulators may not be able to handle the
multitude of PVT-related problems for some fields. This will demand
continuing improvements in the PVT capabilities of reservoir simulators. But in
lieu of these improvements, some improvisation may be required to solve our
problems. For further discussion, see the Norsk Hydro publication "Handbok for
1
Reservoar Simulering.

4.2 Eclipse 100 PVT Formats

2
The following sections are taken directly from the ECL100 user's manual.
Alternate ECL100 PVT input formats (simplified oil and gas tables, PVCO and
PVDG) are not given here but may be found in the ECL100 documentation.

Other EOS-based programs such as PVTSIM and Intera's PVT generate files
using ECL100 (PVTO and PVTG) format. Even with identical EOS
characterizations, one fundamental difference will be found between how the
various EOS programs generated ECL100 PVTO (and PVTG) data at pressures
greater than the original saturation pressure.

At pressures greater than the (original) saturation pressure, the various EOS
programs may or may not extend (extrapolate) the saturated properties for p>psat.
PVTx does not extend saturated properties beyond the original saturation
NORSK Field Development & Technology MANUAL
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pressure. This must be done manually, using different feeds with higher
saturation pressures, and then "splicing" the ECL100 output files together.
Section 5.4.5 (Generating Modified Black-Oil PVT) discusses this approach, and
how other EOS programs extrapolate saturated PVT properties.
Basically, the recommended approach for extrapolating saturated data (if at
all) depends on the reservoir process being simulated. Gas injection requires one
approach, while compositional variation with depth requires another approach.
Some gas injection processes cannot be modelled adequately using ECL100.
Alternatives include using a more complicated black-oil PVT formulation such
as found in the ECL200 "GI" approach, or using fully compositional (EOS)
simulation.

4.2.1 PVTO - General Oil PVT Table

The ECL100 PVT table for saturated oil is specified with the PVTO command.
A copy of the current version of the PVTO command from Intera's users manual
is shown on the following page. It is recommended that the PVTO command be
used instead of the alternative PVCO and PVDO commands, unless a particular
application clearly calls for the use of an alternative PVT input format.

The PVTO table is automatically generated by PVTx using the PRINT

ECL100 print keyword (with an optional unit specification), and by specifying
multistage separator commands SEPA in at least one depletion experiment
(CCE, CVD, and/or DLE). For example,
PRINT ECL100 SI
*
DLE FEED=1
DEGC BARA
TEMP=123
* tsp psp
SEPA 60 60
SEPA 25 15
SEPA 15.5 1.0135
DATA
345 / psat
500 / at least one pressure > psat must be input !!!
400
350
325
300
...
/end

Note, at least one pressure greater than the calculated saturation pressure must be
input when generating ECL100 PVT files.

Don't forget to put the ECLIPSE file-opening command in the file pvtxfil.
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4.2.2 PVTG - General Gas PVT Table

The ECL100 PVT table for saturated gas (including "vapourized oil", i.e.
dissolved condensate) is specified with the PVTO command. A copy of the
current version of the PVTG command from Intera's users manual is shown on
the following page. It is recommended that the PVTG command be used instead
of the alternative PVDG command, unless the particular application clearly calls
for the use of PVDG (the gas is truly "dry").

The PVTG table is automatically generated by PVTx using the PRINT

ECL100 print keyword (with optional unit definition), and by specifying
multistage separator commands SEPA in at least one depletion experiment
(CCE, CVD, or DLE). For example,
PRINT ECL100 SI
*
CVD FEED=1
DEGC BARA
TEMP=136
* tsp psp
SEPA 50 45
SEPA 23 12
SEPA 15.5 1.0135
DATA
382 / psat
500 / at least one pressure > psat must be input !!!
400
350
325
300
...
/end

Note, at least one pressure greater than the calculated saturation pressure must be
input when generating ECL100 PVT files.

Don't forget to put the ECLIPSE file-opening command in the file pvtxfil.
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4.2.3 PVTW - General Water PVT Table

Water properties are input to ECL100 using the water PVT table PVTW. This
input basically consists of specifying a reference pressure (e.g. initial reservoir
pressure), water FVF and viscosity at the reference pressure, and water
compressibility and "viscosibility" at the reference pressure.

These data can be obtained from generalized correlations in the Fluid Data
Book (Charts x-x), or for a specific reservoir system using the BIPWAT Lotus 1-
2-3 spreadsheet and PVTx (see section 5.8 for an example of the latter).
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4.3 PVT Data from Production Test Results

4.3.1 What Data Are Available?
Results from production testing of a discovery oil well will provide sufficient
information to generate a complete set of PVT data for most reservoir
engineering calculations, including screening simulation studies. The basic data
required are:

• Reservoir temperature, TR
• Stock-tank oil gravity, γo
• Total average surface gas gravity, γg
• Producing (solution) gas-oil ratio, Rs

Reservoir temperature is measured during logging and pressure transient tests.

Separator gas and oil measurements are made on site during production testing.

4.3.2 Separator Rates

Field measurement of GOR is based on test separator gas rate given as a
o
standard gas volume (at 1 atm and 15 C), and either (a) separator oil rate
reported at separator conditions, or (b) stock-tank oil rate. Table 3-12 gives
corrections for separator gas rates that influence the recombination GOR used
for calculating the wellstream composition.

The relation between stock-tank oil rate and separator oil rate is given by a
shrinkage factor, the inverse of separator oil FVF (bosp=1/Bosp),

1 volume stock - tank oil

Shrinkage = = bosp =
Bosp volume oil at separator conditions

The shrinkage factor bosp usually ranges from 0.8 to 0.95 for offshore test
separator conditions. It is important to determine which oil rate has actually
been reported in a given test.

Stock-tank oil rates are usually denoted SM3/D or STB/D, although it is not
uncommon that they are misleadingly labeled M3/D or BBL/D. Separator rates
are usually denoted M3/D or BBL/D. If you are lucky, both rates are reported,
together with the shrinkage factor used. If in doubt about what oil rate is
reported, ask the well testing engineer or call the testing/sampling company who
reported the rate.

The oil rate equation that yields stock-tank volumetric rate qo from metered
test separator rate qmeter is

qo = q meter C meter bosp (1 - f BSW )

where Cmeter is a correction to the meter reading (calibration factor), and fBSW is
the BS&W (basic sediments and water) fraction.
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In closing, several precautions should be made to obtain a representative

GOR. First, the well should be produced at sufficiently high rates to ensure
stable flow conditions. The GOR should be constant or changing smoothly and
gradually on a fixed choke. It is more important to have a stable GOR condition
with a higher rate, than to maintain a high wellbore flowing pressure to avoid
two-phase flow near the wellbore.

4.3.3 Using Separator Test Data

Before separator test data from an oil well can be used in PVT correlations it is
necessary to estimate surface data that are not usually measured. Figure 4-1
illustrates a typical separator test, where measured and calculated data are
indicated. Measured data usually include:
3
• First stage separator gas rate, qg1, Sm /d
3
• First stage separator oil rate, qosp, sep. m /d, or stock-tank oil rate, qo,
3
Sm /d

• First stage separator gas gravity, γg1

• Stock-tank oil gravity, γo

Shrinkage (1/Bosp) is either measured or estimated from a correlation.

Based on the reported test information, the following additional quantities

should be calculated:

1. Additional gas in solution in separator oil, Rs+ (scf/STB), and the specific
gravity of the solution gas, γg+
A1 A2
R s+ =
(1 - A1 A3) (4-1)
γ g+ = A 2 + A3 R s+

where
1.205
 psp1  
A1 =  + 1.4 10(0.0125γ API-0.00091T sp 1)  (4-2)
 18.2  

A 2 = 0.25 + 0.02 γ API

(4-3)
A3 = - 3.57(10 ) γ API
-6

o
with psp given in psia and Tsp given in F.
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2. Separator oil volume factor, Bosp (if not reported)

-5 1.2
Bosp = 0.9759 + 12(10 ) A
γ g+ (4-4)
A = R s+ ( )0.5 + 1.25 Tsp
γo
o
with Rs+ given in scf/STB and Tsp given in F.

3. First stage separator GOR relative to STO, Rs1 (if not reported)
qg1
R s1 = = R sp1 Bosp (4-5)
qo

4. Total solution gas-oil ratio, Rs

R s = R s 1 + R s+ (4-6)

5. Total average gas specific gravity γ g

γ g 1 R s 1 + γ g+ R s+
γg= (4-7)
R s 1 + R s+

The quantities Rs, γ g , γo (or γAPI) and reservoir temperature are used in the oil
correlations discussed below.

4.4 Oil PVT Correlations

This section discusses how to use PVT correlations to generate PVT data used in
reservoir engineering calculations, including black-oil data for reservoir
simulation.

Oil PVT correlations are useful in several situations. Primarily we use them
for estimating key PVT properties of new discoveries, before laboratory PVT
data are available (one to six months after discovery). Correlations also can be
used to fit measured PVT data, with the intention of interpolating and
extrapolating in temperature and composition (i.e. API gravity). Finally, oil
PVT correlations are often used for production calculations (e.g. pressure loss in
tubing) and estimating separator oil shrinkage factors; PVT properties are
required at temperatures lower than studied in the standard PVT tests conducted
at reservoir temperature.

4.4.1 Solution Gas-Oil Ratio

The variation in solution GOR with pressure, Rs(p), can be estimated from a
bubblepoint pressure correlation. The traditional form of bubblepoint pressure
correlations is
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pb = f ( R s , T, γ o , γ g )
3
For example, the Standing correlation is
pb = 18.2(A- 1.4)
(4-8)
A = ( R s )0.83 × 100.00091 T - 0.0125γ API
γg
4
The Glasø correlation is also recommended, as it was developed for North Sea
5
fields. The Lasater correlation is also recommended.

Assuming a saturated condition at some pressure p, this relation can be solved

for Rs,

R s = F (p, T, γ o , γ g )

where F is the inverse function of f. The pressure p can be less than or greater
than the original bubblepoint pressure predicted at reservoir temperature.

For the Standing bubblepoint correlation, Rs(p) is given by

1.205
 (0.055 p+ 1.4)100.0125γ API 
Rs = γ g 
  (4-9)
 
0.00091T
10

o
with p in psia, T in F, and Rs in scf/STB.

4.4.2 Solution GOR Above Initial Bubblepoint Pressure

Usually the solution GOR is assumed constant at pressures greater than the
original bubblepoint pressure. However, this is strictly true only when the
pressure decreases monotonically. Two situations in a reservoir may cause the
oil to be saturated with more gas than originally in solution:

• Gas is injected at a pressure above the initial bubblepoint.

• Pressure builds up in a region of the reservoir with relatively high gas

saturation (e.g. near the wellbore, or at the top of a layer undergoing
gravity segregation).

In either situation, the oil can locally become saturated with more gas than
originally in solution.

2 illustrates the behavior of Rs(p). The upper figure shows the behavior that
will be predicted by most empirical PVT correlation, where a monotonic
relationship exists between Rs and pressure. The only correlation that does not
give an approximately linear increase in Rs with pressure is the Lasater
correlation, which has the limiting condition p=0.84T/γg for infinite Rs (T is in
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Curtis H. Whitson (PERA a/s) November 1998

o
R and p is in psia).

The lower figure shows the actual behavior that would be expected for a
leaner gas and a richer gas dissolving into a reservoir oil. A "rich" gas might be
primary separator gas, and a "lean" gas might be a highly-processed, methane-
rich gas. Several points are worth noting.

• Lean gas elevates the bubblepoint faster (more readily) than a rich gas.
Therefore it takes more rich gas to elevate the bubblepoint to a given
pressure.

• Extrapolating the Rs(p) curve with an empirical bubblepoint correlation

will result in a function that is more applicable to a "richer" gas.

• A critical point is reached where the addition of more gas results in a

mixture exhibiting a dewpoint instead of a bubblepoint.

• The Rs(p) is not monotonic forever. A maximum pressure will

eventually be reached for most systems.

• The arrows indicate the initial direction that will be traversed on a

particular curve. However, depending on the situation, it is possible to
move either direction on any of the curves.

4.4.3 Saturated Oil Volume Factor

Saturated oil FVF correlations are given by a function of the form

Bob = f ( R s , T, γ o , γ g )

Subscript b indicates that the oil is saturated at the current pressure, which is the
bubblepoint pressure of the oil, containing dissolved gas given by Rs. Note that
pressure does not enter the calculation of Bob directly, but only indirectly through
Rs(p).
3
The Standing correlation for Bob is given as
-5 1.2
Bob = 0.9759 + 12(10 ) A
γ (4-10)
A = R s ( g )0.5 + 1.25 T
γo
4
The Glasø correlation , developed for North Sea reservoirs, is also
recommended.

Referring now to Figure 4-2, the saturated part of the curve is shown with a
solid line and dashed lines are used for the undersaturated states. The saturated
oil FVF must be calculated along the solid line using an appropriate correlation.
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4.4.4 Undersaturated Oil FVF and Compressibility

The oil FVF can be very important to the reservoir performance of highly-
undersaturated oils. In fact, pressure depletion and recovery of these reservoirs
are almost solely determined by Bo (in the absense of water drive).

Undersaturated oil FVF is calculated from undersaturated oil

compressibility. With several simplifying assumptions, the common relation
Bo ≈ Bob [1 - co (p- p b)] (4-11)
can be derived. In this relation co is assumed to be constant for all pressures
greater than the bubblepoint. The result is a linear relationship between Bo and p
3 3
for p>pb. This assumption is not really valid for oils with GOR>150 Sm /Sm .
6
The Vazquez correlation for undersaturated oil compressibility is frequently
used,
co = A/p
A = (5 R sb + 17.2 T - 1180 γ gc + 12.61 γ API - 1433) × 10-5 (4-12)

o
with p in psia, T in F, and Rs in scf/STB. γgc is a corrected separator gas gravity
given by
p
γ gc = γ g [1 + 0.5912(10-4) γ API Tsp log( sp )] (4-13)
114.7

o 7
with Tsp in F and psp in psia. McCain notes that this correlation tends to
underpredict oil compressibility, particularly at highly undersaturated conditions.

Using the pressure depedence given by the Vazquez correlation, an exact

relation for undersaturated oil FVF relation can be derived from the definition of
isothermal compressibility, c=-(dV/dp)/V,
pb

Bo = Bob exp[ ∫ co (p) dp]

p
pb
(4-14)
1
=B ob exp[A ∫p
p
dp]

resulting in
A
Bo = Bob (pb /p ) (4-15)
where A is given by the Vazuez correlation (Eq. (4-12)), or determined from
experimental data (e.g. from the slope of a log-log plot of Vo/Vob versus p/pb).

For highly undersaturated, light-oil reservoirs (e.g. Embla Field),

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undersaturated Bo can be significantly nonlinear (Figure 4-2). For such

reservoirs the integral relation above should be used for oil FVF, where the
pressure dependence of co is taken into account.

4.4.5 Oil Density

3
Density of reservoir oil varies from 0.5 g/cm for light volatile oils to 0.95
3
g/cm for heavy crudes with little or no solution gas. Several methods have
successfully been used to correlate oil density, including extensions of ideal-
solution mixing, equations of state, corresponding-states correlations, and
empirical correlations.

Oil density based on black-oil properties is given by

1000 γ o + 1.224 γ g R s
ρo = (4-16)
Bo
3 3 3 3 3
with ρo in kg/m , Bo in m /Sm , and Rs in Sm /Sm . Correlations can be used to
estimate Rs and Bo from γo, γg, pressure, and temperature.

Standing-Katz Method
3,8,9
Standing and Katz give an accurate method for estimating oil densities
using an extension of ideal-solution mixing,
ρ o = ρ po + ∆ ρ p - ∆ ρ T (4-17)

where ρpo is the pseudoliquid density at standard conditions, and the terms ∆ρT
and ∆ρp give corrections for temperature and pressure, respectively.

Pseudoliquid density is calculated using ideal-solution mixing and

correlations for the apparent liquid densities of ethane and methane at standard
conditions. Given oil composition xi, ρpo is calculated from
N

∑x M i i

ρ po = i =1
N
(4-18)
∑
i =1
x i Mi
ρi
3
where Standing and Katz show that apparent liquid densities ρi (kg/m ) of C2
3
and C1 are a function of the densities ρ2+ and ρpo (also in kg/m ), respectively
(Chart x, Fluids Data Book),
ρ 2 = 245.1 + 0.3167 ρ2 +
(4-19)
ρ1 = 4.998 + 0.45 ρ po

where
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C7+

∑x M i i

ρ 2+ = i = C2
C7 +
(4-20)
∑ x i Mi
i = C2 ρ i

Application of these correlations results in an apparent trial-and-error calculation

10
for ρpo. Standing presents a graphical correlation (Chart x, Fluids Data Book)
based on these relations, where ρpo is found from ρ3+ and weight fractions of C2
and C1 (w2 and w1).

The pressure correction ∆ρp is a function of ρpo, and ∆ρT is a function of

(ρpo+∆ρp). Madrazo introduced modified curves for ∆ρp and ∆ρT which
11
3
improve predictions at higher pressures and temperatures. Standing gives best-
fit equations for his original graphical correlations of ∆ρp and ∆ρT,
∆ ρ p = 0.2323 [0.167 + 16.181(10-0.00265ρpo )] p
(4-21)
- 3.364 × 10-5 [0.299 + 263(10- 0.00376 ρpo )] p
2

[
∆ ρT = 16.02 (1.8 T- 28) 0.0133 + 1.363 × 105 ρpo + ∆ ρ p ( ) -2.45
] (4-22)
- 16.02 (1.8 T- 28 ) 2 [8.1(10- 6 ) - 0.0622 × 10- 0.00477( ρpo + ∆ ρp ) ]

3 o
with ρ in kg/m , p in bara, and T in C. These equations are not recommended at
o
temperatures greater than 115 C; instead, Madrazo's graphical correlation can be
used. The correction factors can also be used to determine isothermal
compressibility and oil formation volume factor at undersaturated conditions.

The treatment of nonhydrocarbons in the Standing-Katz method has not

received much attention, and the method is not recommended when
3
concentrations of nonhydrocarbons exceed 10 mole percent. Standing suggests
3
that an apparent liquid density of 479 kg/m can be used for nitrogen, but he
does not address how the nonhydrocarbons should be considered in the
calculation procedure - i.e., as part of the C3+ material or following the
calculation of ρ2 and ρ1. Madrazo indicates that the volume contribution of
nonhydrocarbons can be neglected completely if the total content is less than 6
12
mole percent. Vogel and Yarborough suggest the weight fraction of nitrogen
should be added to the weight fraction of ethane.
13
In the absence of oil composition, Katz suggests that the pseudoliquid
3
density ρpo (in kg/m ) be calculated from stock-tank oil gravity γo, solution gas-
oil ratio Rs, and apparent liquid density of the surface gas ρga taken from a
graphical correlation (Chart x, Fluid Data Book),
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1000 γ o + 1.224 R s γ g
ρ po = (4-23)
Rs γ g
1 + 1.224
ρ ga

Standing gives an equation for ρga,

ρga = 16.02 [38.52 × 10-0.00326 γ API
(4-24)
+ (94.75 - 33.93 log γ API ) log γ g ]

3 3 3
with ρga in kg/m and Rs in Sm /Sm .
14
The Alani-Kennedy method for calculating oil density is a modification of
the original van der Waals' EOS, with constants a and b given as functions of
temperature for normal paraffins C1 to C10, and iso-butane; two sets of
coefficients are reported for methane (for temperatures from 20° to 150°C, and
from 150° to 240°C) and two sets for ethane (for temperatures from 38° to
15
120°C, and from 120° to 240°C). Lohrenz et al. give Alani-Kennedy
temperature-dependent coefficients for nonhydrocarbons N2, CO2, and H2S.

The Alani-Kennedy method has been outdated by more predictive cubic

equations of state, such as the Peng-Robinson or Soave-Redlich-Kwong EOS
using volume translation.
16 17,18
Rackett and Hankinson et al. give accurate correlations for pure
component saturated liquid densities, and although these correlations can be
extended to mixtures, they have not been tested extensively for reservoir
systems.

Cubic EOS with Volume Translation

The Standing-Katz method is limited somewhat by a temperature constraint
o
of about 250 F. Given oil composition (and C7+ molecular weight and specific
gravity), the most general and accurate method for estimating densities (and
other volumetric properties) is the PR or SRK EOS with volume translation.
It is highly recommended to use the default PVTx fluid characterizations
a
generated using the PVTxIN data set generator program ; either the Whitson C7+
splitting routine for the PR EOS, or the Pederen et al. C7+ procedure for the SRK
EOS. Three C7+ fractions is recommended, as oil volumetric properties are not
very sensitive to the total number of C7+ fractions.

a
The C7+ characterization method, and particularly the correct use of volume translation
dictates the accuracy of cubic EOS oil volumetric predictions. The volume translation coefficients
are usually constants for pure components, determined by matching the saturated liquid density at
T=0.7Tc, where the volume shift for C7+ fractions is determined by matching the specific gravity of
each fraction.
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4.4.6 Saturated Oil Viscosity

Oil viscosity can not be estimated reliably, perhaps within ±30% at best. The
recommend correlations are based on two criteria:

• The correlations should extrapolate reasonably for light and heavy stock-
tank crudes.

• In the exploration phase, when little data is available, it is important to

make conservative estimates of key reservoir parameters.
19
Most correlations have the functional form given by Chew and Connally ,
µ ob = A1 ( µ oD )A 2
(4-25)

where µoD is dead-oil viscosity estimated as a function of temperature and stock-

tank oil gravity. A1 and A2 are functions of solution GOR, Rs.

The recommended correlation for µoD is given by Bergman ,

20

ln ln(µ oD + 1) = a 0 + a1 ln(T+ 310)

a 0 = 22.33 - 0.194 γ API + 0.00033 γ API
2
(4-26)
a1 = - 3.20 + 0.0185 γ API

with µoD in cp and T in F. This correlation is recommended because it is

o

applicable at reservoir temperatures and at seabed temperatures approaching

o 4
0 C. The Glasø correlation is also well suited for this wide temperature range,
µ oD = 3.141(1010) T -3.444
(4-27)
× (log γ API )
[10.313(log T) - 36.447]

with µoD in cp and T in F. The Bergman correlation predicts dead-oil

o

viscosities slightly higher than the Glaso correlation (Figure 4-2).

21
The recommended correlations for A1 and A2 are given by Aziz et al. ,
A1 = 0.20 + 0.80 × 10
-0.00081 R s
(4-28)
A 2 = 0.43 + 0.57 × 10
- 0.00072 R s

with Rs in scf/STB. These correlations predict slightly higher viscosities than

most other correlations (for A1 and A2). The functional form of the Aziz et al.
correlations are well-behaved at high Rs values, approaching constant values
A1=0.2 and A2=0.43 (there is no physical meaning attached to these constants).
22
The Beggs and Robinson correlations for A1 and A2, which are commonly
used, also behave reasonably at high Rs values. However, the Beggs and
Robinson correlation predicts considerably lower saturated oil viscosities than
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3 3
the Aziz correlation for Rs<150 Sm /Sm (see Figure 4-2).

4.4.7 Undersaturated Oil Viscosity and "Viscosibility"

Undersaturated oil viscosity is very nearly a linear function of pressure, even at
high pressures and for relatively volatile oils. Two correlations are

µ o = µ ob (p/ p b )
A

(4-29)
exp(-11.513 - 8.98 × 10-5 p)
1.187
A = 2.6 p
6
recommended. The first, which is commonly used, is given by Vazquez ,
with p in psia and viscosities in cp.
10
The second correlation is given by Standing (originally as a chart , and later
23
fit to the following equation ),
µ o - µ ob
= 2.4 × 10-5 µ1.6
ob + 3.8 × 10
-5
µ ob
0.56
(4-30)
p- p b

with p in psia and viscosities in cp. Based on this correlation, undersaturated oil
viscosity is a linear function of pressure, with the slope given as a function of
bubblepoint oil viscosity µob. Note that the quantity "viscosibility" used in the
ECL100/ECL200 models is given by (see Figure 4-2)
1 d µo
Viscosibility = ( ) p = pb
µ ob dp (4-31)
≈ 2.4 × 10-5 µ + 3.8 × 10-5 µ
0.6
ob
- 0.44
ob

with viscosibility in 1/psi. Multiply by 14.5 to get 1/bar.

The Vazquez correlation predicts somewhat higher viscosities than the

Standing correlation, up to about p=2pb. At higher pressures, the Vazquez
correlation may give considerably higher viscosities, as shown in Figure 4-2.

The Standing correlation is recommended in general. The Vazquez

correlation may have an abrupt increase in viscosity at higher pressures, a
behavior that cannot be readily explained physically. The Standing correlation is
only slightly more optimistic (lower µo values) than the Vazquez correlation, the
Standing correlation is simpler, and it extrapolates in a physically consistent
manner at high pressures.

4.5 Gas PVT Correlations

This section gives correlations for PVT properties of natural gases, including:

• Gas Volumetric Properties - Review

• Z-factor Correlations
• Gas Pseudocritical Properties
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• Wellstream Gravity of Wet Gases and Gas Condensates

• Gas Viscosity
• Total Volume Factor

4.5.1 Gas Volumetric Properties

Most gases at low pressure follow the ideal-gas law,
pV = nRT (4-32)
where
3 o -1 -1
R=10.73146 psia ft R lbmol
3 -1 -1
R=8.3143 kPa m K kmol
3 -1 -1
R=0.083143 bar m K kmol

Application of the ideal-gas law results in two useful engineering

approximations.

First, the standard molar volume representing the volume occupied by one
mole of gas at standard conditions is independent of the gas composition:
(Vg )sc RTsc
( v g )sc = =
n psc
= 379.5 scf / lbmol (4-33)
= 23.69 Sm / kmol 3

Second, the specific gravity of a gas defines the gas molecular weight,
(ρg )sc M g Mg
γg = = =
(ρair )sc M air 28.97 (4-34)
M g = 28.97 γ g

For gas mixtures at moderate to high pressure or at low temperature the

ideal-gas law does not hold because the volume of the constituent molecules, as
well as their intermolecular forces, strongly affect the volumetric behavior of the
gas.

pV = nZRT (4-35)
The real gas law includes a correction term, the Z-factor,
This is the standard equation for describing the volumetric behavior of reservoir
gases. All volumetric properties of gases can be derived from the real-gas law.

Gas density is given by

pM g pγ g
ρg = = 28.97 (4-36)
ZRT ZRT
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For wet-gas and gas-condensate mixtures, wellstream gravity γw should

always be used instead of γg in calculating pseudocritical properties.

Gas compressibility cg is given by

1 ∂ Vg
cg = - ( )
Vg ∂ p
(4-37)
1 1 ∂Z
= - ( )
p Z ∂p T
For sweet natural gas (i.e., not containing H2S) at pressures less than about 70
bara, the second term in Eq. (4-37) is negligible and cg≈1/p is a reasonable
approximation.

Gas volume factor Bg is defined as the ratio of gas volume at specified p and
T to the ideal-gas volume at standard conditions,
psc Z T
Bg = ( ) (4-38)
Tsc p
which for SI units (psc=1.013 bara and Tsc=15.56°C=288.7 K) is
Z T
Bg = 0.00351 (4-39)
p
with temperature in K and pressure in bar.

Because Bg is inversely proportional to pressure, the inverse volume factor

bg=1/Bg is commonly used. For SI units (bara and K),
3 3 p
bg (Sm / Sm ) = 285 (4-40)
Z T

4.5.2 Z-Factor and Compressibility

24
Standing and Katz present a generalized Z-factor chart which has become an
industry standard for predicting the volumetric behavior of natural gases. Many
empirical equations and equations of state have been fit to the original Standing-
25
Katz chart. For example, Hall and Yarborough present an accurate
representation of the Standing-Katz chart using a Carnahan-Starling hard-sphere
equation of state,
α p pr
Z=
y
α = 0.06125 t exp[-1.2(1 - t ) 2] (4-41)
t = 1 / T pr
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where the reduced density y (the product of a van der Waals covolume and
density) is obtained by solving the relation

y + y 2 + y3 − y 4
F( y) = 0 = −αp pr +
(1 − y)3
- (14.76 t - 9.76 t 2 + 4.58 t 3 ) y 2 (4-42)
+ (90.7 t - 242.2 t 2 + 42.4 t 3 ) y1.18 + 2.82 t
with
dF 1 + 4 y+ 4 y2 - 4 y3 + y4
= 4
- (29.52 t- 19.52 t 2 + 9.16 t 3) y
dy (1 - y )
(4-42)
2 3 1.18 + 2.82 t
+ (2.18 + 2.82 t)(90.7 t- 242.2 t + 42.4 t ) y

The derivative ∂Z/∂p used in the definition of cg is given by

 α ppr 
 
∂Z α  1 y2 
( ) = - (4-43)
∂ p T ppc  y dF 
 
 dy 

An initial value of y=0.001 can be used with a Newton-Raphson procedure

-8
where convergence should be obtained in 3 to 10 iterations for F(y)=10 .
26
Based on Takacs comparison of 8 correlations representing the Standing-
27
Katz chart, the Hall-Yarborough and Dranchuk-Abou-Kassem equations give
the most accurate representation for a broad range of temperature and pressure.
Both equations are valid for 1≤Tr≤3 and 0.2≤pr≤25-30.
28
For many petroleum engineering applications the Brill and Beggs equation
gives a satisfactory representation (±1-2%) of the original Standing-Katz Z-
factor chart for 1.2<Tr<2. Also, this equation can be solved explicitly for Z. The
main limitations are that reduced temperature must be greater than 1.2 (≈25°C)
and less than 2.0 (≈170°C), and reduced pressure should be less than 15 (≈700
bara).

The Standing-Katz Z-factor correlation may require special treatment for wet
gas and gas condensate fluids containing significant amounts of heptanes-plus
material, and for gas mixtures with significant amounts of nonhydrocarbons.
Also, several authors have noted an apparent discrepancy in the Standing-Katz
Z-factor chart for 1.05<Tr<1.15, which has been "smoothed" in the Hall-
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Yarborough correlations.

The Hall-Yarborough (or the Dranchuk-Abou-Kassem) equation is

recommended for most natural gases. With today's computing capabilities it is
normally unnecessary to choose simple, less reliable equations such as the Brill
and Beggs equation.

4.5.3 Gas Pseudocritical Properties

Z-factor, viscosity and other gas properties have been accurately correlated using
corresponding-states principles, where the property is correlated in terms of
reduced pressure and temperature:
Z = f ( pr , T r )
(4-44)
µ g / µ og = f (pr , T r )

where pr=p/pc and Tr=T/Tc. Such corresponding-states relations should be valid

for most pure compounds when component critical properties pc and Tc are used.
The same relations can be used for gas mixtures if the mixture pseudocritical
properties ppc and Tpc are used. Pseudocritical properties of gases can be
estimated using gas composition and mixing rules, or from correlations based on
gas specific gravity.
29
Sutton suggest the following correlations for hydrocarbon gas mixtures,

T pcHC = 169.2 + 349.5 γ gHC - 74.0 γ gHC

2

(4-45)
p pcHC = 756.8 - 131 γ gHC - 3.6 γ gHC
2

He claims his equations are reliable for calculating pseudocritical properties with
the Standing-Katz Z-factor chart; he even suggests that this method is superior to
using composition and mixing rules(?).
30
Kay's mixing rule is typically used when gas composition is available,
N

T pc = ∑ yi Tci
i =1
N
(4-46)
p pc = ∑y i pci
i =1

where the pseudocritical properties of the C7+ fraction can be estimated from the
3,31
Matthews et al. correlations ,
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T c 7 + = 608 + 364 log(M 7 + - 71.2)

+ (2450 log M 7 + - 3800) log γ 7 +
(4-47)
pc 7 + = 1188 - 431 log(M 7 + - 61.1)
+ [2319 - 852 log(M 7 + - 53.7)](γ 7 + - 0.8)

Kay's mixing rule is usually adequate for lean natural gases in the absense of
nonhydrocarbons. Sutton suggests that pseudocriticals calculated using Kay's
mixing rule are adequate up to γg_0.85, but that errors in calculated Z-factors
increase linearly at higher specific gravities, reaching 10 to 15% for γg>1.5.
When significant quantities of nonhydrocarbons CO2 and H2S are present,
32
Wichert and Aziz suggest corrections to arrive at pseudocritical properties that
yield reliable Z-factors from the Standing-Katz chart. The Wichert and Aziz
corrections are given by,
T pc = T pc - ε
*

p pc (T*pc - ε)
*

p pc = (4-48)
T pc + y H2 S (1 - y H2 S)ε
*

ε = 120 [ ( y CO2 + y H2 S ) - ( y CO2 + y H2 S ) ] + 15( y H2 S - y H2 S)

0.9 1.6 0.5 4

where Tpc* and p*pc are mixture pseudocriticals based on Kay's mixing rule. This
method was developed from extensive data from natural gases containing
nonhydrocarbons, with CO2 molar concentration ranging from 0 to 55% and H2S
ranging from 0 to 74%.

If only gas gravity and nonhydrocarbon content are known, the hydrocarbon
specific gravity is first calculated from
γ g - ( y N M N + yCO MCO + yH S M H S) / Mair
γ gHC = 2 2 2 2 2 2
(4-49)
1 - y N - yCO - yH S
2 2 2

Hydrocarbon pseudocriticals are then calculated from Eqs. (4-45), and these
values are adjusted for nonhydrocarbon content based on Kay's mixing rule,
*
p pc = (1 - y N2 - y CO2 - y H2 S) p pcHC
+ y N2 p cN2 + y CO2 p cCO2 + y H2 S p cH2 S
*
(4-50)
T pc = (1 - y N2 - y CO2 - y H2 S) T cHC
+ y N2 T cN2 + y CO2 T cCO2 + y H2 S T cH2 S

Tpc* and p*pc are used in the Wichert-Aziz equations using CO2 and H2S mole
fractions to obtain mixture Tpc and ppc.
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The Sutton correlations (Eqs. 4-45)) are recommended for hydrocarbon

pseudocritical properties. If composition is available, Kay's mixing rule should
be used with the Matthews et al. pseudocriticals for C7+. Gases containing
significant amounts of nonhydrocarbons CO2 and H2S should always be
corrected using the Wichert-Aziz equations. Finally, for gas-condensate fluids
the wellstream gravity γw (discussed below) should replace γg in the equations
above.

4.5.4 Wellstream Gravity

Gas mixtures that produce condensate at surface conditions usually exist as a
single phase gas in the reservoir and production tubing. This can be verified by
determining the dewpoint pressure at the prevailing temperature. If properties of
the wellstream are desired at conditions where the mixture is single-phase, it is
necessary to convert surface gas and surface oil properties to a wellstream
specific gravity γw. This gravity should be used instead of γg to estimate
pseudocritical properties.

Wellstream gravity represents the average molecular weight of the produced

mixture (relative to air) and it is readily calculated from the producing
oil(condensate)-gas ratio rp, average surface gas gravity γ g , surface condensate
gravity γo, and surface condensate molecular weight Mo,
γ g + 816 r p γ o
γw = (4-51)
1 + 2.368 × 10 4 r p ( γ /M )o
3 3
with rp in Sm /Sm . Average surface gas gravity is given by
Nsp

∑ GOR i γ gi
γg= i =1
Nsp
(4-52)
∑ GOR
i =1
i

Eq. (4-51) is presented graphically in Chart 22 of the Fluid Properties Data

33
Book .

When Mo is not available, the recommended correlation for estimating Mo is

34,35
given by Cragoe ,
6084
Mo = (4-53)
γ API - 5.9
This correlation gives reasonable values of Mo for both surface condensates and
stock-tank oils.

A typical problem is that all of the data required to calculate wellstream gas
volumes and wellstream specific gravity are not available and must be estimated.
In practice, we often have reported only the first stage separator GOR (relative
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to STO volume) and gas specific gravity, Rs1 and γg1, the stock-tank oil gravity
γo, and the primary separator conditions psp1 and Tsp1.

The same approach as discussed in the section on oil PVT correlations can
be used here (Eqs. (4-1) to (4-7)). The total producing oil-gas ratio is simply

rp = rs = 1/Rs = 1/(Rs1+Rs+)

The wellstream gravity γw is calculated using rp, γo, Mo, and γ g in Eq. (4-51).

4.5.5 Wet Gas and Dry Gas Volume Factors

Thus far Bg has been defined assuming that the gas volume at p and T remains as
a gas at standard conditions. For wet gases and gas condensates the surface gas
will not contain all of the original gas mixture because surface condensate is
produced after separation. For these mixtures the traditional definition of Bg
may still be used, but we refer to this quantity as a hypothetical wet-gas volume
factor (Bgw) calculated from Eq. (4-38).

If the reservoir gas yields condensate at the surface, the dry-gas volume
factor Bgd is sometimes used (for example in modified black-oil simulators),
psc ZT
Bgd = ( ) (1 + Cog rs )
Tsc p (4-54)
= Bgw (1 + Cog r s)

3 3 3 3
with rs in Sm /Sm , Bgd and Bgw in m /Sm , T in K, p in bara; Cog is a conversion
3 3
from surface oil volume in Sm to an "equivalent" surface gas in Sm ,
scf 3 γ lbmol
Cog = 379 ( ) × 5.615 ( ft ) × 62.4 og ( 3 )
lbmol STB M og ft
γ scf
= 133,000 og ( ) (4-55)
M og STB
γ og Sm 3
= 2.368 × 104 ( 3)
M og Sm

If condensate molecular weight Mog is not measured then it can be estimated

with the Cragoe correlation,
6084
Mo = (4-56)
γ API - 5.9

-1
The term (1+Cogrs) represents the mole fraction of reservoir gas that
becomes dry surface gas after separation and usually ranges from 0.85 for rich
gas condensates to 1.0 for dry gases.
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An approximate correlation for estimating solution oil-gas ratio is (Whitson,

1994, unpublished)

r s = r s (0.08 + 4 × 10 p )
* -7 2.5

(4-57)
r s = 1.25 × 10 R s ; R s = R s at 345 bara (5000 psia)
* -6 * *

3 3 3 3
with rs and r in Sm /Sm , Rs and R in Sm /Sm , and p in bara. R is the solution
gas-oil ratio of a hypothetical reservoir oil in equilibrium with the reservoir gas
at 5000 psia (345 bara). A bubblepoint correlation can be used to estimate R
using the approximate relations

(γg)reservoir oil ≈ (γg)resrevoir gas

(γAPI)reservoir oil ≈ 90 - (γAPI)reservoir gas

The correlation given by Eq. 4-54 is shown in Figure 4-9.

The correlation estimates reasonable magnitude and pressure
dependence of rs, but it is probably not more accurate than about 10 to 20%.

4.5.6 Total Formation Volume Factor

The total formation volume factor Bt is defined as the volume of a two-phase,
gas-oil mixture at elevated pressure and temperature, divided by the stock-tank
oil volume resulting when the two-phase mixture is brought to surface
conditions,
Vo + Vg
Bt = (4-58)
(Vo )sc

Bt is used for calculating the oil in-place for gas-condensate reservoirs,

3
where Vt=Vg Assuming one reservoir m of hydrocarbon pore volume, the
3
initial condensate in place in Sm is given by N=1/Bt, and the initial "dry"
separator gas in place is Gd=NRp. Rp is the initial producing gas-oil ratio.

When reservoir pressure is greater than or equal to the dewpoint pressure,

Bt=Vg/(Vo)sc, and Bt is given by
Bt = Bgd R p
p ZT γ (4-59)
= ( sc ) (R p + 2.368 × 10 4 o )
T sc p Mo
3 3
with Rp in Sm /Sm . Condensate molecular weight Mo can be estimated from
the Cragoe correlation,
6084
Mo = (4-60)
γ API - 5.9
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4.5.7 Gas Viscosity

Viscosity of reservoir gases generally ranges from 0.01 to 0.03 cp at standard
and reservoir conditions, reaching up to 0.1 cp for near-critical gas condensates.
Gas viscosities are rarely measured because most laboratories do not have the
required equipment.

The most common gas viscosity correlation is given by Lee, Gonzales, and
36
Eakin
µ g = A 0 exp(A1 ρgA2 )
(9.379 + 0.46555 γ g ) T1.5
A 0 = 10 ×
-4

209.2 + 558.0 γ g + T (4-61)

A1 = 3.448 + (986.4 /T) + 0.29231 γ g
A 2 = 2.447 - 0.2224 A1

3 o
with ρg in g/cm and T in R. This correlation is used by most reservoir
laboratories when reporting gas viscosities based on measured specific gravities.
7
McCain claims that the correlation is reliable within 2-4% for gases with γg<1,
with errors approaching 20% for rich gas condensates with γg>1.5.

Gases at very high pressure or with significant amounts of nonhydrocarbons

37
should use the Lucas viscosity correlation . Another correlation frequently used
38
is the Carr, Kobayashi, and Burrows correlation .

4.6 Water/Brine PVT Correlations

4.6.1 Introduction
The connate or "original" water found in petroleum reservoirs usually contains
dissolved salts, consisting mainly of sodium chloride (NaCl), and solution gas
consisting mainly of CO2, methane and ethane. Initial water saturation can range
from 5 to 50% of the pore volume in the net-pay intervals of a reservior where
production is primarily oil and gas. Higher water saturations are found in non-
net pay, in the aquifer, and where water has swept oil or gas during a waterflood
or water influx.

From a reservoir depletion point of view, the amount of water connected

with a reservoir is as important as the properties of the water, particularly in
material balance calculations where the water expansion (compressibility times
water volume) may contribute significantly to pressure support. From a
production point of view, the mobility of water is important, requiring the
determination of water saturations (i.e. relative permeability) and water
viscosity. For surface processing calculations, the composition of water, the
water content in the produced wellstream, and the conditions where water and
hydrocarbons coexist must be defined.
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The three most important aspects of water-hydrocarbon phase behavior are:

• Mutual solubilities of gas and water

• Volumetric behavior of reservoir brines
• Hydrate formation and treatment

This section presents PVT correlations for water-hydrocarbon systems. The

standard PVT properties, solution gas-water ratio Rsw, isothermal water
compressibility cw, water formation volume factor Bw, water viscosity µw, and
water content in gas rsw are correlated in terms of pressure, temperature, and
salinity using graphical charts and empirical equations. Correlations for water-
hydrocarbon interfacial tension σwh are also presented.

At high temperatures and pressures, some correlations and the existing

water-property data base are not adequate. Equations of state have been used
with reasonable success in predicting mutual solubilities and phase properties of
hydrocarbon-water systems at temperatures up to 200°C and pressures greater
than 700 bara,. The effect of salinity on gas-water phase behavior has also, to
some extent, been treated by EOS methods.

4.6.2 Properties and Correlations

Like all reservoir fluids, the properties of formation waters depend on
composition, temperature, and pressure. Reservoir water is seldom pure, and it
usually contains dissolved gases and salts. Total dissolved solids (TDS) usually
consist mainly of NaCl, ranging from 10,000 ppm to about 300,000 ppm. Sea
water has a salinity of about 30,000 ppm. Table 4-1 gives the composition of
several reservoir brines.

Water is limited by how much salt it can keep in solution. The limiting
concentration for NaCl brine is given by,
* 2
Csw = 262,180 + 72 T + 1.06 T (4-62)

with T in °C and C*sw in ppm. If reservoir temperature is known but a water

sample cannot be obtained, this relation gives the limiting salinity of the
reservoir brine. Usually the salinity of a brine is less than 80% of the value
given by Eq. (4-62). Otherwise, the best estimate of brine salinity can be taken
from a neighboring reservoir in the same geological formation.

Scale buildup in tubing and surface equipment is caused by the precipitation

of salts in produced brine. Scale is usually caused by precipitation of calcium
carbonate, calcium sulfate (e.g. gypsum), barium or strontium sulfates, and iron
compounds. Temperature, pressure, total salinity and salt composition are the
primary variables determining the severity of scaling. Note that Eq. (4-62)
should not be used for the detection of conditions that result in scale buildup.

Dissolved gas in water is usually less than 30 scf/STB (about 0.4 mol
percent) at normal reservoir conditions. The effect of salt and gas content on
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water properties can be important, and the following discussion gives methods to
estimate fluid properties in terms of temperature, pressure, dissolved gas, and
salinity. Methods for estimating the PVT properties of formation water are
usually based on first estimating the properties of pure water at reservoir
temperature and pressure, then correcting the pure-water properties for salinity
and dissolved gas.

4.6.3 Salinity
+ + ++ ++
The cations dissolved in formation waters usually include Na , K , Ca , Mg ,
- -- -
and the anions include Cl , SO4 , HCO3 . Most formation waters contain
primarily sodium chloride (NaCl). Suspended salts, entrained solids, and
corrosion-causing bacteria may also be present in reservoir waters, but these
constituents do not usually affect the PVT properties of formation waters. The
geochemistry of formation waters can be useful in detecting foreign water
encroachment, and in determining its source. Table 4-1 gives example
compositions of reservoir brines.

Salinity defines the concentration of salts in a saline solution (brine), and it

may be specified as one of several quantities: weight fraction (ws), mole fraction
(xs), molality (csw), molarity (csv), parts per million by weight (Csw), and parts per
million by volume (Csv). These quantities are formally defined in Table 4-2,
where ms is the mass of salt in g, m ow is the mass of pure water in g, ns is the
moles of salt in gmol, n ow is the moles of pure water in gmol, and Vw is the
3
volume of the brine mixture in cm .

Some common conversions for the various concentrations are

Csv = ρ w Csw
Csv = 6
Csw = 10 w s
ρw
17.1 (4-63)
csw = 6 -1
10 Csw - 1
6
10
Csw =
17.1c-sw1 + 1

where the last two equations apply for NaCl brines. If brine density ρw at
standard conditions (1.0135 bara and 15.5°C) is not reported, it can be estimated
from the Rowe-Chou density correlation{Rowe, 1970 #342} for NaCl,
ρ w (psc , Tsc) = (1.0009 - 0.7114 w s + 0.26055 w s2 )-1 (4-64)
3
with ρw in g/cm and ws in weight fraction TDS. For many engineering
3
applications ρw=1 g/cm is assumed, and the mass of salt is considered
negligible compared with the mass of pure water, resulting in the approximate
relations:
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csv ≈ csw = cs
Csw ≈ Csv = Cs (4-65)
cs ≈ 17.1(10 − 6 )Cs

-6
where the constant 17.1(10 ) applies for NaCl brines.

4.6.4 Gas Solubilities in Water/Brine

The solubility of natural gases in water is rather complicated to estimate from
empirical correlations. However, the effect of gas solubility is usually minor
except at high temperatures. At temperatures less than about 150°C and
pressures less than 350 bara, solubility is usually less than 0.4 mol percent, or
3 3 40
about 5.5 Sm /Sm . According to Dodson and Standing's results , this amount
of dissolved gas causes an increase of about 25 percent in water compressibility,
-5 -5 -1
e.g. from 5.5(10 ) to 7.0(10 ) bar . Experimental gas solubilities for C1-C4,
non-hydrocarbons, natural gas, and a few binaries and ternaries are available in
the literature.

At reservoir conditions the solubility of methane in water and the effect of

salinity are the most important variables affecting water properties. The
following empirical equation gives a reasonable fit of the Culbertson and
41
McKetta solubility data for methane in pure water at conditions 38<T<175°C
and 0<p<700 bara,
 3  3  
∑  ∑ Aij T j  pi 
-3
x C1 = 10   (4-66)
 i = 0  j= 0  
where

A00 = 0.299E+00 A10 = 2.283E-03

A01 = -1.273E-03 A11 = -1.870E-05
A02 = 0.000E+00 A12 = 7.494E-08
A03 = 0.000E+00 A13 = -7.881E-11

A20 = -2.850E-07 A30 = 1.181E-11

A21 = 2.720E-09 A31 = -1.082E-13
A22 = -1.123E-11 A32 = 4.275E-16
A23 = 1.361E-14 A33 = -4.846E-19

with T in °F and p in psia. Gas solubility expressed as a solution gas-water ratio

Rsw at standard conditions is given by
xg
R sw = 1313 _ 1313 x g (4-67)
1- xg
3 3
with Rsw in Sm /Sm ; replacing the constant 1313 with 7370 yields Rsw in
scf/STB.

A standard two-phase flash calculation using a cubic EOS gives surprisingly

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accurate prediction of gas solubilities, as discussed later in this chapter. This

approach is the recommended procedure for estimating gas solubilities of
hydrocarbon-water/brine mixtures at high pressures and temperatures.

4.6.5 Salinity Correction for Solubilities

42
Setchenow (sometimes written Secenov) gives the following relation for
correcting the hydrocarbon solubility in pure water for salt content,
 (φi∞ )w 
k s = lim cs-1 log ∞ o  (4-68)
cs → 0  (φi )w 

where ks is the Setchenow constant and cs is salt concentration; (φ)w and (φ) w
o

are the fugacity coefficients of component i at infinite dilution in the salt solution
and in pure water, respectively. Both molality and molarity have been used in
the literature for defining Setchenow constants, though molality (csw) is now
considered the preferred concentration, where the Setchenow constant has the
-1
unit molality (i.e., kg/gmol).

The ratio of infinite-dilution fugacity coefficients is traditionally assumed to

give an accurate estimate of the ratio of solubilities, yielding the relation
R sw ≈ x g = - ks cs ≈ -17.1(10-6 ) ks Cs (4-69)
o o 10 10
R sw x g

where R osw is the solubility of gas in pure water and Rsw is the solubility of gas in
brine. For ks>0 the gas solubility is less in brines than in pure water, a fact
which has led to the use of "salting-out coefficient" for ks.

The Setchenow constant is more or less independent of pressure, though it is

a strong function of temperature. Cramer gives a detailed treatment of
Setchenow (and Henry's) constants for the C1-NaCl system using data at
43
temperatures up to 300°C and pressures up to 135 bara. Søreide and Whitson
44
give a best-fit relation for the Cramer correlation ,
(k s )C1- NaCl = 0.1813 - 7.692(10-4) T
(4-70)
+ 2.6614(10- 6) T 2 - 2.612(10- 9) T 3
-1
with ks in molality and T in °F. Using relations suggested by Pawlikowski and
42
Prausnitz relating ks of methane to ks of other hydrocarbons, Søreide and
Whitson propose the following relation for hydrocarbon ks,
k si = (k s )C1- NaCl + 0.000445(T bi - 111.6) (4-71)
-1
with ks in molality and the normal boiling point Tbi in K.
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45
Clever and Holland give salting-out correlations for C1-NaCl and CO2-
NaCl systems. The correlation for CO2-NaCl is
(k s )CO2 - NaCl = 0.257555 - 0.157492(10-3) T
(4-72)
- 0.253024(10-5) T 2 + 0.438362(10-8) T 3
-1
with T in K and ks in molality . The temperature range for Eq. (4-72) is
4<T<350°C. The Setchenow coefficient varies somewhat with pressure for the
CO2-NaCl system, thereby making Eq. (4-72) less accurate than hydrocarbon-
NaCl correlations.

4.6.6 Equilibrium Conditions in Oil/Gas-Water Systems

All phases - oil, gas, and water - in a reservoir are initially in thermodynamic
equilibrium. This implies that the water phase contains finite quantities of all
hydrocarbon and nonhydrocarbon components found in the hydrocarbon phases,
and that the hydrocarbon phases contain a finite quantity of water. The amount
of lighter compounds (C1, C2, N2, CO2, and H2S) in the water phase can be
significant, depending mainly on the amount of each component in the
hydrocarbon phase(s). The amount of C3+ hydrocarbons found in water is
usually small and can be neglected.
The K-value representing the ratio of the mole fraction of component i in the
hydrocarbon phase to the mole fraction of component i in the water phase,
Ki=zi,HC/xi,AQ, is approximately constant at a given pressure and temperature,
independent of overall hydrocarbon composition and whether the hydrocarbon is
single phase or two-phase. For example, the amount of methane dissolved in
water for a methane-rich natural gas will be higher than the amount of methane
dissolved in water for an oil (above its bubblepoint). Furthermore, the amount
of methane dissolved in water for a gas-oil system with overall methane content
of 40 mol-% will probably be about the same as for a single-phase oil with 40
mol-% methane.

An oil that is undersaturated (with respect to gas) is still in equilibrium with

the water phase. When pressure is lowered, a new equilibrium state is reached
between the gas-undersaturated oil and water. The result is that some of the
methane will move from the water to the oil (without forming free gas). That is,
the solution gas-water ratio decreases. At some lower pressure the oil will reach
its bubblepoint (with respect to gas), and further reduction in pressure will yield
two sources of free gas: (1) gas coming out of solution from the oil, and (2) gas
coming out of solution from the water.

Therefore, for an undersaturated oil reservoir, the solution gas-water ratio of

reservoir brine will continuously decrease from the initial reservoir pressure
down to the reservoir oil's bubblepoint pressure, and further at lower pressures.
Correspondingly, the reservoir oil solution GOR will increase (albeit slightly)
from initial pressure to the bubblepoint pressure, thereafter decreasing below the
bubblepoint. An EOS can be used to quantify the changing solution gas-water
and gas-oil ratios in this situation.
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4.6.7 Water/Brine FVF and Compressibility

The FVF of reservoir water Bw depends on pressure, temperature, salinity, and
dissolved gas. Contrary to saturated oil volumetric behavior, the liquid volume
of a gas-saturated water increases with decreasing pressure. That is, the
expansion due to isothermal compressibility is larger than the shrinkage due to
gas coming out of solution.
40
The pressure dependence of Bw given by Dodson and Standing for gas-
saturated water/brine will apply to all gas reservoirs and oil reservoirs with
appreciable solution gas. Even if the oil is undersaturated, as discussed earlier,
the solution gas-water ratio will decrease continuously from the initial pressure
to the oil bubblepoint pressure and further thereafter.
The formation volume factor Bow of brine at atmospheric pressure, reservoir
temperature, and without dissolved gas is given by

o ρ w (psc , Tsc) vow (psc , T)

Bw = = (4-73)
ρ ow (psc , T) v w (psc , Tsc)
46
Long and Chierici give experimental data and correlations for the density of
pure water and NaCl brine solutions, though the proposed correlations
extrapolate poorly at temperatures greater than about 120°C.
39
The following correlation is given by Rowe and Chou for water and NaCl
brine specific volume at zero pressure (also applicable at atmospheric pressure),
o 1
v w (psc , T) = = A 0 + A1 w s + A 2 w s2
ρ (psc , T)
o
w
-5 2
A 0 = 5.916365 - 0.01035794 T+ 0.9270048(10 ) T
- 1127.522 T -1 + 100674.1T - 2 (4-74)
-4 2
A1 = - 2.5166 + 0.0111766 T- 0.170552(10 ) T
-4 2
A 2 = 2.84851 - 0.0154305 T+ 0.223982(10 ) T

3
with in cm /g, T in K, and ws as weight fraction of NaCl. The effect of pressure
on FVF can be calculated using the definition of water compressibility,
* 1 ∂ Bw
cw = - ( )C , T (4-75)
Bw ∂ p s
which when integrated gives
p
B*w (p, T )
ln o = − ∫ c*w (p, T)dp (4-76)
Bw (psc , T) 0

Using the compressibility data reported by Rowe and Chou covering the
conditions 20<T<175°C, 10<p<310 bara, and 0<ws<0.3, a general correlation
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for the compressibility of a brine (without solution gas), c*w , is

* -1
c w (p, T) = (A 0 + A1 p )
6 -4
A 0 = 10 [0.314 + 0.58 w s + 1.9(10 ) T (4-77)
- 1.45(10- 6) T 2]
A1 = 8 + 50 w s - 0.125 w s T

* -1
with c w in psi , p in psia, T in °F, and ws in weight fraction of NaCl. Solving
*
Eq. (4-76) for the FVF of a brine without solution gas, B w gives
A1 p (-1 / A1)
Bw (p, T) = B w (psc , T) × (1 +
* o
) (4-78)
A0

where A0 and A1 are given in Eq. (4-77). Eq. (4-78) results in water and brine
densities that are within 0.5 percent of values given by the highly accurate
47
correlation of Rogers and Pitzer for 15<T<200°C, 0<p<1,000 bara, and
0<Cs<300,000 ppm. For the same range of conditions, Eq. (4-77) calculates
isothermal compressibilities within about five percent of the values given by
Rogers and Pitzer.

Using Dodson and Standing's data for pure water saturated with a natural
gas, an approximate correction for dissolved gas on water/brine FVF at saturated
conditions is given by
Bw (p, T, R sw ) = Bw (p, T) × (1 + 0.0001 R sw )
* 1.5
(4-79)

with Rsw in scf/STB. This relation fits the Dodson-Standing data at 150, 200,
and 250°F, but overpredicts the effect of dissolved gas at 100°F.

Dodson and Standing also give a correction for the effect of dissolved gas on
water/brine compressibility,
c w (p, T, R sw ) = c w (p, T) × (1 + 0.00877 R sw )
*
(4-80)

with Rsw in scf/STB. This relation is only valid for undersaturated oil-water
systems above the oil bubblepoint pressure.

4.6.8 Water/Brine Viscosity

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The viscosity of pure water and NaCl brines are functions of temperature and
salinity, and can be estimated from the following equations presented by Kestin
48
et al. who report an accuracy of ±0.5% in the range 20<T<150°C, 0<p<350
bara, and 0<Csw<300,000 ppm (0<csw<5 molality),
µ w = (1 + A 0 p) µ w
*

µw µ
* o
log = A1 + A 2 log o w
µw µ w 20
o

-3
A 0 = 10 [0.8 + 0.01(T- 90) exp(-0.25 csw )]
3

A1 = ∑ a1i csw
i
(4-81)
i =1
3

A 2 = ∑ a 2 i csw
i

i =1

µw (20 - T )i
o 4
log = ∑ 96 + T
µ w 20o i =1
a 3 i

µ w 20o = 1.002 cp

where
a11 = 3.324E-2 a21 = -3.96E-2 a31 = 1.2378
a12 = 3.624E-3 a22 = 1.02E-2 a32 = -1.303E-3
a13 = -1.879E-4 a23 = -7.02E-4 a33 = 3.060E-6
a34 = 2.550E-8

with µ in cp, T in °C, and p in MPa. The pressure correction A0 given by Kestin
et al. contains 13 constants and does not extrapolate well at high temperatures.
The pressure correction for A0 given above is a more well-behaved equation,
with only small deviations from the original Kestin et al. correlation (at low
temperatures).

The effect of dissolved gas on water viscosity has not been reported.
Intuitively, one might suspect that water viscosity decreases with increasing gas
solubility, though Collins suggests that dissolved gas may increase brine
viscosity. Systems saturated with CO2 do show an increase in viscosity with
increasing gas solubility.

4.6.9 Solubility of Water in Natural Gas

41
The solubility of pure water in methane is given by McKetta and Wehe who
give charts for correcting pure water solubilities for salinity and gas gravity
(based mainly on the results of Dodson and Standing). A best-fit equation for
these charts is
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o
y w = y w Ag As
0.05227 p+ 142.3 ln p- 9625
ln yow = - 1.117 ln p+ 16.44
T+ 460
(4-82)
γ g - 0.55
Ag = 1 +
1.55(10 ) γ g T -1.446 - 1.83(104) T -1.288
4

-9 1.44
A s = 1 - 3.92(10 ) Cs

with T in °F, p in psia, and Cs in ppm or mg/L. Eq. (4-82) yields an absolute
average deviation of 2.5 percent for y ow , with a maximum error less than 10
percent for 35<T<240°C and 15<p<700 bara. Mole fraction of water in gas yw
can be converted to a water-gas ratio rsw using the relation
yw
r sw = 7.58 × 10 ≈ 7.58 × 10- 4 y w
-4
(4-83)
1 - yw
3 3 -4
with rsw in Sm /Sm . Replacing the constant 7.58⋅10 with 135 yields rsw in
STB/MMscf, and replacing with 47,300 yields rsw in lb/MMscf.

The correction term for salinity As proposed by Dodson and Standing is

based on limited results for one low-salinity brine. The salinity correction given
49
by Katz, et al. (given in Eq. (4-82)) is based on the lowering of vapor pressure
for brine solutions at 100°C, where the assumption is made that
y w p vw (100° C, Cs)
≈ o (4-84)
p vw (100° C)
o
yw

where pvw is the brine vapor pressure and p ovw is the pure-water vapor pressure,
both measured at 100°C. Very little data is available to confirm these two
salinity corrections. However, EOS calculations indicate that the Katz et al.
correlation is probably valid up to a molality of about 3; at larger molalities the
EOS-calculated ratio y w / y ow is less than predicted by the Katz et al. correlation.

Finally, water that is dissolved in reservoir gas and oil mixtures will not
contain salts (i.e. it is fresh water), a fact that can help in identifying the origin of
produced water.

4.6.10 Water/Brine-Hydrocarbon Interfacial Tension

The interfacial tension of water-hydrocarbon systems σwh varies from about 72
mN/m (72 dynes/cm) for water/brine-gas systems at atmospheric conditions to
20-30 mN/m for water/brine-STO systems at atmospheric conditions. The
variation in σwh is nearly linear with the density difference between water and
the hydrocarbon phase ∆ρwh (i.e., ∆ρwo or ∆ρwg), where σwh=72 mN/m at
∆ρwh=∆ρwg=1 g/cm3. This can be expressed in equation form as
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σ wh = σ o + (72 - σ o)∆ ρ wh (4-85)

where σ is the intercept at ∆ρwh=0.

o

Ramey , in an unpublished SPE paper, proposes a correlation for σwh based

50

on the Macleod parameter σ /∆ρ. This parameter was plotted versus ∆ρ using
1/4

data for brines with stock-tank oil, saturated and undersaturated reservoir oils,
and natural gases. Ramey's graphical correlation is represented surprisingly well
with Eq. (4-85), where σ =15; a near-exact fit of his correlation is given by
o

σ wg = 20 + 36 ∆ ρ wh (4-86)
Data presented by Ramey which do not lie on his general correlation are
represented accurately by Eq. (4-85) with σ ranging from 5 to 30.
o

51
Firoozabadi and Ramey consider the interfacial tension of water and
hydrocarbons using data for distilled water and pure hydrocarbons. They arrive
at a similar graphical relation to the original Ramey correlation, with the addition
of reduced temperature as a correlating parameter. Their correlation does not,
unfortunately, predict water/brine-oil IFTs with more accuracy than the original
Ramey correlation (or Eq. (4-85)). Water-gas IFTs reported by various authors
show considerable scatter, and it would seem that any correlation will only give
approximate IFT values for such systems until consistent data becomes
available.

Mutual solubility effects of gas dissolved in water and water dissolved in gas
may affect interfacial tensions, perhaps explaining some of the difference in
methane-brine and methane-water IFTs reported in the literature. Otherwise, the
seemingly erratic behavior of some water/brine-oil IFT data may be explained by
aromatic compounds and asphaltenes. Also, crude oil samples exposed to
atmospheric conditions for longer periods of time may experience oxidation that
can affect IFT measurements.

4.6.11 Equation-of-State Predictions

Mutual solubilities and volumetric properties of water-hydrocarbon systems can
be predicted with reasonable accuracy using one of several modifications to
existing cubic equations of state. Other types of equations of state also have
been applied to these systems, but without a clearly superior predictive
capability. Although cubic EOSs are not widely used for reservoir water-
hydrocarbon systems, it is expected that this approach will eventually replace the
empirical correlations presently being used.

To improve vapor pressure predictions of water (and solubilities of water in

52
the non-aqueous phase), Peng and Robinson propose a modified correction
term α (applied to the EOS constant a) for pure water in the temperature range
43
0.44<Tr<0.72 (15<T<200°C). The recommended Søreide-Whitson relation for
αH2O of pure water (or NaCl brine) to be used with the Peng-Robinson EOS is
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α H 2 O = 1 + 0.453 [1 - T r H 2 O (1 - 0.0103 csw )

0.5 1.1

+ 0.0034(T -r3H 2 O - 1)]

(4-87)

With this α term for water/brine, the PR EOS will predict the vapor pressure of
pure water within 0.2 percent of steam-table values for the range 0.44<TrH2O<1
(i.e. T>15°C); it also can be used to predict vapor pressure of NaCl solutions
with the same accuracy.

With a correction for salinity in the α term it is expected that the predicted
solubilities of water in nonaqueous phases will be fairly accurate.

The most important modification of existing cubic EOSs for water-

hydrocarbon systems is the introduction of alternative mixing rules for EOS
constant A, where different binary interaction coefficients kij are used for the
aqueous and non-aqueous (hydrocarbon) phases.

Peng and Robinson propose a simple EOS modification for hydrocarbon-

water systems; namely, two sets of kij are defined, kij,HC for the hydrocarbon
phase(s) and kij,AQ for the aqueous phase. The EOS constant A is therefore
calculated separately for the aqueous and hydrocarbon phases,
N N

A HC = ∑ ∑ yi, HC y j, HC Ai A j (1 - kij, HC )
i =1 j=1
N N
(4-88)
A AQ = ∑ ∑ x i, AQ x j,AQ Ai A j (1 - kij, AQ )
i =1 j=1

where yi,HC is the hydrocarbon composition (gas or oil) and xi,AQ is the
composition of the water phase. Using two sets of kij has been successfully
applied to correlate mutual solubilities of hydrocarbon-water and
nonhydrocarbon-water binary systems.

Table 4-3 gives recommended kij relations for both aqueous and non-
aqueous phases for the Peng-Robinson EOS, where these interaction coefficients
must be used with the general αH2O relation (Eq. (4-87)). The CO2-water/brine
correlation gives best results at pressures less than about 350 bara, as data in this
region have been given more weight when developing the correlation.

Considerable data on solubilities of hydrocarbon and nonhydrocarbon gases

in brine solutions were used in making the salinity corrections for aqueous
phases kij. Similar data were not available for solubilities of water in the
nonaqueous phase for mixtures containing brines. Until more data become
available it will be necessary to assume that the effect of salinity is adequately
treated by the modified αH2O term (Eq. (4-87)).

Simultaneous application of both aqueous and non-aqueous phase interaction

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coefficients requires modification of the standard EOS implementation (which

uses a single set of kij).

A standard implementation of the PR EOS can still be used with the BIPs
given in Table 4-3. If only gas solubility in the water phase is needed then
accurate gas solubilities are predicted using the aqueous phase kij,AQ for both
phases. However, the calculated water content in the hydrocarbon phase will not
be accurate. Likewise, if only water solubility in the hydrocarbon phase is
needed then the hydrocarbon phase kij,HC can be used for both phases; the
calculated HC content in the aqueous phase will not, however, be accurate.

Several non-cubic equations of state have been proposed for water-

hydrocarbon systems, including conventional activity coefficient models that are
limited to relatively low pressures, and more general electrolyte EOS models.
However, these models do not appear to be better than the simpler modifications
of cubic EOSs.

4.6.12 Converting EOS Results to Bw, Rsw, and rsw

Physical properties of gas-water systems used in petroleum engineering can
be derived from equation of state (EOS) calculations as shown below. The EOS
52
calculations are based on the Peng-Robinson EOS with interaction coefficients
43
proposed by Søreide and Whitson. Volumetric properties are also calculated
with the EOS using volume translation, where shift parameters are determined to
ensure accurate volumetric properties of water-free gas and gas-free water (using
53
the MATCh command in PVTx ).

A constant volume depletion (CVD) experiment is simulated with PVTx

using as initial feed the reported water-free gas composition (e.g. summing to
100). A specified amount of brine component (e.g. 100) is also included in the
feed. The amount of brine component added determines the initial water
saturation when the overall feed (normalized automatically by PVTx) is flashed
at initial reservoir conditions. For the Washita Creek reservoir, adding 49.0
moles of brine to 100 moles of water-free gas resulted in an initial water
saturation of 10%.

Note that the PSAT=OFF option in PVTx must be used when simulating the
CVD experiment for this type of analysis. To make water-hydrocarbon
calculations with PVTx, several special commands are used:

1. The PROP command defines the properties of the brine component.

2. The interaction parameters for the non-aqueous phase (BIPS) and the
aqueous phase (BIPS WATER) are specified.

3. The MATCh command is needed to define the volume translation parameter

of the brine component.

4. The KCOR WATER command is used to initialize K-values.

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BIPWAT (Lotus 1-2-3) Spreadsheet

All input parameters required for PVTx can be generated using the Lotus 1-2-3
spreadsheet BIPWAT.WK3 (Søreide and Whitson correlations). Note that for
the Washita Creek study, the volume translation coefficients of both methane
and CO2 were modified slightly to fit water-free gas Z-factors calculated using
3 25
the Standing-Katz chart (Hall-Yarborough EOS correlation ).

The spreadsheet also calculates brine viscosity as a function of pressure and

temperature (the effect of non-aqueous component solubilities on viscosity is not
included). Results can be used to calculate the viscosibility

Cvw = (dµw/dp)µ

where µ ow is the water viscosity at the reference pressure (e.g. initial reservoir
pressure).

Gas-Water Physical Properties

EOS calculations yield the following basic results needed for calculation of
gas-water physical properties:

1. Reservoir gas Z-factor Zg.

2. Reservoir water density ρw.
3. Compositions of reservoir gas (yj) and reservoir water (xj).
4. Reservoir water saturation (Sw); variable "vro" in PVTx.

Component molecular weights are also used, as is the component brine density
at standard conditions, ρbrine.

The Lotus 1-2-3 spreadsheet BIPWAT.WK3 results and PVTx input data set
for example Visund gas-water and oil-water systems are included in section 5.8.

Some of the properties calculated with equations below are also reported by
PVTx (e.g. reservoir water molecular weight Mw and reservoir gas specific
gravity γg). The calculated values should be the same as output by PVTx; use as
a check.
a
Solution Water-Gas Ratio (rsw)
M brine )( ybrine )
R vw = rsw = 0.0423( (4-89)
ρ brine 1 - ybrine

a
Water in solution in the reservoir gas is actually fresh water. Because the EOS does not
"know" that the water partitioning into gas is salt-free, the correct equation for rsw (based on pure
water) can not be used,
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Solution Gas-Water Ratio (Rsw)

ρ brine 1 - x brine
R sw = 23.66 ( ) ( ) (4-90)
M brine x brine

Reservoir Water FVF (Bw)

(ρbrine )sc + 1.22 γ gds R sw
Bw = (4-91)
ρw
Reservoir Gas Specific Gravity (γg)
n
∑ yjM j
j =1
γg = (4-92)
n
28.97 ∑ y j
i= j

Reservoir Gas Density (ρg)

28.97 p γ g
ρg = (4-93)
Zg RT

Reservoir Gas FVF (Bg)

Zg T
Bg = 0.00351 (4-94)
p

Free Dry (Water-Free) Gas Specific Gravity (γgd)

∑ yjMj
j≠ brine
γ gd = (4-95)
28.97 (1 - ybrine)

Solution Dry (Water-Free) Gas Specific Gravity (γgds)

∑ x jM j
j ≠ brine
γ gds = (4-96)
28.97 (1 - x brine)

3 3 3
where units are p in bara, T in K, ρ in kg/m , rsw and Rsw in Sm /Sm , and FVFs
3 3
Bg and Bw in m /Sm .
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4.7 References
1. "Handbok for Reservoar Simulering," Norsk Hydro.

2. "ECL100 User's Manual," Intera (1993).

3. Standing, M.B.: Volumetric and Phase Behavior of Oil Field Hydrocarbon

Systems, 8th printing, Society of Petroleum Engineers, Dallas (1977).

4. Glasø, Ø.: "Generalized Pressure-Volume-Temperature Correlations," JPT

(Nov. 1980) 785-795.

5. Lasater, J.A.: "Bubble Point Pressure Correlation," Trans., AIME (1958)

213, 379.

6. Vazquez, M. and Beggs, H.D.: "Correlations for Fluid Physical Property

Prediction," JPT (June 1980) 32, 968-970.

7. McCain, W.D., Jr.: "Reservoir Fluid Property Correlations - State of the

Art," SPERE (May 1991) 6, No. 2, 266-272.

8. Standing, M.B. and Katz, D.L.: "Density of Crude Oils Saturated with
Natural Gas," Trans., AIME (1942) 146, 159-165.

9. Standing, M.B.: Oil-System Correlations, P.P. Handbook (ed.),

McGraw-Hill Book Co. (1962).

10. Standing, M.B.: Petroleum Engineering Data Book, Norwegian Institute of

Technology, Department of Petroleum Engineering and Applied Geophysics,
Trondheim (1974).

11. Madrazo, A.: "Liquid-Density Correlation of Hydrocarbon Systems," Trans.,

AIME (1960) 219, 386-389.

12. Vogel, J.L. and Yarborough, L.: "The Effect of Nitrogen on the Phase
Behavior and Physical Properties of Reservoir Fluids," paper SPE 8815
presented at the 1980 SPE Annual Technical Conference and Exhibition,
Tulsa, April 20-23.

13. Katz, D.L.: "Prediction of the Shrinkage of Crude Oils," Drilling and
Production Practice, API (1942) 137-147.

14. Alani, G.H. and Kennedy, H.T.: "Volumes of Liquid Hydrocarbons at High
Temperatures and Pressures," Trans., AIME (1960) 219, ?-?

15. Lohrenz, J., Bray, B.G., and Clark, C.R.: "Calculating Viscosities of
NORSK Field Development & Technology MANUAL
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Curtis H. Whitson (PERA a/s) November 1998

Reservoir Fluids from Their Compositions," JPT (Oct. 1964) 1171-1176;

Trans., AIME, 231.
16. Rackett, H.G.: "Equation of State for Saturated Liquids," J. Chem. Eng. Data
(1970) 15, No. 4, 514-517.

17. Hankinson, R.W. and Thomson, G.H.: "A New Correlation for Saturated
Densities of Liquids and Their Mixtures," AIChE J. (1979) 25, No. 4,
653-663.

18. Hankinson, R.W., et al.: "Volume Correction Factors for Lubricating Oils,"
Oil & Gas J. (Sept. 28, 1981) 297-308.

19. Chew, J.N. and Connally, C.A.: "A Viscosity Correlation for Gas-Saturated
Crude Oils," Trans., AIME (1959) 216, 23-25.

20. Bergman, D.F.: "Oil Viscosity Correlations," Personal Communication

(1992).

21. Aziz, K., Govier, G.W., and Fogarasi, M.: "Pressure Drop in Wells
Producing Oil and Gas," J. Can. Pet. Tech. (July-Sept. 1972) 38-48.

22. Beggs, H.D. and Robinson, J.R.: "Estimating the Viscosity of Crude Oil
Systems," JPT (Sept. 1975) 27, No. 9, 1140-1141.

23. Whitson, C.H. and Brule, M.R.: Phase Behavior, Monograph, SPE of
AIME, Dallas (1994) (in print).

24. Standing, M.B. and Katz, D.L.: "Density of Natural Gases," Trans., AIME
(1942) 146, 140-149.

25. Hall, K.R. and Yarborough, L.: "A New Equation of State for Z-factor
Calculations," Oil & Gas J. (June 18, 1973) 82-90.

26. Takacs, G.: "Comparisons Made for Computer Z-factor Calculations," Oil &
Gas J. (Dec. 20, 1976) 64-66.

27. Dranchuk, P.M. and Abou-Kassem, J.H.: "Calculation of Z-Factors for

Natural Gases Using Equations of State," J. Can. Pet. Tech. (July-Sept.
1975) 14, No. 3, 34-36.

28. Brill, J.P. and Beggs, H.D.: "Two-Phase Flow in Pipes," U. Tulsa (1974)
INTERCOMP Course, The Hague.

29. Sutton, R.P.: "Compressibility Factors for High-Molecular Weight Reservoir

Gases," paper SPE 14265 presented at the 1985 SPE Technical Conference
and Exhibition, Las Vegas, Sept. 22-25.

30. Kay, W.B.: "Density of Hydrocarbon Gases and Vapors at High Temperature
NORSK Field Development & Technology MANUAL
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and Pressure," Ind. Eng. Chem. (1936) No. 28, 1014-1019.

31. Matthews, T.A., Roland, C.H., and Katz, D.L.: "High Pressure Gas
Measurement," Proc., NGAA, 41 (1942).

32. Wichert, E. and Aziz, K.: "Calculate Z's for Sour Gases," Hydro. Proc. (May
1972) 51, 119-122.

33. Whitson, C.H.: Petroleum Engineering Fluid Properties Data Book,

Trondheim, Norway (1994).

34. Cragoe, C.S.: "Thermodynamic Properties of Petroleum Products," U.S.

Dept. Commerce (1929) 97.

35. Amyx, J.W., Bass, D.M., Jr., and Whiting, R.L.: Petroleum Reservoir
Engineering, McGraw-Hill Book Co., New York (1960).

36. Lee, A.L., Gonzalez, M.H., and Eakin, B.E.: "The Viscosity of Natural
Gases," JPT (Aug. 1966) 997-1000; Trans., AIME, 237.

37. Lucas, K.: Chem. Ing. Tech. (1981) 53, 959.

38. Carr, N.L., Kobayashi, R., and Burrows, D.B.: "Viscosity of Hydrocarbon
Gases Under Pressure," Trans., AIME (1954) 201, 264-272.

39. Rowe, A.M. and Chou, J.C.S.: "Pressure-Volume-Temperature-Correlation

Relation of Aqueous NaCl Solutions," J. Chem. Eng. Data (1970) 15, 61-66.

40. Dodson, C.R. and Standing, M.B.: "Pressure, Volume, Temperature and
Solubility Relations for Natural Gas-Water Mixtures," Drill. and Prod.
Prac., API (1944) 173-179.

41. McKetta, J.J. and Wehe, A.H.: "Hydrocarbon-Water and Formation Water
Correlations," Petroleum Production Handbook, T.C. Frick and R.W. Taylor
(ed.), SPE, Dallas (1962) Volume II, 22-13.

42. Pawlikowski, E.M. and Prausnitz, J.M.: "Estimation of Setchenow Constants

for Nonpolar Gases in Common Salts at Moderate Temperatures," Ind. Eng.
Chem. Fund. (1983).

43. Soreide, I. and Whitson, C.H.: "Peng-Robinson Predictions for

Hydrocarbons, CO2, N2 and H2S With Pure Water and NaCl-Brines," Fluid
Phase Equilibria (1992) 77, 217-240.
o
44. Cramer, S.D.: "Solubility of Methane in Brines From 0 to 300 C," Ind. Eng.
Chem. Proc. Des. Dev. (1984) 23, No. 3, 533-538.
NORSK Field Development & Technology MANUAL
HYDRO Reservoir Technology PVT ANALYSIS

Chapter 4 PVT Requirements and Correlations Rev. 0.6

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Curtis H. Whitson (PERA a/s) November 1998

45. Clever, H.L. and Holland, C.J.: "Solubility of Argon Gas in Aqueous Alkali
Halide Solutions," J. Chem. Eng. Data (July 1968) 13, No. 3, 411-414.

46. Long, G. and Chierici, G.: "Salt Content Changes Compressibility of

Reservoir Brines," Pet. Eng. (July 1961) B-25 - B-31.

47. Rogers, P.S.Z. and Pitzer, K.S.: "Volumetric Properties of Aqueous Sodium
Chloride Solutions," J. Phys. Chem. Ref. Data (1982) 11, 1, 15-81.

48. Kestin, J., Khalifa, H.E., and Correia, R.J.: "Tables of the Dynamic and
Kinematic Viscosity of Aqueous NaCl Solutions in the Temperature Range
o
20-150 C and the Pressure Range 0.1-35 MPa," J. Phys. Chem. Ref. Data
(1981) 10, No. 1, 71-87.

49. Katz, D.L., et al.: Handbook of Natural Gas Engineering, McGraw Hill
Book Co., Inc., New York (1959).

50. Ramey, H.J., Jr.: "Correlations of Surface and Interfacial Tensions of

Reservoir Fluids," paper SPE 4429 unsolicitated.

51. Firoozabadi, A. and Ramey, H.J., Jr.: "Surface Tension of

Water-Hydrocarbon Systems at Reservoir Conditions," paper 873830
presented at the 1987 SPE Annual Technical Conference and Exhibition,
Calgary, June 7-10 (1987).

52. Peng, D.Y. and Robinson, D.B.: "A New-Constant Equation of State," Ind.
Eng. Chem. Fund. (1976) 15, No. 1, 59-64.

53. Whitson, C.H.: "An Equation-of-State Based Program for Simulating &
Matching PVT Experiments with Multiparameter Nonlinear Regression,"
Pera a/s, Trondheim, Norway (1994) Version 94-02,.
 NORSK Field Development & Technology MANUAL
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Table 4-1

Dodson-Standing Visund
* **
Sea (ppm) Arun Amundsen/ Kansas Kansas
Water Field Statfjord Wilcox Wilcox
Component (ppm) (mg/L) (mg/L) (mg/L) (mg/L)
Brine Brine
A B
Sodium (Na) 10,560 3,160 12,100 5,212 11,300 10,800 142,500
Calcium (Ca) 400 58 520 80 650 790 14,400
Magnesium (Mg) 1,270 40 380 5 90 5,560 68,500
Sulfate (SO4) 2,650 0 5 262 0 80 300
Chloride (Cl) 18,980 4,680 20,000 7,090 19,200 10,870 142,600
Bicarbonate 140 696 980 1,536 800 20 530
(HCO3) 0 0 130 0 0 0 3
Iodide (I) 65 0 0 0 0 80 350
***
Bromide (Br) 515 0 0 0 1,104 0 0
Others
Total 34,580 8,630 34,110 14,190 33,144 28,200 369,180
Specific Gravity 1.0243 (1.006) (1.024) 1.014 1.0235 1.015 1.140
o o o
@ @ @ @ @ 20 C @ 60 F @ 60 F
o o o o
20 C 60 F 60 F 60 F

*
Minimum salt-containing composition reported for the field/formation.
**
Maximum salt-containing composition reported for the field/formation.
***
Potasium (K): 600; Stronium (Sr): 230; Barium (Ba): 270; Iron (Fe): 4 mg/L.
Specific gravities in parentheses are estimated using Eq. 4-61.
NORSK Field Development & Technology MANUAL
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Table 4-2

Quantity Symbol Unit Definition

Weight Fraction ws g/g ms/(ms+m)

Mole Fraction xs gmol/gmol ns/(ns+n)

3
Molality csw gmol/kg 10 ns/m
3
Molarity csv gmol/L 10 ns/Vw
6
PPM (weight basis) Csw mg/kg 10 ms/(ms+m)
6
PPM (volume basis) Csv mg/L 10 ms/Vw
ns = Moles salt
ms = Mass salt
n = Moles pure water
m = Mass pure water
Vw = Volume brine solution
 NORSK Field Development & Technology MANUAL
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Table 4-3

AQUEOUS PHASE
Hydrocarbons (i=HC ; j=water/brine):
2
k ij, AQ = (1 + a 0 csw ) A0 + (1 + a1 csw ) A1 T ri + (1 + a 2 csw ) A 2 T ri

a 0 = 4.7863(10 ) ωi
-13 4

a1 = 0.01438
a 2 = 0.0021547

A0 = 1.112 - 1.7369 ωi
-0.1

A1 = 1.1001 + 0.836 ωi
A 2 = - 0.15742 - 1.0988 ωi
Nitrogen (i=N2 ; j=water/brine):
0.75 0.75
k ij, AQ = - 1.70235(1 + 0.025587 csw ) + 0.44338(1 + 0.08126 csw ) Tri
Carbon Dioxide (i=CO2 ; j=water/brine):
0.75 0.98
k ij, AQ = - 0.31092(1 + 0.15587 csw ) + 0.2358(1 + 0.17837 csw ) T ri
- 21.2566 exp(-6.7222 T r - csw )

Hydrogen Sulfide (i=H2S ; j=water/brine):

k ij, AQ = - 0.20441 + 0.23426 T ri

The acentric factors used in developing HC-water BIPs are:

C1 0.0108
C2 0.0998
C3 0.1517
C4 0.1931

NON-AQUEOUS PHASE
i kij,HC (j=water)
C1 0.4850
C2 0.4920
C3 0.5525
C4 0.5091
C5+ 0.5000
N2 0.4778
CO2 0.1896
H2S 0.19031-0.0.05965Tri
NORSK Field Development & Technology MANUAL
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Table 4-4
NORSK Field Development & Technology MANUAL
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Curtis H. Whitson (PERA a/s) November 1998

Figure 4-1
NORSK Field Development & Technology MANUAL
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Chapter 4 PVT Requirements and Correlations Rev. 0.6

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Curtis H. Whitson (PERA a/s) November 1998

Figure 4-2
NORSK Field Development & Technology MANUAL
HYDRO Reservoir Technology PVT ANALYSIS

Chapter 4 PVT Requirements and Correlations Rev. 0.6

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Curtis H. Whitson (PERA a/s) November 1998

Figure 4-3
NORSK Field Development & Technology MANUAL
HYDRO Reservoir Technology PVT ANALYSIS

Chapter 4 PVT Requirements and Correlations Rev. 0.6

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Curtis H. Whitson (PERA a/s) November 1998

Figure 4-4
NORSK Field Development & Technology MANUAL
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Chapter 4 PVT Requirements and Correlations Rev. 0.6

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Curtis H. Whitson (PERA a/s) November 1998

Figure 4-5
NORSK Field Development & Technology MANUAL
HYDRO Reservoir Technology PVT ANALYSIS

Chapter 4 PVT Requirements and Correlations Rev. 0.6

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Curtis H. Whitson (PERA a/s) November 1998

Figure 4-6
NORSK Field Development & Technology MANUAL
HYDRO Reservoir Technology PVT ANALYSIS

Chapter 4 PVT Requirements and Correlations Rev. 0.6

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Curtis H. Whitson (PERA a/s) November 1998

Figure 4-7
NORSK Field Development & Technology MANUAL
HYDRO Reservoir Technology PVT ANALYSIS

Chapter 4 PVT Requirements and Correlations Rev. 0.6

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Curtis H. Whitson (PERA a/s) November 1998

Figure 4-8
NORSK Field Development & Technology MANUAL
HYDRO Reservoir Technology PVT ANALYSIS

Chapter 4 PVT Requirements and Correlations Rev. 0.6

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Curtis H. Whitson (PERA a/s) November 1998

Figure 4-9