PROPERTIES OF RESERVOIR

FLUIDS

René MIGNOT

PVT DEG 2009 2010

 OIL AND GAS PHYSICAL PROPERTIES

1. Generalities
2. Chemical composition of petroleum fluids
3. Pure components,binary mixtures and petroleum fluids
4. Oil and Gas main properties
5. Correlations to estimate hydrocarbons properties
6. Equations of state
7. Sampling
8. Oil PVT Study
9. Gas condensate PVT study
10. Water properties

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 OIL AND GAS PHYSICAL PROPERTIES AND PVT STUDIES

1.GENERALITIES

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 GENERALITIES

• Goal of a PVT study

Determine characteristics (chemical and physical) of the

reservoir fluids so as to predict its behaviour when
pressure and temperature vary.

• During the production process in the reservoir, fluids are

depleted at constant temperature.

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 GENERALITIES

• Conclusions of a PVT study

Parameters for hydrocarbons in-place evaluation

Recovery-factor calculations
Fluid composition analysis
Phase behaviour during production
Input to reservoir numerical simulation

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 GENERALITIES

Who uses PVT data ?

Reservoirs engineers
- Understanding of the oil and gas behaviour in the reservoir
- Establish a coherent development plan
- Use for compositional simulation (equation of state)

Process engineers
- Choice of the separation process
- Surface separation optimization

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 GENERALITIES

• THE PVT FLUID analyzed must be the most representative

of the RESERVOIR FLUID.

• Representativity guarantees an accurate production

prediction, exactness of the bubble or dew point, nature of
the fluid in the reservoir, amount of oil produced.
Requirements are:
- acquisition of adequate volume of representative fluid
samples
- exact PVT data measurements with strict quality-
assurance/quality control (QA/QC)
• The PVT cost is minimal in regard to economical benefits
or losses brought by the lack of knowledge of the fluid
properties present in the reservoir.

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 GENERALITIES

Consequences

¾ Don’t hesitate to sample fluids for PVT analysis

¾ Representativity of the sampling is essential

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 UNITS

Quantity Symbol Unit Conversion Factor

Pressure Pa Pascal SI unit (10-5 bar)

bar Bar 105 Pa or 14.5 psi
atm Atmosphere 1.01325 bars
psi Pound per square inch 0.06895 bar
Mpa Mega Pascal 10 bars

Temperature K Kelvin T(°K)=T(°C)+273.15

°C Degree Celsius T(°C)=T(°K)-273.15
°F Degree Fahrenheit T(°F)=32+1.8T(°C)
T(°C)=[T(°F)-32]/1.8
°R Degree Rankine T(°R)=T(°F)+459.67

Volume cu ft Cubic foot 0.02831 m3

bbl Barrel 0.158987 m3
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 UNITS

Quantity Symbol Unit Conversion Factor

GOR cu ft/bbl cu ft/bbl 0.17706 m3/m3

Salinity ppm part per million 10-3 g/m3

mg/l milligram per liter 10-3 g/l

Viscosity cp centipoises 1 mPa.s

mPa.s millipascal.second 1 cp
Pa.s Pascal.second Unit SI (1000cp)

Interfacial dyne/cm dyne per cm mN/m or 10-3N/m

tension mN/m milliNewton per meter 1 dyne/cm or 10-3 N/m
N/m Newton per meter Unit SI (1000 dyne/cm)

Compressibility bar-1 bar inverse 0.06895 psi-1

psi-1 square inch per pound 14.5 bar-1

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 GENERALITIES

Definitions
Reference conditions generally used throughout
Petroleum Industry

Standard Conditions
. Ps.c= 1.013 bara (ou 14.7 psia)
. Ts.c= 15.6 °C (or 60 °F)

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 UNITS

metric Units Customary units

Length m feet ft
Surface m2 ft2
Volume m3 ft3, cu ft
Mass kg pound, lbm
Time day day
rate m3/day bbl/d, STB/d, scf/d
GOR m3/m3 scf/STB
pressure bar psi
Viscosity cp cp
Density kg/m3 lbm/cu ft
Temperature °C, °K °F, °R
Permeability md md

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 OIL AND GAS PHYSICAL PROPERTIES AND PVT STUDIES

2. CHEMICAL COMPOSITION OF
PETROLEUM FLUIDS

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 OIL AND GAS PHYSICAL PROPERTIES and PVT STUDIES

Hydrocarbon maturity
Immature zone

Biogenic gas

Heavy Hydrocarbons
60 °C
Oil

Oil
Condensate
130 °C

Catagenic Gas
CH4
Dry Gas
180 °C

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 CHEMICAL COMPOSITION OF PETROLEUM FLUIDS

• Petroleum fluids are mainly constituted of organic

elements as hydrocarbons

• Hydrocarbons contains only carbon and hydrogen

• Also crude oils contains non hydrocarbons as nitrogen

(N2), hydrogen sulfide (H2S), carbon dioxyde (CO2), carbon
monoxyde (CO), and mercaptans (R-S-H)

• Also contains elements as traces Hg, Ni, Va, S, O

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 CHEMICAL COMPOSITION OF PETROLEUM FLUIDS

.Compositional analysis of the gas phase by

gas chromatography; N2, CO2, C1-C10
•Compositional analysis of the liquid phase
by gas chromatography up to C20+, often
(C11+, C7+) and/or distillation from C10 to
C20+.

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 GAS CHROMATOGRAM

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 MAIN FAMILIES OF HYDROCARBONS

Hydrocarbons
AROMATICS
(ex. benzene, toluene, Aliphatics
xylene)
SATURATED
Unsaturated
(or Alkanes)

Normal alkanes Iso-alkanes Cycloalkanes

Alkenes Alkynes
(ex. methane, (ex. iso-butane ) (or Naphthenes)
(ex. ethylene) (ex. acetylene)
ethane, propane)
(ex. cyclohexane)

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 CLASSIFICATION OF PETROLEUM RESERVOIR FLUIDS

ALKANES or PARAFFINS
(saturated hydrocarbons)

Normal alkanes Iso-alkanes Cycloalkanes

Straight chain branched chain or naphtenes
CnH2n+2 CnH2n+2 CnH2n

Methane CH4 i-butane i-C4H10 cyclopentane C5H10

ethane C2H6 i-pentanes i-C5H12 cyclohexane C6H12
propane C3H8
n-butane C4H10

AROMATICS
Benzene C6H6
Asphaltenes (ex naphtalene, anthracene)

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 COMPOSITION OF A PETROLEUM FLUID

Cut Component Molar fraction Cut Component Molar fraction

H2S hydrogen sulfide 0.000 C9 iso nonanes 0.242
N2 nitrogen 0.075 aromatics in C8 0.134
CO2 carbon dioxide 1.536 cyclanes in C9 0.180
C1 methane 77.872 n nonane 0.146
C2 ethane 7.691 C10 iso decanes 0.348
C3 propane 3.511 aromatics in C9 0.094
C4 iso butane 0.469 n decane 0.095
n butane 1.267 C11 undecanes 0.427
C5 iso pentane 0.343 C12 dodecanes 0.315
n pentane 0.581 C13 tridecanes 0.295
C6 iso hexanes 0.391 C14 tetradecanes 0.239
n hexane 0.304 C15 pentadecanes 0.229
C7 iso heptanes 0.338 C16 hexadecanes 0.166
benzene 0.201 C17 heptadecanes 0.168
cyclanes in C7 0.423 C18 octadecanes 0.134
n heptane 0.154 C19 nonadecanes 0.070
C8 iso octanes 0.367 C20+ eicosanes plus 0.685
toluene 0.150
cyclanes in C8 0.239
n octane 0.121

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 COMPOSITION OF A CRUDE OIL

• Nonpolar hydrocarbons such as

- paraffins, naphtenes, aromatics of moderate M

• Polar polyaromatic materials sudbdivided in

resins (less polar than asphaltenes)
asphaltenes
Definitions
asphaltene: fraction of crude oil insoluble in excess nC5, but soluble in
excess benzene and toluene at room temperature
resins: fraction of crude oil soluble in excess C3 liquid at room
temperature

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 ASPHALTENICS CRUDES

• Asphaltenes are the components of crude oil with maximum molecular

weight (up to several hundreds of atoms). Their concentration varies from
0 to 15% by weight.
• Their structure is highly aromatic, but aliphatic structures and
hetero-atoms (oxygen, nitrogen, sulfur) are also present.
• In reservoir conditions, asphaltenes are solubilized in the crude oil.
• When thermodynamic conditions change (depletion, gas injection...)
asphaltenes may gather in larger and larger clusters. This process, called
flocculation, is responsible for solid deposits in wells or pipes..

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 ASPHALTENICS CRUDES

•Asphaltenes precipitation occurs

- in the reservoir
- in production facilities
- in pipelines
And according to the type of fluids
- light oils
- not for some heavy oils
- not for gas condensate
Temperature has little effect on asphaltene precipitation
Pressure decreases causes asphaltene precipitation

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 PARAFFINIC CRUDES

Temperature has a strong effect on wax precipitation

Pressure increase slightly increases cloudpoint T

WAX: solid precipitate can occur

- in well
- production facilities
- pipelines
Wax precipitation for:
- gas condensate
- light-oil fluid at T < 150°F
- heavy-oil fluid at T < 150°F

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 PARAFFINIC CRUDES

• Pour point : the lowest temperature, expressed as a multiple of

5°F, at which the liquid is observed to flow when cooled under
prescribed conditions.

• Cloud point : temperature at which paraffin wax begins to solidify

and is identified by the onset of turbidity as the temperature
is lowered.

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 PHYSIOLOGICAL EFFECTS OF H2S

Concentration

Danger of instant death 700 ppm

Danger of death after 30 minutes 350 ppm
Loss of sense of smell (within a few minutes) 100 ppm
Danger if exposure lasts several hours 50 ppm
Time weighted average for 8 hours exposure (TWA) 10 ppm
Initial sensitivity to smell 1 ppm

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 OIL AND GAS PHYSICAL PROPERTIES AND PVT STUDIES

3. PURE COMPONENTS
BINARY MIXTURES &
PETROLEUM FLUIDS

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 PURE COMPONENTS PROPERTIES

Physical properties of petroleum fluids are function of

=> PRESSURE, TEMPERATURE and COMPOSITION.

= >PURE COMPONENTS PROPERTIES

- Phase notion
- Vapor pressure curve
- Diagram Pressure-Volume (Clapeyron diagram)
- Continuity of liquid and gaseous state
- Isothermal compressibility
- Isobaric compressibility

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 BINARY MIXTURES PROPERTIES

PROPERTIES OF BINARY MIXTURES

- Pressure-Temperature Relationship
- Pressure-Volume Relationship
- Composition influence of the mixing
- Retrograde condensation

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 PURE COMPONENTS PROPERTIES

• Pure components properties

a pure component is characterized by one equation of state f(P,V,T) = 0

P-T CURVE

• Critical point
Pressure

Liquid

Solid Gas

•
Triple Point
Temperature

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 PURE COMPONENTS PROPERTIES

• Pure component properties :

a pure component is characterized by one equation of state f(P,V,T) = 0

Vapor pressure curve

Pressure Pc C
•

Liquid

Gas
Tc
Temperature

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 PURE COMPONENTS DEPLETION

OIL GAS

Psat P2 = Psat P3 = Psat P4 = Psat P5 = Psat

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 P -V CURVE PURE COMPONENTS

Pressure T1 T2 T3

L
C
V
P sat
Bubble point dew
point
L+V

Volume
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 PURE COMPONENTS PROPERTIES

Vapor pressure of normal paraffins

Pressure Bar a.

Temperature °C
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 BINARY MIXTURES PROPERTIES

Binary mixtures Properties

. Diagram P-V

. Diagram P-T

. Composition influence of mixing

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 P -V CURVE MULTICOMPONENT SYSTEM

T1 T2 T3
Pressure

L
CC
V
Bubble
P point
sat
Dew
L+V point

Volume

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 BINARY MIXTURES PROPERTIES

P - T diagram for C2/n-C7 mixture with 96,83 mol % ethane

(from Standing26)

Pc

Pressure, psia

Tc
Temperature, °F 37
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 BINARY MIXTURES PROPERTIES

P-T diagram for the C2/n-C7 system at various concentration of C2

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 PETROLEUM FLUIDS

Petroleum fluids properties

• Crude oil • Different gases

- saturated oil - dry gas
- undersaturated oil - gas condensate
- wet gas

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 PETROLEUM FLUIDS / BUBBLE POINT - DEW POINT

Saturated fluid :
One phase fluid at P and T conditions under study but which forms
two phases if a P and T variation occurs (inside the phase envelope).
In most cases, penetration inside the phase envelope creates a new
phase, minor, with a different composition and density, while the
preexisting phase is almost unchanged.
Bubble point :
Thee pressure at which the first gas bubble appears (out of solution).
Example : opening of a champagne bottle.
Dew point :
The new phase is a liquid phase (mist or tiny droplets).
Example : condensation of water vapor when breathing out in cold air.

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 PETROLEUM FLUIDS

• Saturated oil
Pressure

Critical point
C
Tres, Pres

Separator

Tc
Temperature
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 PETROLEUM FLUIDS

• Undersaturated oil
Pressure

Tres, Pres Critical point

C

Separator

Tc
Temperature

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 PETROLEUM FLUIDS

• Dry Gas

Critical point
Pressure

C Tres, Pres P1

Separator Tc
Temperature
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 PETROLEUM FLUIDS

• Wet Gas

Tres, Pres
Critical point
Pressure

Separator

Tc
Temperature
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 PETROLEUM FLUIDS

• Gas condensate

Tres, Pres
Critical point
Pressure

Séparateur

Tc
Temperature
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Pressure
PETROLEUM FLUIDS / PHASE ENVELOPE OF A MIXTURE

œ  Ÿ
Oil reservoirs with
dissolved gases Cricondenbar
Pcc Gas reservoirs without
retrograde condensation
rve ž
Pc u Critical point
n tc
p oi
ble
b Cricondentherm
Bu Liquid + gas
Dry gas

Zone œ : No or poor contribution

100% of dissolved gases
75%
50% 30% Zone  : Appreciable contribution
20% of dissolved gases
e
10% t curv
5% po i n Zone ž : Retrograde with liquid
0% De w deposit in the reservoir
Zone Ÿ : Dry or wet gas
Tc Tcc T
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 PETROLEUM FLUIDS / PHASE ENVELOPE OF A MIXTURE

Pressure Tcc
T1 Tc T2 T1 < Tc < T2 < Tcc
Gas Gas

RR2

Pc
R2
B1
Liquid

Liquid + vapor R1

Volume

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 TERNARY DIAGRAMS

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 TERNARY DIAGRAM

The petroleum mixture is reduced to three

components :
- a light component (like methane)
- intermediates (like C2 - C5)
- a heavy component (like C6+)

The phase behaviour of this three-component

mixture is represented through an equilateral
triangle, called the ternary diagram

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 TERNARY DIAGRAM
Lights

20% C6+
30% C2-C5

50% C1
M

Heavies Intermediates

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 TERNARY DIAGRAM

- each corner of the triangle corresponds to 100 %

of a single component
- each side represents two-component mixtures
- points within the triangle represents three-
component mixtures

Composition is plotted in mole fraction

For a ternary diagram the pressure and the

temperature are constant, only the composition
changes
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 TERNARY DIAGRAM

Lights

Dew point curve

G
Bubble point curve Critical equilibrium line

..
M
CP

Heavies L Intermediates
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 VARIOUS FORMATION FLUIDS COMPOSITION (% mol.)

Components Oil Oil Oil Condensate Condensate Wet Dry

gas gas gas gas

Nitrogen+CO2 2.16 4.49 2.12 2.37 4.09 1.01 0.40

H2S - 3.45
Methane 30.28 50.12 63.91 64.19 73.80 88.54 94.32
Ethane 6.28 7.78 8.29 11.18 9.43 5.32 3.90
Propane 10.21 5.18 4.37 6.20 4.43 2.30 1.17
Isobutane 1.23 1.04 0.94 0.75 0.87 0.56 0.08
n-Butane 5.75 2.65 2.21 2.31 1.63 0.59 0.13
Isopentane 1.62 1.11 0.72 0.64 0.71 0.27
n-Pentane 2.71 1.43 1.15 1.03 0.66 0.23
C6 3.28 1.92 1.86 1.22 0.91 0.27
C7+ 36.58 20.83 14.43 10.11 3.47 0.91

Total 100.00 100.00 100.00 100.00 100.00 100.00 100.00

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 PETROLEUM FLUIDS CLASSIFICATION

• Difficulty to distinguish between oil and gas

• Requirement to determine:
- fluid state in the reservoir
- fluid properties in-situ

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 GRAVITY OF STOCK TANK OIL

Definition of API Gravity °API = 141.5/d -131.5

with d as oil density as referred to water to 60°F

Condensate, very light oils : d ≤ 0.8 (more than

45°API)
Light oils 0.8 ≤ d ≤ 0.86 (33 à 45°API)
Black oils 0.86 ≤ d ≤ 0.92 (22 à 33°API)
Heavy oils0.92 ≤ d ≤ 1 (less than 22°API)

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 PETROLEUM FLUIDS CLASSIFICATION

BASIC DATA CHARACTERIZING WELL EFFLUENT

1 - Production data
- A.P.I. Gravity
if SG >0.8 (A.P.I.<45°) OIL
if SG <0.8 (A.P.I.>45°) CONDENSATE

- Gas-Oil Ratio
GOR < 500 m3/m3 OIL
500 < GOR < 1000 m3/m3 OIL OR GAS CONDENSATE
GOR > 1000 m3/m3 GAS CONDENSATE

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 PETROLEUM FLUIDS CLASSIFICATION

BASIC DATA CHARACTERIZING WELL EFFLUENT

2 - Chemical composition

- heavy oil C1 < 20% C7+ >40%

- black oil 20% < C7+ < 40%
- light oil C1 – C5 > 60% 13% < C7+ < 20%
- volatile oil/rich condensate 8% < C7+ < 13%
- gas condensate C7+ < 8%
- wet gas C1 > 80%

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 CLASSIFICATION OF HEAVY OILS

• Medium heavy oil 25°> d°API > 18°

100 cp > µ > 10 cp mobile at reservoir conditions

. Extra heavy oil 20° > d°API > 7°

10 000 cp > µ > 100 cp mobile at reservoir conditions

. Tar sands and bitumen 12° > d°API > 7°

µ > 10 000 cp non mobile at reservoir conditions

. Oil shales
Reservoir = Source rock, no permeability
Mining extraction only

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 PETROLEUM FLUIDS CLASSIFICATION

GAS
Pressure O OTres, Pres
GAS
O CONDENSATE
OVOLATILE OIL
BLACK
OIL
O
critical
point
Temperature
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 PETROLEUM FLUIDS CLASSIFICATION

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 OIL AND GAS PHYSICAL PROPERTIES AND PVT STUDIES

4. OIL & GAS

MAIN PROPERTIES

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 MAIN OIL PROPERTIES

Surface conditions
Reservoir conditions

200 m³ gas

1 m³ oil

0,8 m³ oil

Formation volume factor (FVF) :

Bo = 1/0.8 = 1.25 m³/m³
Gas oil ratio :
GOR = 200/0.8 = 250 Sm³/m³

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 MAIN OIL PROPERTIES (BO, RS, CO)

Formation Volume Factor

Vo Volume of oil in reservoir P, T conditions

Bo = Vstd ref = Volume of stock tank oil in standard conditions

Solution gas/oil ratio (Rs)

Vg std Volume of gas in standard conditions
Rs = =
Vstd ref Volume of oil in standard conditions

Rs quantifies the amount of gaseous components which are dissolved in

the oil at reservoir conditions.
Compressibility (Co)
1 ∂V )
Co = - V ( ∂P T

Co quantifies the volume changes arising from pressure depletion at

reservoir temperature, above the bubble point pressure.
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 MAIN OIL PROPERTIES (BO, RS, CO)

Compressibility (Co)

Average oil compressibility is often assumed constant (valid except for

volatile oil at high pressure)
and then:
Bo = Bob [ 1 – Co (p-pb)]

Oil compressibility varies between

1 * 10-4 bar -1 black oil 7 * 10-6 psi -1
4 * 10-4 bar -1 volatile oil 30 * 10-6 psi -1

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 MAIN OIL PROPERTIES

VOLATILE OIL

Volatile oils are light oils where the liquid recovered in

surface comes from one side of the oil phase and from the
other side by liquid condensation of the gas phase.

For a volatile oil

- gravity sto > 35° API
- Bo > 1.5 v/v and Co ≥ 30 * 10-6 psi -1
- 1,000 < Rs < 3,000 scf/STB
- the bubble point is close to the critical point
- oil behavior cannot be represented by traditional black oil PVT

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 MAIN OIL PROPERTIES

DEFINITIONS FOR OIL

Bo =f(P)
Bo

VOLATILE OIL
1.9

1.6

BLACK
1.3 OIL

P (barg)
1.0
100 200 300 400 500

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 MAIN OIL PROPERTIES

DEFINITIONS FOR OIL Rs = f(P)

Rs ( m3/m3)

300

VOLATILE OIL
200

BLACK OIL
100

P (barg)

100 200 300 400 500

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 MAIN OIL PROPERTIES

Viscosity
The viscosity varies with the pressure, temperature and quantity of
dissolved gas. In the reservoir, the following prevail for the hydrocarbon
liquid:
Order of magnitude: from 0,2 cP (very light oil) to 1 P, called heavy oil
above 1 P, up to about 100 P.
µo (cP)
1,5

1 30°API

0,5

45°API
100 200 300 400 P (bar)

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 MAIN GAS PROPERTIES

Surface conditions
Reservoir conditions
200 m³ gas

1 m³ gas

0,2 m³
condensate

Formation volume factor :

Bg = 1/200 m³/m³
Ratio condensate/gas :
CGR = 0.2/200 = 0.001 Sm³/m³
GOR = 1/CGR = 1000 Sm³/m³

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 MAIN GAS PROPERTIES (Bg)

Formation Volume Factor dry gas

Vg Volume of gas in reservoir P, T conditions
Bg = Vgstd ref = Volume of dry gas in standard conditions

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 TWO PHASE FORMATION VOLUME FACTOR

OIL + GAS FORMATION VOLUME FACTOR

Bt = Bo + Rl * Bg Rl : Free gas in the reservoir

Rl = Rsi - Rs Bt = Bo + ( Rsi - Rs ) Bg

Bo Rs

Bt

Rsi

Pb P Pb
P
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 MAIN GAS PROPERTIES (Bg)

DEFINITIONS
One mole of a material is a quantity of that material whose mass, in
the unit system selected, is numerically equal to the molecular
weight.
According to Avogadro law, one mole of any gas contains the same
number of molecules as one mole of any other gas, that is the
Avogadro number.
One mole of any gas occupies the same volume at a given pressure
and temperature.
At standard conditions the molar volume is
379.5 cu.ft/lb.mole at 14.7 psia and 60°F
23.646 l/gr.mole at 1 atm and 15°C

The conversion factor is 1 lb.mole is equivalent to 453.6 gr.mole

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 MAIN GAS PROPERTIES / GAS SPECIFIC GRAVITY

Gas Specific gravity is defined as ratio of gas density to

that of air at standard conditions (60°F, 1 atm).
γ (air =1) = ρgas/ρair = Mgas/Mair
ρgas = Mgas/Vmolar

MW
Gravity =
MWa

Where MWa is the molar mass of air (28.97 g/mol)

The molar mass could be determined from gas
composition

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 MAIN GAS PROPERTIES / GAS SPECIFIC GRAVITY

Definitions for gas :

Vmolar = 23.645 l (1 atm, 15°C)

Vmolar = 23.694 l (1 atm, 60°F)
Vmolar = 379.4 scf/lbm mol (1 atm, 60°F)
Mair = 28.9784
ρair =28.97/23.645 =1.225 kg/m³

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 MAIN GAS PROPERTIES / COMPRESSIBILITY FACTOR

Compressibility factor: Z

for a perfect gas : PV = nRT

for a real gas : PV = ZnRT

Gas Formation Volume Factor:
Bg = V/Vsc = PscZT / PZscTsc
Expansion factor:
E = 1 / Bg
Density:
m = nM et ρ = m/V
ρ = PM/ZRT

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 MAIN GAS PROPERTIES (Bg)

Formation Volume Factor dry gas

Vg Volume of gas in reservoir P, T conditions
Bg = Vgstd ref = Volume of dry gas in standard conditions

Formation Volume Factor wet gas

Vg Volume of gas in reservoir P,T conditions
Bg = =
Vgstd equ Volume of dry gas + equivalent gas vol of liquid in std

Equivalent gas volume of liquid is the number of moles of liquid multiplied by

the molar volume or:
Vsto * ( ρoil / Moil ) * 23.6
and the total volume of gas at std conditions:
Vg std equ = Vsto [R + ( ρoil / Moil ) * 23.6]

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 MAIN GAS PROPERTIES / GAS RICHNESS

GAS RICHNESS

Definitions:

in metric units : g/m3

in British units : GPM gallon per thousand cuft

also most usually expressed in stb/MMscf

Examples

Poor gas condensate 50 stb/mmscf

Rich gas condensate 250 stb/mmscf

Colombian gas in the foothills 280 stb/MMscf

Qatar gas 40 stb/mmscf

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 MAIN GAS PROPERTIES / GAS RICHNESS

GAS RICHNESS

Calculation in metric units : g/m3

m
C3+ (g/m3) = Σ yiMi * 1000/23.6
i=3

m
C4+ (g/m3) = Σ yiMi * 1000/23.6
i=4

m
C5+ (g/m3) = Σ yiMi * 1000/23.6
i=5

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 MAIN GAS PROPERTIES / GAS RICHNESS

GAS RICHNESS

Calculation in british units :

GPM = gallons per thousand cubic feet

m
GPM (C3+) = [Σ yiMi/ρi] * (28.3 / 3.785) / 23.6
i=3

m
GPM (C4+) = [Σ yiMi/ρi] * (28.3 / 3.785) / 23.6
i=4

m
GPM (C5+) = [Σ yiMi/ρi] * (28.3 / 3.785) / 23.6
i=5

79
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 PURE COMPONENTS PARAMETERS

Characteristic properties of
pure compounds

1°/ This list is far from

containing all hydrocarbons
present in the light fraction
of crude oils and natural
gases (more than 250
individual hydrocarbons can
be identified by gas
chromatography)

2°/ Beyond C10, hydrocarbons

decompose before their
critical point can be properly
investigated. Then critical
parameters are extrapolated.

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PVT DEG 2009 2010
 OIL AND GAS PHYSICAL PROPERTIES AND PVT STUDIES

5. CORRELATIONS

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PVT DEG 2009 2010
 CORRELATIONS

Knowledge of the fluid properties in PRESSURE and

TEMPERATURE (P.V.T. properties) is required for reservoir
evaluation

P.V.T. properties of petroleum fluids are obtained:

- from empirical laws
- from P.V.T. analysis (laboratory)
- by calculation from an equation of state (matching)

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PVT DEG 2009 2010
 CORRELATIONS

•From experimental data obtained from a great number of

fluids, various authors have established useful correlations
concerning hydrocarbons fluids.
– Bubble point pressure
– Volumetric Factor
– viscosities
– densities
– compressibility Factor

•Using little experimental data, one can obtain relatively

precise figures concerning fluid properties (whether it is oil or
gas).

• PVT coherence (measures) can be checked using

correlations.
83
PVT DEG 2009 2010
 CORRELATIONS

• Black oil correlations are usually based on regional fluid

data as for example North Sea, Middle East or Egypt
• these correlations should not be used outside the range of
data for which there were derived.
• EOS matched against PVT data are used for reasonable
extrapolation outside the data range

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 CORRELATIONS OF OIL PROPERTIES

DETERMINATION OF OIL PROPERTIES FROM EMPIRICAL LAWS

based on GOR, gravity of stock-tank oil, gas gravity

1. Bubble point pressure

Standing correlation (old Californian fields)
Glaso correlation (derived from North Sea)
Vasquez and Beggs
etc…

2. Oil Formation Volume Factor

Standing correlation
Glaso correlation
Vasquez and Beggs
etc…

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 CORRELATIONS OF OIL PROPERTIES

3. Oil density

( ρg × Rs ) + ρo
ρo (P,T) = -----------------------
Bo

4. Compressibility
STANDING correlation for Isothermal oil compressibility
VASQUEZ and BEGGS correlation

5 . Viscosity
CARLTON BEAL and, CHEW and CONALLY correlations

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 STANDING CORRELATION / BUBBLE POINT PRESSURE

Pb = 18.2 ( A – 1.4 )
A = (Rsb/dg)0.83 10 (0.00091 Tr - 0.0125 χ API )

with :

Pb bubble pressure (psia)

Rsb solution GOR at bubble point (scf/STB)
dg gas gravity (air=1)
Tr reservoir temperature (°F)
χ API gravity of sto (° API)

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PVT DEG 2009 2010
 Pb and GOR

GOR = 350 dg = 0.75

T = 180°F

ρo = 30 API

Pb = 1900 psi

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PVT DEG 2009 2010
 STANDING CORRELATION OIL FORMATION VOLUME FACTOR

Bo = 0.9759 + 0.00012 A1.2

avec :

A = Rs (dg/do)0.5 + 1.25T
Rs solution GOR , (scf/STB)
dg gas gravity (air = 1)
do gravity of sto (water = 1)
T temperature (°F)

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PVT DEG 2009 2010
 OIL FORMATION VOLUME FACTOR

Standing

90
PVT DEG 2009 2010
 GLASO CORRELATION / BUBBLE POINT PRESSURE / FVF

Bubble point pressure:

log pb = 1.7669 + 1.7447 log A – 0.30218 (log A)2

where A = (Rs/γg)0.816 (T0.172 / γAPI0.989 )

Oil formation volume factor:

log(Bob – 1) = - 6.585 + 2.9133 log A – 0.2768(logA)2

where A = Rs(γg/γo)0.526 + 0.968 T with
pb psia
Rs solution GOR , (scf/STB)
γg gas Specific Gravity (air = 1)
γo gravity of sto (water = 1)
T temperature (°F)

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 OIL DENSITY

⇒ OIL
. determination of density of saturated oil at reservoir
conditions knowing the Bo.

ρg × Rs + ρost
ρo (p,T) = ----------------------------
Bo
. ρg being gas density at reference conditions (SG * ρ air)
. ρost sto density in kg/m3
. Rs solution gas oil ratio in m3/m3 at ref cond
. ρo (p,T) density at p and T in kg/m 3

92
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 OIL COMPRESSIBILITY

Compressibility (Co)

Average oil compressibility is often assumed constant (valid except for

volatile oil at high pressure)
and then:
Bo = Bob [ 1 – Co (p-pb)]
and
ρo = ρob [1 – Co (pb-p)]

oil compressibility varies between

1 * 10-4 bar -1 black oil 7 * 10-6 psi -1
4 * 10-4 bar -1 volatile oil 30 * 10-6 psi -1

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 OIL COMPRESSIBILITY

⇒ OIL
determination of undersaturated oil compressibility

- Vazquez and Beggs correlation for instantaneous oil

compressibility
Co = A/p

A = 10-5 (5 Rsb + 17.2 T – 1.180 γgc + 12.61 γAPI - 1.433)

with Co psi-1 Rsb scf/STB T °F p psia

then Bo = Bob (pb/p)A

Other correlations are available for Co (SPE Feb 2007)

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 OIL VISCOSITY

⇒ OIL
.determination of oil viscosity at reservoir conditions

1. Dead oil viscosity (sto) at reservoir temperature

correlations of Beal, Standing, Beggs and Robinson,
Vasquez,etc...
2. Bubblepoint oil viscosity
Chew and Connaly, Standing, Beggs and Robinson etc…

3. Undersaturated oil viscosity

same authors

- Lohrenz relationship for both phases (used in

compositional reservoir simulation)
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 OIL VISCOSITY

« Beal » dead-oil (stock-tank-oil) viscosity correlation including data in

« Frick » (from Standing)

Oil viscosity, cp

Oil gravity, *API

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PVT DEG 2009 2010
 OIL VISCOSITY

Live-oil (saturated) viscosity as a function of dead-oil viscosity and solution

gas/oil ratio (from Standing33, after Beal72 correlation)

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 MAIN GAS PROPERTIES

⇒ LAW OF CORRESPONDING STATES

The ratio of the value of any intensive property to the

value of that property at the critical point, is related
to the ratio of the prevailing absolute temperature and
pressure to the critical temperature and pressure by
the same function for all similar substances.

Fluids are said in CORRESPONDING STATES when any

of the two reduced variables Pr, Vr et Tr are the same.

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 MAIN GAS PROPERTIES

⇒ CRITICAL POINT : that state of pressure and

temperature (Pc) and (Tc) at which the intensive
properties of liquid and gas are identical.

⇒ REDUCED VARIABLES =

Pr = P/Pc reduced pressure

Tr = T/Tc reduced temperature

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PVT DEG 2009 2010
 MAIN GAS PROPERTIES

Determination of Z:
Experimental : P-V analysis of a mass of gas m at T (m known)
Calculations and charts
These methods are based on the law of corresponding states.
A chart has been prepared giving Z, based on studies of many
gases, as a function of :
- Pseudoreduced pressure = absolute pressure / absolute
pseudocritical pressure
- Pseudoreduced temperature= absolute temperature / absolute
pseudocritical temperature
The pseudocritical pressure and temperature of a given gas
(different from the critical pressure and temperature) are obtained
by calculation from the composition, or by chart from the specific
gravity.
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PVT DEG 2009 2010
 GAS COMPRESSIBILITY FACTOR

⇒PSEUDO-CRITICAL PROPERTIES FROM KNOWN COMPOSITION

m Ppc = pseudo critical pressure

Ppc = Σ yi Pci Tpc = pseudo critical temperature
i=1 Pci = critical pressure of i constituent
Tci = critical temperature of i const.
yi = molar fraction of i constituent
m m = number of constituents
Tpc = Σ yi Tci
i=1

If not available pseudocritical properties of C7+ are obtained from

Matthews correlation.
TcC7+ = 608 + 364 log(MC7+ - 71.2) + (2.450 logMC7+ - 3.800) logγC7+
pcC7+ = 1.188 - 431 log(MC7+ - 61.1)+[2.319-852(logMC7+ -53.7)](γC7+-0.8)

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 GAS COMPRESSIBILITY FACTOR

⇒ PSEUDO-CRITICAL PROPERTIES FROM CORRELATIONS

1. From Sutton correlation, derived for Associated gas and gas

condensate

- for Associated gas:

TpcHC = 120.1 + 429 γgHC – 62.9 γg2HC in ° R
and ppcHC = 671.1 + 14 γgHC - 34.3 γg2HC in psia

- for gas condensate:

TpcHC = 164.3 + 357.7 γgHC – 67.7 γg2HC in ° R
and ppcHC = 744 – 125.4 γgHC + 5.9 γg2HC in psia

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 GAS COMPRESSIBILITY FACTOR

⇒ PSEUDO-CRITICAL PROPERTIES FROM CORRELATIONS

Associated gas is defined as gas liberated from oil:

- high gravity
- rich C2-C5
- low C7+ (except for low separation presure and vollatile crude
oil)

Gas condensate being:

- rich in C7+

2. From Standing correlation as represented in the following chart

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PVT DEG 2009 2010
 GAS : Determination of Tpc AND Ppc

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PVT DEG 2009 2010
 GAS COMPRESSIBILITY FACTOR

⇒ GAS

.determination of gas compressibility factor Z

by Standing and Katz chart

- determination of Tpc
- determination of Ppc
- calculation of Tpr and Ppr

.or by Hall and Yarborough equations or Dranchuk and

Abou-Kassem (DAK) which are digital representation of
the Standing and Katz chart

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PVT DEG 2009 2010
 GAS COMPRESSIBILITY FACTOR

Standing & Katz 106

PVT DEG 2009 2010
 GAS COMPRESSIBILITY FACTOR

Compressibility factors for natural gas near atmospheric pressure (McKetta

et al. 4-83a)

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PVT DEG 2009 2010
 GAS COMPRESSIBILITY FACTOR

⇒ GAS

.determination of gas compressibility factor Z when

nonhydrocarbons are present, as N2, CO2 and H2S.

The correlation derived by Wichert and Aziz allows to

calculate pseudocritical properties of the mixture that
will give reliable Z factors from the Standing correlation.

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PVT DEG 2009 2010
 GAS VISCOSITY

Oil & Gas journal, May 1949

109
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 OIL AND GAS PHYSICAL PROPERTIES AND PVT STUDIES

6. EQUATIONS OF STATE

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 EQUATIONS OF STATE

Equations of state : f(P, V, T, n) = 0

. ideal gas law : (Mariotte, 1650) PV = nRT

. equation of state for real gas : PV = ZnRT

. cubic equations of state

Van der Waals P = RT/(V-b) - a/V2 (1873)
Redlich-Kwong P = RT/(V-b) -a/V(V-b)T½ (1949)
Soave-Redlich-Kwong P = RT/(V-b) - a(T)/V (V+b) (1972)
Peng-Robinson P = RT/(V-b) - a(T)/(V2+2bV-b2) (1976)

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 EQUATIONS OF STATE

Van der Waals equation of state

P = RT/(V-b) - a/V2
or (P+ a/V2) (V-b) = RT
a : attraction parameter, the pressure exerted on the walls (cell) is reduced
by the attraction between molecules
b : repulsion parameter or covolume,volume occupied by the molecules
reducing the total volume available
a and b are determined from the law of corresponding state and are
function of Pc,Tc and Vc.
writting at the critical point (δP/δV)T = 0 and (δP2/δV2)T = 0

Van der Waals EOS can also be expressed in reduced parameters

(Pr + 3/Vr2) (3Vr - 1) = 8 Tr

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 EQUATIONS OF STATE

Cubic equations of state :

These equations are called « cubic » because volume determination
at fixed pressure and temperature needs to solve a third order
polynomial equation.

Simple cubic equation of state

Z3 + UZ2 + VZ + W = 0
with
Z = PV/RT and U, V, W depending of two constants A and B.
A = aP/R2T2 and b = bP/RT

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 EQUATIONS OF STATE

Acentric factor ω :
Reflect the deviation from the law of corresponding states of the
vapor pressure curve for pure substances
ω = - 1 - log10 (Pvap/Pc) for Tr = 0.7 (defined by Pitzer)

the vapor pressure curve becomes:

log10 (Pr) = -7/3 (1+ ω) [1/Tr-1]

Originally represented the nonsphericity of a molecule, at present it

is used as a parameter supposed to measure the complexity of a
molecule with respect to geometry and polarity. It increases with
molecular weight and polarity.

Mixing rule for mixture

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PVT DEG 2009 2010
 DEFINITION of ACENTRIC FACTOR

Critical 1
point 0 1/Teb 1/0.7 1/Tr

log(Patm/Pc)

ω=0
-1

-1- ω

(ω = 0) Ideal behaviour

log 10 (Pr) -2

115
PVT DEG 2009 2010
 EQUATIONS OF STATE

Redlich-Kwong : the second term is made dependent of

temperature by 1/T½

Soave-Redlich-Kwong : α correcting factor dependent of

composition

a = α * 0.42748 R2Tc2/Pc
α depends of m and Tr
m depends of ω

Peng-Robinson : very similar to SRK

m expression is slightly different

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PVT DEG 2009 2010
 EQUATIONS OF STATE

Parameters of the Peng-Robinson equation (for a pure

component)

P = RT/(V-b) - a(T)/(V2+2bV-b2)

b = 0.077796 RTc / Pc

a(T) = α * 0.457235 R2Tc2/Pc α ={ 1 + m [1-(T/Tc)½]}2

m = 0.37464 + 1.54226 ω - 0.26992 ω2 for ω ≤ 0.49

m = 0.379642 + 1.48503 ω - 0.164423 ω2 + 0.016666 ω3 for ω > 0.49

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 EQUATIONS OF STATE

Mixing rule : previous equations were developed for pure

components
n n
for mixtures a = Σ Σ xi xj (1-kij) (ai.aj)½
j=1 i=1

n
b = Σ xi bi
i=1

kij = binary interaction coefficient, between ith and jth component,

independent of pressure and temperature. It is equal to zero for
HC/HC interactions, except C1/C7+, and different from zero
between HC and non HC and between non HC together.

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 EQUATIONS TO STATE

VOLUME TRANSLATION

Peneloux shift :

Purpose : improve the computation ol liquid densities, which are poorly

predicted by classical cubic equations of state, without changing vapour-
liquid phase equilibria. Gas density is little affected.

- If V is the molar volume computed from the equation of state the corrected
volume is :
Vcorr = V -c where c is the volume translation (cm3/mol)

-For a monophasic mixture of composition, xi

c = Σ xi c i
i

where ci is the volume translation of component i

-Correlations are available for ci determination

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 EQUATIONS TO STATE

APPLICATION TO PHASE EQUILIBRIA

Definitions
zi = component i mole fraction in the mixture

Σ zi = 1

L = liquid molar fraction in the mixture

V = vapour molar fraction in the mixture

L + V = 1 molar fraction in equilibrium

xi = component i mole fraction in the liquid in equilibrium

yi = component i mole fraction in the vapour in equilibrium

Σ xi = 1 Σ yi = 1

Overall balance in the mixture:

zi = xi L+ yi V zi = xi (1-V)+ yi V

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 EQUATIONS TO STATE

RACHFORD-RICE EQUATION

Equilibrium constants
ki = component i equilibrium ratio

k i = y i / xi

zi = (1-V) xi + V yi = (1-V) xi + V ki xi = xi [1+V(ki-1)]

xi = zi / [1+V(ki-1)] yi = kizi / [1+V(ki-1)]

Rachford-Rice equation

Σ ( yi- xi) = Σ zi(ki-1)/[1+V(ki-1)] = 0 or F(V) = 0

With mixture composition and k values known, the remaining unknown is V

and F(V) is solved mathematically by iteration using the Newton-Raphson
algorithm

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 EQUATIONS TO STATE

DETERMINATION OF EQUILIBRIUM CONSTANT

K values are a function of pressure, temperature and overall composition

They are derived either by

- calculation from laboratory data

- empirical correlation

Calculations of phase equilibrium by EOS use values derived

by correlations to initiate the iterative calculation

- for low pressure Wilson equation

- for high pressure Whitson and Torp equation

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 EQUATIONS TO STATE

THERMODYNAMICAL EQUILIBRIUM

From EOS
Liquid Phase composition xi
Gas Phase composition yi

They should be in chemical equilibrium

Condition: chemical potential of each component identical in the

liquid and gas phase

condition satisfied by the equal fugacity constraint, fugacity

calculated by the equation of state

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 EQUATIONS OF STATE

APPLICATION TO PHASE EQUILIBRIA

Step by step procedure

- Estimate k values from empirical correlations

- Solve the Rachford-Rice equation for V

- Compute xi and yi
- Compute components fugacity coefficients in each phase from the
EOS and check the equal fugacity constraint

- If convergence is not reached update the k values

Same approach apply to
- liquid-vapour equilibria
- bubble point calculation V=0 xi = zi
- dew point point calculation L=0 yi = zi

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 EQUATIONS TO STATE

Rachford-Rice equation Σ zi(ki-1)/[1+V(ki-1)] = 0

APPLICATION TO BUBBLE POINT V=0

Σ zi(ki-1) = 0
Σ ziki = Σ zi = 1
Σ ziki = 1

APPLICATION TO DEW POINT V=1

Σ zi(ki-1)/ki = 0
Σ (zi- zi/ ki) = 0
Σ zi/ki = 1

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 EQUATIONS OF STATE

APPLICATION OF EQUATION OF STATE

Data : Detailed composition from GC (10 to 200 components)

Experimental PVT data

Matching parameters : to reproduce PVT data

Tc heavy fraction
Pc heavy fraction
acentric factor
kij C1 - C7+
molecular weight heavy fraction

Simplified composition : 2 to 7 pseudo-components

ex : C1-N2, C2-CO2-C3, C4-C5, C6-C10, C11+ (5 comp)

C1-N2, C2-CO2, C3-C4, C5-C6, C7-C8, C9-C10,C11+ (7comp)

pseudo component properties calculated according to mixing rules

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 EQUATIONS OF STATE

MATCHING PARAMETERS

Crude oils :
Pb increases when Pc, Tc, kij increase
GOR sep increases when Pc increases
GOR sep decreases when Tc increases

Gas condensates :
. Tc heavy fraction : when Tc increases
- dewpoint pressure increases
- liquid deposit increases
- GOR sep decreases

. Pc heavy fraction :
- when Pc increases, dew point pressure sensible at low temperature
and liquid deposit decreases

127
PVT DEG 2009 2010
 EQUATION OF STATE

FLUID MODELING

Reservoir Fluid modeling is necessary for Simulation studies

as :
- natural depletion: volatile oil
- gas injection: gas cycling, miscible gas injection
- composition changing with depth: compositional gradient
with rich gas condensate, near-critical fluids, highly
volatile oil, light oil etc…
- regional thermodynamic studies: geochemistry, oil
migration, oil degradation etc..

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PVT DEG 2009 2010
 SATURATION PRESSURE GRADIENT

Saturation pressure - Depth

Depth

Dew point
Reservoir
pressure

Transition zone

Bubble point

Pressure

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PVT DEG 2009 2010
 EQUATION OF STATE

FLUID MODELING

C7+ characterisation and component selection

C7+ is a mixture of paraffinic, naphtenic and aromatic

compounds and is a key parameter in fluid modeling and
fluid behaviour

C7+ pseudocomponent selection will depend of the fluid type

and the production process

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 EQUATIONS OF STATE

CONCLUSIONS

. Cubic equations like Peng-Robinson and Soave-Redlich-

Kwong
used with volume translation are commonly used and give
good results after matching

. EOS matching against Experimental PVT data is

indispensable.

. EOS as predictible tool without matching is of low value

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 OIL AND GAS PHYSICAL PROPERTIES AND PVT STUDIES

7. SAMPLING

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 SAMPLING

Objectives :
The first requirement - and difficulty - in taking
measurements is that of obtaining a truly representative
sample of the formation fluid.

The fluid which gets into the production casing must be

identical to the formation fluid.

In any case, one has to know that the formation fluid is not
homogeneous on the full height of the reservoir.

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PVT DEG 2009 2010
 SAMPLING

Representativity :
- monophasic flow at the bottom of the well
- only one layer per sampling
- stabilized flow regime for well flowing in surface
→ pressure
→ GOR
→ flow rates, etc...

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 SAMPLING

Surface sampling:
. fluids are collected at the well head or the production line :
- one phase flow (rarely)
- or isokinetic sampling
. Fluids collected in the separator, gas and oil, (most frequent
case).
Gas and oil samples collected in the separator are
recombined in the laboratory in proportion to their flow
rates.
For this purpose, we must have :
good precision of the measured flow rates, stabilized well
production, oil and gas sampling realized almost
simultaneously.
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PVT DEG 2009 2010
 SAMPLING

Gas sampling
bottle
gas

Psep, Tsep
GORsep = Qgas/Qoil

Oil sampling
bottle
Psto, Tsto
GORsto

Reservoir fluid Tank oil

Pr, Tr ambient conditions

136
PVT DEG 2009 2010
 SAMPLING

Surface sampling :
Essential data for the recombination :
- pressure and temperature in the separator
- gas flow rate at the separator (orifice meter)
- oil flow rate at the separator (oil meter)
- gas density and compressibility factor for the gas
measurement flow rate
- oil tank flow rate (shrinkage)

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PVT DEG 2009 2010
 SAMPLING

Surface sampling of an oil under saturated reservoir:

. bottom hole flowing pressure ≥ bubble pressure
. no liberation of gas in the reservoir

The well being stabilized

GOR remains constant during sampling

138
PVT DEG 2009 2010
 SAMPLING

Surface sampling of an oil saturated reservoir:

. bottom hole flowing pressure < bubble pressure
. liberation of gas in the reservoir should be minimized
. gas saturation should remain below the critical gas
saturation

Recommendations
. sample the well initially
. produce the well with small drawdown

GOR should remain constant and minimum during sampling

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PVT DEG 2009 2010
 PRESSURE PROFILE IN THE DRAINAGE AREA

140
PVT DEG 2009 2010
 GAS- OIL RELATIVE PERMEABILITIES

2 π r h k k rg dp g
qg = ( )
µg
Relative permeability

dr

2 π r h k k ro dp o
qo = ( )
µo dr

k rg µo
qg / qo = x
k ro µg

Liquid saturation, % PV

141
PVT DEG 2009 2010
 SAMPLING

TEST SEQUENCE

1980/12/16-0800 : OIL
500.

Pws
pressure BARS

480.

Pwf
460.
440.

0. 20. 40. 60. 80. 100. 120.

Qmaxi
rates M3/D

Dégorgement
Clean up Surface
Echantillonnage
300.

Echantillonnage
de surface Stabilized rate Bottom
fond hole sampling
sampling
tp
Initial Built UP
100.

shut-in dt Qmin
0.

0. 20. 40. 60. 80. 100. 120.

T Decimal Hours

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PVT DEG 2009 2010
 SAMPLING

Bottom hole sampling :

This type of sampling is preferred since it guarantees the best fluid
representativity.

Disadvantage : high cost

Two possibilities
Open hole: wireline tools RFT (Repeat Formation Tester) , MDT
(Modular Formation Dynamics Tester, Schlumberger), RCI
(Baker), RCI (Halliburton)

Cased hole: DST Tools, wireline samplers

143
PVT DEG 2009 2010
 SAMPLING
Bottom hole sampling : MDT
Sampling configuration:
Pump out module to eliminate the filtrate in the sample
pumping time duration up to one hour

Analyzer module to monitor fluid quality during pumping time by

- resistivity measurement
- optical measurement by LFA (Life fluid analyzer)

-Sample module: 6×450 cc bottles or 4l,10l and 23 l chambers

Drawback: contamination by filtrate (oil base mud)

144
PVT DEG 2009 2010
 145
PVT DEG 2009 2010
 146
PVT DEG 2009 2010
 SAMPLING

Bottom hole sampling : wireline

during production : tools are lowered in the string.

.SRS (Single-phase Reservoir Sampler)

Transfer :
In sample bottles (oil or gas), under pressure, for
transportation.

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PVT DEG 2009 2010
 SAMPLING

Bottom hole sampling : DST

Under saturated oil reservoir:

- well flowing with BHFP ≥ Bubble point pressure
on minimal choke to control drawdown

Saturated oil reservoir

- well closed and reopened just before sampling
- well flowing at smaller drawdown allowing to remain at
constant GOR

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PVT DEG 2009 2010
 SAMPLING GAS CONDENSATE RESERVOIR

Bottom hole sampling is not recommended for gas condensate

or wet gas
. volume of fluid sampled gives low liquid recovery and
unrepresentative heavy components analysis
. possible segregation of the liquid at the well bottom
. liquid not totally recovered during transfer of bottom hole sample

Surface sampling
. sample the well initially
. produce the well with small drawdown to minimize formation
of a condensate ring near the well bore
. stabilize the well rate above minimum gas velocity

Difficulties encountered during surface sampling of gas condensate

. possible liquid carryover at the separator

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PVT DEG 2009 2010
 SAMPLING CONDENSATE GAS

DST
Water, Bottom sample
mud oil Pressure

Packer Reservoir
pressure

P, T

Dew point

Perforation Distance

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PVT DEG 2009 2010
 SAMPLING : SUMMARY

Produced fluid Fluid flow and Sampling type

reservoir
characteristics Bottom hole sampling Surface sampling

Undersaturated oil GOR=GORi=Ct Well in production Stabilized well

with Pwf > Pb with Pwf>Pb
Saturated oil GOR > GORi To bean back To bean back to
Pwsi = Pb progressively. Well closed have GOR≈ GORi
and stabilized. Sampling at Stabilized flow rate
minimum flow rate. with ∆P min

Gas GOR=GORi=Ct Not recommended Minimum flow rate

possible ; compatible
with
- homogeneous flow
in the tubing
- separator stability

151
PVT DEG 2009 2010
 SAMPLING

Fluid amount necessary :

For oil :
The sampling type is also dependent on the necessary fluid
quantity :
- bottom hole sampling enough for a normal PVT study
- not enough for a heavy fraction decomposition for which
surface sampling is necessary

For gas :
No bottom hole sampling, as the liquid fraction collected is
insufficient, again surface sampling is necessary

152
PVT DEG 2009 2010
 SAMPLING

FLUID QUANTITY TO SAMPLE

BOTTOM HOLE SAMPLING

minimum of 3 representatives samples

SURFACE SAMPLING

. Liquid
2 samples of 600 cm3 minimum
. Gas
GOR < 1500 cuft/bl 2 bottles ( 20 liters)
1500 < GOR < 3000 cuft/bl 3 bottles
GOR > 3000 cuft/bl 4 bottles

153
PVT DEG 2009 2010
 SAMPLING : MOBILE PVT LABORATORY

Purpose : obtain PVT properties on site, analysing the sample

immediately after collection
Equipment : HP cell, Gas chromatograph, viscosimeter
Physical properties obtained : bubble point at T reservoir, Rs,
Bo,
reservoir fluid composition, oil API gravity, dead oil viscosity,
viscosity at T reservoir above Pb, oil mud contamination
Objectives :
- decision on testing
- obtain earlier PVT information

154
PVT DEG 2009 2010
 SAMPLING : DOWN HOLE ANALYSIS OF
FORMATION FLUID SAMPLES

Purpose : know nature of formation fluid, GOR and composition in

down hole conditions
Equipment : Wireline tool associated to MDT
Based on optical absorptions of crude oil in the Near Infrared
Region(NIR)

Crude oils have two types of absorption :

- color absorption
- molecular vibration absorption

155
PVT DEG 2009 2010
 SAMPLING : DOWN HOLE ANALYSIS OF
FORMATION FLUID SAMPLES

Tools developed on these techniques

Life Fluid Analyser (LFA) gives

- GOR
- gas detection by refraction index
Composition Fluid Analyser (CFA) gives
- weight % C1 , C2-C5 , C6+ , CO2 (eventually)
- retrograde due detection by fluorescence

156
PVT DEG 2009 2010
 SAMPLING : OIL BASE MUD
DECONTAMINATION
OBM filtrate miscible with reservoir fluid and modify composition
fluid sampled by MDT
OBM composition
limited to C11 - C20
no aromatic compound
OBM Decontamination Procedure
- Scaling method : with reference uncontaminated sample
- Statistical method : with samples of different contamination levels
- Skimming method : based on regular trend of hydrocarbone molar
percentage versus carbon number
157
PVT DEG 2009 2010
 SAMPLING : OIL BASE MUD
DECONTAMINATION

Obvious contamination between C12/C16

MDT decontamination

2.5
171
447
2
mole fraction (scaled)

83
653
1.5 857
429
1 167
651
0.5

0
5 7 9 11 13 15 17 19 21
cuts

158
PVT DEG 2009 2010
 SAMPLING : OIL BASE MUD
DECONTAMINATION

PVT properties of Decontaminated oil

- using trend versus contamination rate

- mixing rules - the fluid being divided in 3 fractions ( C11- ,
C11+ and mud )
- EOS

159
PVT DEG 2009 2010
 OIL AND GAS PHYSICAL PROPERTIES AND PVT STUDIES

8. OIL PVT STUDY

160
PVT DEG 2009 2010
 PVT STUDIES

• Objectives
- compositional analysis
- volumetric properties and phase behaviour
- production simulation (from bottom to surface)

• High pressure equipment

- high pressure pumps
- oil PVT cell
- gas PVT cell (window cell)
- etc...

• Low pressure equipment

- gas meters
- vacuum pump
- gas chromatographs
- density meters
- etc...
161
PVT DEG 2009 2010
 SAMPLING AND RECOMBINATION

WELL SITE LABORATORY

Gas sampling
bottle
gas
Reservoir
Psep, Tsep fluid
GORsep = Qgas/Qoil
GORsep
Oil
sampling
bottle Psto, Tsto
GORsto Oil Gas
separator separator
Reservoir Tank oil
fluid
ambient conditions
Pr, Tr GORsto

Oil tank Gas tank

162
PVT DEG 2009 2010
 OIL PVT STUDY - PROGRAMME

1. Quality control of samples

- opening pressure (surface sampling)
- saturation pressure (bottom or surface sample)

2. Compositional analysis
- gas analysis : gas chromatography (C9)
- oil analysis ( atmospheric sample)
. gas chromatography C11+ composition
. distillation simulated by chromatography: C20+
composition or atmospheric and subatmospheric
distillation
. density, paraffins content, naphtenes or aromatics
analysis
163
PVT DEG 2009 2010
 OIL PVT STUDY - PROGRAMME

3. Physical recombination
- field GOR correction

4. Mass constant study

- P-V curve at reservoir temperature
. bubble point pressure
. relative volume
. specific volume (calculated)
. isothermal compressibility

164
PVT DEG 2009 2010
 MASS CONSTANT STUDY / OIL

OIL GAS

P1>P sat P2>Psat P3=Psat P4<P3 P5<P4

P1 Saturation pressure
P2 (at T reservoir)
P3
P4
P5

165
PVT DEG 2009 2010
 P - V CURVE

pressure

Volatile oil

P sat

P sat

volume
166
PVT DEG 2009 2010
 OIL PVT STUDY - PROGRAMME

5. Differential vaporization

- objective: simulate the initial liquid fraction remaining in

the reservoir

- realization: depletion and gas production at reservoir

temperature by successive pressure drops

- result: GOR cumulated, oil volume at each pressure step

167
PVT DEG 2009 2010
 DIFFERENTIAL VAPORIZATION

OIL GAS
gas gas

P1>P sat P2<Psat P2 P3<P2 P3

volume
V13
v12

v02

v03 P3 P2 Psat P1 pressure

168
PVT DEG 2009 2010
 DIFFERENTIAL LIBERATION

DIFFERENTIAL LIBERATION
LIQUID DENSITY vs PRESSURE
0.850

0.800
Density (g/cm3)

CALCULATED
0.750

0.700

0.650

0.600
0 500 1000 1500 2000 2500 3000 3500 4000 4500 5000
Pressure (psia)

ρos + Rs ρgs
ρo =
Bo
Surface (dead) oil density measured (gg/cc or Deg API)
169
PVT DEG 2009 2010
 DIFFERENTIAL LIBERATION

DIFFERENTIAL SEPARATION
VISCOSITY OF LIBERATED GAS
0.026

0.024

0.022
Viscosity (cP)

0.020

0.018

0.016

0.014

0.012

0.010
0 500 1000 1500 2000 2500 3000 3500 4000 4500 5000
Pressure (psia)

170
PVT DEG 2009 2010
 DIFFERENTIAL LIBERATION

DIFFERENTIAL SEPARATION
COMPRESSIBILITY FACTOR (Z), GAS FORMATION VOLUME FACTOR (Bg)
OF LIBERATED GAS
1.000 0.20
0.990 0.18

Bg (cfRESERVOIR / scf)
0.980 0.16
0.970 0.14
Z (dimless)

0.960 0.12
0.950 0.10
0.940 0.08
0.930 0.06
0.920 0.04
0.910 0.02
0.900 0.00
0 500 1000 1500 2000 2500 3000 3500 4000 4500 5000
Pressure (psia)

n . R . Tres Pst .Tres

1/Z = Bg = .Z
Pres .Vres Pres .Tst
171
PVT DEG 2009 2010
 OIL PVT STUDY - PROGRAMME

6. Flash separation

- objective: obtain the highest recovery at stock tank

conditions

- realization: in one or several stages in a laboratory

separator

- result:
. GOR
. oil formation volume factor (Bo)
. stock tank oil gravity
. compositional analysis
172
PVT DEG 2009 2010
 ONE STAGE FLASH SEPARATION

• OIL PVT STUDY

→ One stage Flash
Gas

Oil

Oil
Pi ,Ti
“standard conditions”
• GOR
• Formation volume factor (FVF) or Bo
• OIL and gas composition

173
PVT DEG 2009 2010
 TWO STAGES SEPARATION

• OIL PVT STUDY

→ Two stages separation

. at each stage :
- GOR
- Bo
- oil specific volume
- gas gravity (γ)

. and globally :
- total GOR
- total Oil Formation Volume Factor

174
PVT DEG 2009 2010
 TWO STAGES SEPARATION

OIL PVT STUDY

→ Two stages separation

Gas
Gas

Oil

Oil Oil

1st stage 2nd stage

P1 , T1 P2 , T2 P3 , T3

175
PVT DEG 2009 2010
 OIL AND GAS PHYSICAL PROPERTIES AND PVT STUDIES

9. GAS CONDENSATE
PVT STUDY

176
PVT DEG 2009 2010
 GAS CONDENSATE PVT STUDY PROGRAMME

1- Quality control of samples

. opening pressure, saturation pressure

2. Compositional analysis
. reservoir fluids composition up to C11+
or C20+

3. Physical recombination
. field GOR correction

177
PVT DEG 2009 2010
 GAS CONDENSATE PVT STUDY PROGRAMME (cont.)

4. Constant Composition Expansion (CCE)

. P-V relation at reservoir temperature
. dew point, liquid condensation vs pressure

5. Constant Volume Depletion (CVD)

. reservoir simulation of depletion at constant
volume and reservoir temperature
. pressure steps depletion :
- liquid condensation
- gas production and composition

178
PVT DEG 2009 2010
 WINDOW CELL

179
PVT DEG 2009 2010
 CONSTANT COMPOSITION EXPANSION

•
+

P1>Psat P2=Psat P3<P2 P4<P3 P5<P4 P6<P5 P7<P6

oil

gas

180
PVT DEG 2009 2010
 CONSTANT COMPOSITION EXPANSION

Pressure
P1
C •
• P2=Psat
•
P3

P4

P5

P6

P7

Temperature
181
PVT DEG 2009 2010
 GAS CONDENSATE PVT STUDY

⇒ Validity of the recombination

- constant composition expansion : saturation pressure

- most often, gas condensates are saturated, in equilibrium
with an oil ring in the reservoir
- Psat = Pres : gas condensate saturated; production
testing and recombination are correct
- Psat > Pres : impossible ; example : commingle
production from 2 zones, one of each being oil
- Psat < Pres : undersaturated gas condensate, influence
of the GOR, liquid deposit in the wellbore

182
PVT DEG 2009 2010
 CONSTANT VOLUME DEPLETION

OIL GAS

gas gas

Vsat v2 vsat v2

183
PVT DEG 2009 2010
 GAS CONDENSATE PVT STUDY PROGRAMME

6. Flash separation

- objective: verify the compositional analysis of the

recombined sample

- realization: in one stage in a laboratory separator

- result:
. GOR
. gas formation volume factor (Bg)
. stock tank condensate gravity
. compositional analysis

184
PVT DEG 2009 2010
 USE OF PVT FOR
RESERVOIR STUDY

185
PVT DEG 2009 2010
 PVT FOR RESERVOIR STUDY

WHICH PRESSURE

WHICH PVT

GOC

DATUM
X

WOC

186
PVT DEG 2009 2010
 PVT FOR RESERVOIR STUDY

LABORATORY GIVES : Bo Rs

– FLASH LIBERATION THROUGH SEPARATORS Bof, Rsf

– DIFFERENTIAL LIBERATION Bodif, Rsdif

BAD REPRESENTATION OF REALITY

SO COMPOSITE PVT

187
PVT DEG 2009 2010
 PVT FOR RESERVOIR STUDY

DIFFERENTIAL - COMPOSITE
OIL FORMATION VOLUME FACTOR (Bo) vs PRESSURE
2.000

1.900

1.800
Bo (reservoir b / stb)

1.700

1.600
l
e re ntia
1.500
diff
1.400

osite
1.300

1.200
comp
1.100

1.000
0 500 1000 1500 2000 2500 3000 3500 4000 4500 5000
Pressure (psia)

Composite Bo curve deduced from

Ê composite Bo at Pb
188
PVT DEG 2009 2010
 PVT FOR RESERVOIR STUDY

DIFFERENTIAL - COMPOSITE
SOLUTION GAS (Rs) vs PRESSURE

1200

1000
Rs (scf / stb)

800

600

e ntial
er
400 diff

p o site
200 c om

0
0 500 1000 1500 2000 2500 3000 3500 4000 4500 5000
Pressure (psia)

Composite Rs curve deduced from

Ê composite Rs
189
PVT DEG 2009 2010
 PVT FOR RESERVOIR STUDY

PVT ‘‘ Black oil’’ 1 table composite

PVT ‘‘ Black oil ‘‘ 1 table diff for

reservoir
1 table separator
for wells

PVT ‘‘ Compositional ’’ Equation of State

from pseudo-
constituents

190
PVT DEG 2009 2010
 OIL AND GAS PHYSICAL PROPERTIES AND PVT STUDIES

10. WATER PROPERTIES

191
PVT DEG 2009 2010
 WATER PROPERTIES

⇒ reservoir water are systematically associated with

hydrocarbons

. water from petroleum reservoirs

- interstitial water in the hydrocarbon zone
- aquifer water

. water production
- aquifer water
- injected water
- water dissolved in gas

192
PVT DEG 2009 2010
 WATER PROPERTIES

⇒ no downhole sampling, or very seldom (then

no PVT study)

⇒ water properties derived by correlations

⇒ water analysis at atmospheric pressure

. salinity
. chemical analysis
. density,
. Ph
. resistivity
193
PVT DEG 2009 2010
 WATER PROPERTIES

⇒ downhole sample under pressure

. bubble point pressure: Pb
. separation at standard conditions (flash)
→ GWR, Bw
. density
. compressibility

⇒ surface sample at Patm

. salinity
. ionic composition
. density
. pH
. resistivity
194
PVT DEG 2009 2010
 WATER PROPERTIES

• salinity
expressed in g/m3 or mg/liter or P.P.M.(g of solids by million g of
brine)
• ionic analysis
ions most often found :
Na+, K+, Ca++, Mg++, Cl-, So4--, CO3--, HCO3-
graphical representation of water analysis.

• resistivity
• solubility of natural gas in water
• volumetric properties
- isotherm compressibility Cw = - 1/V.(dV/dp) T=cte
(close to 0.4*10-4/bar)
- density (depending of salinity)
- viscosity
195
PVT DEG 2009 2010
 RESERVOIR WATER ANALYSIS

196
PVT DEG 2009 2010
 DIAGRAMS OF WATER ANALYSIS

Stiff diagram

Scale : meg/liter

197
PVT DEG 2009 2010
 WATER PROPERTIES

⇒ IONIC COMPOSITION

cations : Na + }
K+ }
Ca 2+ }
Mg 2+ }

sometimes Sr 2+, Ba 2+, Fe 2+

anions : CO3 2- }
HCO3 - }
Cl - }
SO4 2- }
NO3 - }

198
PVT DEG 2009 2010
 EXAMPLE OF WATER ANALYSIS

WATER ANALYSIS
Water sample under atmospheric pressure
ph = 6.28 @ 20°C

Cations Na+ K+ Ca2+ Mg2+ Sr2+ Ba2+ Iron

mg/l 43498.94 875 1681 307.0 19.0 0.05 38.0

meq/l 1892.08 22.38 84.05 25.27 0.43 0.00 1.36 2025.6

Anions Cl- HCO3- CO3,2- SO4,2- NO3-

mg/l 69450 842 2 2655 2

meq/l 1956.34 13.80 0.07 55.3 0.03 2025.6

TDS (total dissolved salts) 119370 mg/l (calculation)

TDS “ 107000 mg/l (measured)

199
PVT DEG 2009 2010
 WATER ANALYSIS

Conversion to milliequivalents per liter

Component Concentration Component Concentration

mg/l meq/l mg/l meq/l

Na+ 17 595 765 SO4- 2 620 54.6

K+ 0 0 Cl- 33 079 931.8
Ca++ 2 960 148 CO3- 0 0
Mg+ 927 76.3 HCO- 177 2.9
989.3 989.3

equivalent weight = ion atomic weight / valence

example : equivalent of sulfate (SO4-) [ 32 + (4*16) ] / 2 = 48 g/eq wt

and meq/l of SO4- 2620 mg/l / 48 mg/meq = 54.6 meq/l

200
PVT DEG 2009 2010
 WATER PROPERTIES

⇒ DEFINITIONS
Solubility of natural gas in water
Volume of gas dissolved (at s.c.)
Rsw =
Volume of water(s.c.)

for pure water Rs = f (P,T)

for formation water Rs = f (P,T,salinity)

Formation volume factor of water

Bw = Volume of water at res cond. / Volume of water at s.c.

Bw = f (P,T,Rsw)

201
PVT DEG 2009 2010
 SOLUTION GAS - WATER RATIO

Dodson & Standing

202
PVT DEG 2009 2010
 WATER PROPERTIES

⇒ DEFINITIONS

⇒ example : calculate solubility and water FVF for

salinity = 20 mg/l, T = 200 °F, P = 3000 psig

Rsw = 15.3 cuft/bl pure water

Rsw = 15.3*0.92 = 14 cuft/bl brine

Bw = 1.027 pure water

Bw = 1.032 brine

203
PVT DEG 2009 2010
 WATER PROPERTIES

• Water Formation Volume Factor (Bw)

Water formation volume factor, bbl/bbl

Pressure, psia
Water-formation volume factor for pure water (dashedlines) and pure water
saturated with natural gas (solid lines) as a function of pressure and
temperature (from Dodson and Standing)
204
PVT DEG 2009 2010
 WATER PROPERTIES

⇒ DEFINITIONS

water compressibility
Cw = f (P,T,Rsw)
Cw = - 1/V (dV/dP)T

water density
ρ = f (P, T, salinity)
correlation or ρw (p,t) = ρw (patm,15°C) / Bw ( neglecting the gas
weight)

water viscosity
µ = f (T, salinity)
see corelation

205
PVT DEG 2009 2010
 WATER PROPERTIES

⇒ DEFINITIONS

example : calculate water compressibility and water density for

salinity = 20 mg/l, T = 200 °F, P = 3000 psig, Rsw = 14 cuft/bl brine

Cw = 3.1 10-6 psi-1 pure water

Cw = 1.12 * 3.1 10-6 = 3.5 10-6 psi-1 brine

density =

ρw = 0.985 g/cc (correlation) or ρw = 1.013/10.32 = 0.980 g/cc

viscosity = 0.32 cp (correlation)

206
PVT DEG 2009 2010
 WATER COMPRESSIBILITY

• Effect of dissolved gas upon the compressibility of water (from Dodson

and Standing)

207
PVT DEG 2009 2010
 DENSITIES OF NACL SOLUTIONS

gm/liter at standard conditions

Schlumberger, 1974
208
PVT DEG 2009 2010
 WATER DENSITY VS SALINITY

SATURATION
at 317,9 g/l sol
or 264.000 ppm

Water gravity @ 20°C/4°C

ppm

Water salinity
209
PVT DEG 2009 2010
 WATER VISCOSITY

Temperature, Twf : °C

Water viscosity, µwwf : Centipoises

Temperature, Twf : °F

Schlumberger, 1974
210
PVT DEG 2009 2010
 WATER - HYDROCARBONS SYSTEMS

• Mutual attraction between water and hydrocarbons is

extremely small
- low water solubility in hydrocarbon liquids
- water content in natural gas relatively low
- hydrates formation in natural gas
• Solubility of water in hydrocarbons liquid
not enough data to develop a correlation in P and T,
solubility reported for some hydrocarbons vs
temperature

• Solubility of water in natural gas

see correlation

211
PVT DEG 2009 2010
 SOLUBILITY OF WATER IN HYDROCARBONS LIQUID

Solubility of water in liquid

Mol fraction water in hydrocarbon liquid

Temperature, deg F
212
PVT DEG 2009 2010
 WATER CONTENT OF NATURAL GAS

Water content, lb H2O per million cu ft total gas

Water contents of
natural gas in
equilibrium with
liquid water

Temperature, deg F 213

PVT DEG 2009 2010
 WATER - HYDROCARBON SYSTEMS

• Gas hydrates

Natural gas under pressure in contact with excess water liquid

might form crystalline solids called hydrates.

Crystals like ice with density = 900 kg/m3

Framework : water molecules and in between void spaces
occupied by hydrocarbons molecules.
First five alkanes only give hydrates

Formation conditions :
up to T = 25°C and P = 800 bars according to the nature of the gas

See also the schematic phase diagram

214
PVT DEG 2009 2010
 WATER - HYDROCARBON SYSTEMS

• Gas hydrates

Inhibition :
- by mechanical treament to remove free liquid water.
- increasing the gas temperature or insulating the gas line to
stay above the hydrate formation temperature at that
pressure.
- using an aqueous solutions of antifreezes, like methanol or
glycol, polymers to prevent crystallisation of hydrates or
antiagglomerate (AA)

215
PVT DEG 2009 2010
 PHASE DIAGRAM / WATER - HYDROCARBONS

• Phases in a water-oil system

E D

Hydrate + water + HC liquid

C2
Hydrate C1
+ Ice HC liquid + water
+ HC liquid
Pressure

F G
Hydrate B
+ Ice Hydrate
HC vapor + water
+ HC vapor + water
+ HC vapor
A
J
Ice +
HC vapor

0°C Temperature
216
PVT DEG 2009 2010
 ALKANES HYDRATES

• Hydrate-forming conditions for paraffin hydrocarbons (from

Handbook of Natural Gas Engineering by Katz)

Pressure, psia

Temperature, deg F 217

PVT DEG 2009 2010