PVT Analysis

Lab Experiments
Fluid characterization
Fluid characterization
Bottom hole sampling
DST Separator analysis
Constituents of reservoir fluids

Defined components

TBP fractions

TBP residue
Defined components
GC analysis - Gas
C7+ components
Boling point (carbon number) fractions
Residue
TBP Cuts
TBP analysis
Phase envelops
Experiments depends on fluid types

• Black Oil: Constant Mass Expansion (CME / CCE / PV),

Differential Liberation (DV / DL), Separator Test, Viscosity

• Volatile Oil: CME (with liquid shrinkage), Constant

Volume Depletion (CVD), Separator Test, Viscosity

• Gas Condensate: CME Dew-point, CVD, Gas Viscosity

• Wet Gas: CME Dew-point

• Dry Gas: CME-Z

Constant Mass Expansion

• Carried out in almost all PVT studies irrespective of fluid type

• Performed to determine relation of Pressure and Volume at
Reservoir Temperature
• Also be referred to as: PV or CCE (Constant Composition
Experiments).
CME in phase diagram

CME gas condensate CME oil mixture

CME results – gas condensate
CME results – oil mixture
Constant Volume Depletion

• Carried out on either gas condensates or volatile oils at

Reservoir Temperature to simulate the volumetric and
compositional changes in the reservoir during production
(depletion)
• Carried out in 6 - 8 stages depending on the fluid type.
CVD results
Differential liberation

• Carried out on Black Oils at Reservoir Temperature to simulate

the volumetric and compositional changes in the reservoir
during production
DL results
Separator test

• Separator Tests are mostly carried out on oils to simulate the

volumetric and compositional changes when the reservoir flows
through production separators.
Separator test results

• Gas/oil volumetric ratio – GOR

• Oil density
• Gas gravity
• Oil formation volume factor - FVF
Swelling test
Swelling test results

• Mole% of gas added

• Saturation point
• Swollen volume
• Density
• Viscosity of the swollen oil mixtures
Temperature covered by PVT data

• Reservoir Temperature
- CME
- CVD
- Differential liberation
- Viscosity
• Temperatures < Reservoir temperature
- Separator

• Only Separator data can be used to validate fluid description for

Pipeline and Process conditions
 Case study: Well B – DST 2 sample

Well B PVT test

Production test DST 2

Flow period Flow period 1 - CCE and CVD

: Vapor Z factor, liquid saturation, vapor
Top perforation (m) 2900
density, vapor viscosity
Bottom perforation (m) 3000

Mid perforation (m) 2995 - 40 components can be used for EOS model
Formation Formation 1 as reported by the lab data, but it was not
Date July 2007
practical to be used for characterization in
terms of the required CPU time.
Available PVT data Composition up to
C36+
CCE.CVD at 290F

CGR (stb/MMscf) 55

Separator P (psi) 500

Separator T (F) 80

Dew point pressure (psi) 4600

Temperature (F) 290

EOS development

Name 8comp EOS 17comp EOS New EOS

EOS PR PR PR
Number of Compon
8 17 21
ents

CO2, N2, C1, C2, C3, iC4, n

CO2, N2, C1, C2, C3, iC4, n
CO2, C1N2, C2, C3, C4, C5+, C4, iC5, nC5, C6, C7, C8, C
Components C4, iC5, nC5, C6, C7, C8, C
C12+, C18+ 9, C10, C11, C12, C13, C14,
9, C10, C11, C12+, C19+
C15+, C20+, C36+

Composition B-DST2 composition B-DST2 composition B-DST2 composition

CCE, CVD, CCE, CVD,

Matching data CCE, CVD
CGR at DST CGR at DST

OmegaA, OmegaB, Acentric

Regression OmegaA, OmegaB, Acentric Tc, Pc, Acentric Factor of
Factor, Volume shift parameter
parameters Factor above C6.
of C1N2, C5+, C12+, C18+.

Others For reservoir evaluation. For facility design. Updated after 3 years
Comparison of EOS and Lab. data

• CCE – vapor z-factor at 308 oF

T1DST2 EOS Modeling

- CCE at 308degF
1.25

1.2

1.15

1.1
Vapor Z-factor

1.05
NewEOS
8compEOS
1
17compEOS
Lab-VaporZfactor
0.95

0.9

0.85

0.8
0 1000 2000 3000 4000 5000 6000 7000 8000 9000
Pressure (psig)
• CCE, liquid saturation at 308 oF

T1DST2 EOS Modeling

- CCE at 308degF
0.016

0.014
Liquid Saturation = Vliq/Vtotal (fraction)

0.012 NewEOS

8compEOS
0.01
17compEOS
0.008
Lab-LiqSat

0.006

0.004

0.002

0
0 1000 2000 3000 4000 5000 6000
Pressure (psig)
• CVD, vapor z-factor at 308 oF

T1DST2 EOS Modeling

- CVD at 308degF
1.25

1.2
NewEOS

1.15 8compEOS

1.1 17compEOS
Vapor Z-factor

Lab-VaporZfactor
1.05

0.95

0.9

0.85

0.8
0 1000 2000 3000 4000 5000 6000
Pressure (psig)
• CVD, liquid saturation at 308 oF
Offshore process flow diagram
Process simulation

• Offshore facility – CPF (natural gas export)

Dehydration
Gas export
compression

Liquid flow to FPSO

Separation
 • Offshore facility – FPSO (condensate export)

To CPF

Fuel gas

From CPF separation

stabilization

To storage
Lean MEG
Rich MEG
• Product comparison
: New EOS yield less GEP export gas due to fewer heavy components than
17comp EOS model
: Condensate rate for new EOS model is 3wt% larger

Offshore Process Block Diagram

27
CPF
27
Fuel
2300 (1745MMscfd) 27
2300 (1745MMscfd)
2300 (1744MMscfd)
Well CPF Export 1833 (1607MMscfd)
Stream Gas 1833 (1607MMscfd)
1841 (1607MMscfd)

FPSO 10
Mass Rate [te/hr] 10
Fuel
10
Case 1 (New EOS, 21 comp)

Case 2 (40 comp)

FPSO 387 (74.9 kstb/d)
Case 3 (17 comp) Condensate
386 (74.8 kstb/d)
377 (73.7 kstb/d)
Thermodynamic analysis
 Ideal gases

• An ideal gas is an imaginary gas that satisfies the following conditions

: Negligible interactions between the molecules,
: Its molecules occupy no volume (negligible molecular volume),
: Collisions between molecules are perfectly elastic (no energy is lost after colliding)
• If we construct the P-v diagram for an ideal gas at a given temperature, we
end up with the isotherm shown as follows,
Real gases

• Typical P-V behavior of a pure substance.

• For a real substance, as pressure increases, there must be a point of

discontinuity that represents the phase change.
• Ideal gas will not condense, no matter what pressure it is subjected to,
regardless of the temperature of the system. In other words, we cannot
hope to reproduce the above P-v behavior using the ideal equation
since no discontinuity is to be found
Cubic EOS

• If we multiply the EOS by V2 and expand the factorized product

by applying the distributive law,
 a   RT  2  a 
P  2 V  b   RT
ab
V 3   b  V   V  0
 V   P  P  P

• This is a third order polynomial in V i.e. it is cubic in molar

volume.
• Thus van der Waals EOS is referred to as cubic because it is a
polynomial of order 3 in molar volume. In general, any equation
of state that is cubic in volume and explicit in pressure is
regarded as a cubic equation of state.
• All the transformations and modifications that it has undergone
during the more than one hundred years since its publication
are also cubic EOS including RK, SRK, and PR.
van der Waals EOS (1873)

• Capable of handling the transition from vapor to liquid

 a 
 2  P  2 V  b   RT
RT a
P 
(V  b ) V  V 

27 R 2 Tc2 1RTc 3 RTc

a ,b  , then Vc 
64 Pc 8 Pc 8 Pc
 Modern cubic EOS
• SRK (1972)
a  a 
V  b   RT
RT
P    P 
(V  b ) V (V  b )  V (V  b ) 
R 2Tc2 RT
a  0.42748 , b  0.08664 c
Pc Pc
  
2
  1  m 1 TR1/ 2 ,m  0.48508  1.55171   0.1561  2

• PR (1976)
RT a  a 
P    P  (V  b )  RT
(V  b ) V (V  b )  b(V  b )  V (V  b )  b(V  b ) 
R 2Tc2 RT
a  0.45724 , b  0.07780 c
Pc Pc
 
  1  m 1 TR 1/ 2
 ,m  0.37464  1.5422    0.26992  
2 2
Comparison of SRK and PR EOS

• RK EOS
- Generally good for gas phase properties, but poor for liquid phase
properties
- Better when used in conjunction with a correlation for liquid phase
behavior.
• SRK and PR EOS
- Serve similar functions as RK EOS but require more parameters
- PR obtains better liquid densities than SRK
- Overall, PR does a better job, slightly, for gas and condensate then
SRK. However for polar systems, SRK always makes a better prediction,
but in the petroleum industry, we do not usually deal with those.
- Peng and Robinson (Uni. Of Calgary) was trying to develop an EOS
specifically focused on natural gas systems. PR EOS shows a slightly
better behavior at the critical point. This slightly better performance
around critical conditions makes the PR EOS somewhat better suited to
gas condensate systems.
Zc to compare EOS performance

• Critical compressibility factor, z at (Tc, Pc)

• Experimental values CO 0.2744
2

CH4 0.2862
C2H6 0.2793
nC5 0.2693
nC6 0.2659

• The experimental values of zc are normally substance dependent, but

close enough among themselves.
• All cubic EOS predict a unique and universal value of z at the critical
point regardless of the substance due to the corresponding sate
principle. Ideal EOS 1.000

van der Waals EOS 0.375

RK EOS 0.333

SRK EOS 0.333

PR EOS 0.301
Pros and Cons

• Advantages of using cubic EOS

- Simplicity of application
- Only a few parameters need to be determined
- Low computational requirement, in the early stages of
computers

• Disadvantages
- Limited accuracy that they can provide, particularly for complex
systems
- Empirical adjustments through the use of the binary interaction
parameters is essential as well as the use of mixing rule
Vapor – Liquid Equilibrium (VLE)

• List of petroleum production systems that involve VLE

- Separators
- Reservoir
- Pipelines
- Wellbore
- LNG Processing
- NGL Processing
- Storage
- Oil and LNG Tankers
• Vapor/liquid equilibrium pertains to all aspects of petroleum
production with which we are concerned
• Depends on the production conditions, phase changes would
affect the design and operation of each production system.
Ex)retrograde condensation, bubble/dew point, phases fraction
Phase equilibrium

• At equilibrium all components will have the same fugacity (fi) in

all phases.
• Fugacity may be understood as effective partial pressures
taking into account non-ideal interactions with other molecules

fVC3=200 bar fVC3=150 bar

fVC1=200 bar fVC1=250 bar

fVC1=300 bar fVC1=250 bar

fVC3=200 bar fVC3=150 bar

Non-equilibrium Equilibrium
Fluid modeling

• Parameters for EOS modeling of reservoir fluids

- Temperature range
- Pressure range
- Composition
- Experimental data (density, viscosity, composition, phase behavior)
- Critical and other properties of components
Tc, Pc, Acentric factor
Molecular weight
Ideal gas heat capacities
Liquid density
Normal boiling point
- Binary interaction parameters (kij)
• The EOS models calculate (for a given composition, T & P):
- Density
- Phase behavior
- Enthalpy & entropy

• They do not calculate (done with other correlations)

- Viscosity
- Thermal conductivity
- Interfacial tension

• Aqueous and polar components require special calculations

Simulation Example – PVTSim
Which EOS to use?

• SRK or PR(78) company standard?

- Choose that one
- PR densities better than SRK if no volume correction
• Peneloux volume correction
- Always to be used when density counts
- SRK and PR equally good with volume correction
• Peneloux(T)

- Recommended for heavy oils (improves shrinkage

factor from reservoir to surface conditions)
Design and Optimization of Separators

• Once oil and gas are brought to the surface, our main goal
becomes that of transportation of the oil and gas from the
wellhead to the refinery (for final processing) in the best
possible form.
• All equipment and processes required to accomplish this are
found at the surface production facility. Hence, all surface
production starts right at the wellhead.
• Starting at the wellhead, the complex mixture of produced fluids
makes its way from the production tubing into the flow line.
Normally, many wells are drilled to effectively produce the
hydrocarbons contained in the field. From each of these wells
emerge one or more flow lines depending on how many layers
are being produced simultaneously.
• The gathered fluids must be processed to enhance their value.
• First of all, fluids must be separated into their main phase
components;namely, oil, water, and natural gas.
• The separation system performs this function. For this, the
system is usually made up of a free water knock-out (FWKO),
flow line heater, and oil-gas (two-phase) separators.
• The physical separation of these three phases is carried out in
several steps. Water is separated first from the hydrocarbon
mixture (by means of the FWKO), and then the hydrocarbon
mixture is separated into two hydrocarbon phases (gas and
oil/condensate).
• A successful hydrocarbon separation maximizes production of
condensate or oil, and enhances its properties. In field
applications, this is accomplished by means of stage
separation.
• Stage separation of oil and gas is carried out with a series of
separators operating at consecutively reduced pressures.
Liquid is discharged from a higher-pressure separator into the
next-lower-pressure separator.
• The purpose of stage separation is to obtain maximum recovery
of liquid hydrocarbons from the fluids coming from the
wellheads and to provide maximum stabilization of both the
liquid and gas effluents.
Three stage separators

• Under the assumption of equilibrium conditions, and knowing

the composition of the fluid stream coming into the separator
and the working pressure and temperature conditions, we could
apply our current knowledge of VLE equilibrium (flash
calculations) and calculate the vapor and liquid fractions at
each stage.
• However, if we are looking at designing and optimizing the
separation facility, we would like to know the optimal conditions
of pressure and temperature under which we would get the
most economical profit from the operation.
• In this context, we have to keep in mind that stage separation
aims at reducing the pressure of the produced fluid in
sequential steps so that better and more stock-tank
oil/condensate recovery will result.
• Separator calculations are basically performed to determine:
 Optimum separation conditions: separator P and T
 Compositions of the separated gas and oil phases
 Oil formation volume factor
 Producing Gas-Oil ratio
 API gravity of the stock tank oil
• In case of three-stage separation, temperature conditions in the
surface separation facility are very much determined by the
atmospheric condition and incoming stream temperatures.
• As for pressures, the very first separator pressure is controlled
by the gathering lines coming from well heads, thus there is not
much room for playing with pressure in the first separator. The
same arguments are valid for the last stage of separation (stock
tank), which usually operates at atmospheric conditions.
• Therefore, we are only left with the middle separator for
optimization.
• What we can do, using our phase behavior knowledge, is to find
this optimum middle stage pressure applying our understanding
of VLE equilibrium.
What we need to achieve

• Here is a typical effect of playing with the middle separator

pressure on the quality and quantity of produced oil/condensate
at the stock tank.
• Quality and quantity are measured in terms of properties, such
as API and Bo, and the overall GOR at the separation facility.
• The optimum value of pressure for the middle stage is the one
that produces the maximum liquid yield (by minimizing GOR
and Bo) of a maximum quality (by maximizing stock-tank API
gravity).
• The smaller the value of GOR and Bo, the larger the liquid yield.
The higher the API gravity of the stock-tank fluid, the more
profitable its commercialization.
• From this figure, we see that P1 is found at neither extreme
(low/high) values of middle stage pressure. There is, in fact, an
optimal value for middle stage pressure.

P1
Natural Gas Pipeline Modeling

• Once natural gas is produced and processed, few to several

hundred kilometers may lie in between it and its final
consumers.
• A cost-effective means of transport is essential to bridge the
gap between the producer and consumer. In the technological
area, one of the challenges pertains to the capacity of the
industry to ensure continuous delivery of natural gas while its
demand is steadily increasing.
• Thus, it is no wonder that pipelines have become the most
popular means of transporting natural gas from the wellhead to
processing — and from there to the final consumer — since it
better guarantees continuous delivery and assures lower
maintenance costs.
• The major variables that affect the design of gas pipelines are
: the projected volumes that will be transported,
: the required delivery pressure (subject to the requirements of
the facilities at the consumer end),
: the estimated losses due to friction,
: the elevation changes imposed by the terrain topography.
• Overcoming such losses will likely require higher pressure than
the one available when the gas is being produced. Thus,
forcing a given gas rate to pass through a pipeline will inevitably
require the use of compressor stations.
• Once a pipeline is deployed, it has a more or less a fixed
operational region. An upper and lower set of operational
conditions allowable within the pipeline (in terms of pressure
and temperature) will exist.
• On the one hand, the upper allowable condition will be set by
the pipe strength, pipe material, diameter, and thickness. These
will determine the maximum pressure that the pipe can endure
without failure (i.e., maximum operating pressure).
• On the other hand, maximum pressure and temperature of the
compressor station discharge (which feeds the inlet of the pipe)
will also contribute to set this upper level. It is clear that the
conditions at the discharge of the compressor station cannot go
beyond the maximum operating pressure of the pipe —
otherwise the pipe will fail.
• The minimum or lower pressure and temperature condition of
the operational region will be assigned by an agreement with
the end consumer.
• The foregoing description of the operational region is shown
schematically as the shaded area in this figure.

• In natural gas flow, pressure and temperature changes (P-T

trace) may cause formation of a liquid phase owing to partial
condensation of the gaseous medium.
• This figure shows four typical phase envelopes for natural
gases, which differ in the extent of their heavy components.
• For a given composition, the prevailing pressure and
temperature conditions will determine if the fluid state is all
liquid (single-phase), all gas (single-phase) or gas-liquid (two-
phase).
• Each envelope represents a thermodynamic boundary
separating the two-phase conditions (inside the envelope) from
the single-phase region (outside).
• Each envelope is made of two curves: the dew point curve
(right arm, where the transition from two-phase to single-gas
occurs) and the bubble point curve (left arm, where the
transition from single-liquid to two-phase occurs). Both arms
meet at the critical point.
• The wetness of the gas is an important concept that helps to
explain the different features in the figure.
• This concept pertains to the amount of heavy hydrocarbons
(high molecular weight) that are present in the gas composition.
• In the figure the driest gas — i.e., the least wet — can be
recognized as that whose left and right arms are the closest to
each other, having the smallest two-phase region (gas A).
• In this figure, it can be seen that the right arm is extremely
susceptible to the presence of heavies in the natural gas
composition. Depending on the gas composition, the pipeline
operational region can be either completely free of liquid (gas A,
the driest) or partially submerged in the two-phase region (gas
B, C). If the gas is wet enough, the pipeline will be entirely
subjected to two-phase conditions (gas D, the wettest).
• In the figure, a pipeline handling a dry gas (gas A) will be
operating a single-phase mode from its inlet through its outlet.
For this case, any of the popular single-phase gas equations
can be used for design purposes and to help to predict the
actual operational curve (P-T trace).
• If a richer gas comes into the system (gas C), it will show a
single-phase condition at the inlet, but after a certain distance
the pressure and temperature conditions will be within the two-
phase region.
• The case might also be that the system is transporting a wetter
gas (gas D), in which case it would encounter two-phase
conditions both at the inlet and at the outlet of the pipe.
Contact: Yutaek Seo

Email: Yutaek.Seo@snu.ac.kr

Thank you