Fsico - Qumica del Petrleo

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Diagramas de Fases
Mtodos de muestreo y tipos de experimentos
de laboratorio
Relacin con las determinaciones volumtricas
 Fsico - Qumica del Petrleo

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 What is the Petroleum?
Its a mixture of Naturally Occurring Hydrocarbons Fluids.

Petroleum may exist in solid, liquid or gaseous states

depending upon the conditions of pressure and temperature of
the volume where its located.
 The molecular constitution of the crude oil differs widely.

Different wells in the same reservoir have different

molecular constitution.
Crude oils are frequently classified by the most frequent
composition:

. -Paraffin - Base: Oils containing predominantly paraffin

series hydrocarbons.

. -Asphalt - Base: Oils containing predominantly

polymethylene or olefin hydrocarbons.

. -Mixed - Base: Oils containing large quantities of both

paraffin and polymethylene hydrocarbons.
The Crude oils are classified according to their physical
properties.

Density (Specific Gravity)

Viscosity (Cinematic and Dynamic or Absolute) of the

liquid petroleum.
Both variables need to be defined at specified thermodynamic conditions
(Temperature and pressure),

Contents of solved gas, water and impurities.

The Specific Gravity of liquids is defined as the ratio of the
density of the liquid to the density of pure water, both at
specified thermodynamic conditions.

m : Liquido / Agua

Since crude oils are generally lighter than water, a Baume-type

scale is used in the Petroleum Industry, referred as API
scale.

API= 141.5 - 131.5

The Viscosity are calculated through a Kinematics
process, that means the viscosity is reported as the time of
efflux (in seconds) of a know volume of liquid through a
standardized orifice at a defined temperature and standard
pressure (atmospheric).
There are many different Kinematics practical systems:
Saybolt Universal, Saybolt Furol, Engler, etc. The times
reported depend on the instrument employed.

The Dynamic viscosity (Absolute) in centipoises is obtained

by multiplying the Kinematics viscosity in centistokes by the
Density of the Fluid (in gr/cm3).
 Fsico - Qumica del Petrleo

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 Phase Behaviour. Basic Concepts.

Oil and Gas are naturally existing hydrocarbon mixtures quite

complex in chemicals composition, which exists at elevated
temperatures and pressures in the reservoir.

The composition of the fluid remaining in the reservoir at any

stage of depletion is not the initial fluid composition and the
change depend on the fraction of oil and gas produced until
this depletion stage.
Phase Behaviour. Basic Concepts.
 Phase Behaviour. Basic Concepts.
The state of the hydrocarbon mixture at the surface depends
upon the composition, pressure and temperature of the
reservoir (at the perforating casing place), bottom and surface
facilities design, and the behaviour of pressure and
temperature along the bottom and surface facilities.

Separator Gas
Well stream
stream
Tank
Separator Oil stream

Separator
 Basic Concepts: Single - Component Systems.

Ethane Phase Diagram

C: Critical Point, the highest value of pressure and temperature

at which two phases can coexist.
 Basic Concepts: Single - Component Systems.
Diag. fase esquemtico de comp puros

P
Mixture phase behaviour depends
on molar composition

Light Molecular
Mass component

Component PC

Intermediate Molecular
Mass component

High Molecular Mass

component
ComponentTC

T
 Basic Concepts: Binary Systems

When a second component is added to a Single hydrocarbon

Component system, the phase behaviour became more
complex. This increase in complexity is caused by the
introduction of another variable, Composition, to the system.
 Basic Concepts: Multicomponent Systems

Naturally the hydrocarbon systems are composed of a wide

range of constituents.

These constituents include not only the paraffin series and

various other series as well as impurities as CO2, SH2 , He,
H2O and others as contaminants.

The phase behaviour of the mixture is dependent on the

composition of the mixture as well as the properties of the
individual components.
 Basic Concepts: Multicomponent Systems
P A B C
Critical Point
Mixture
Crincondentherm
Pc
L Point

L+V
G
V
T
T1 T
Mixture c T2 T3
 Caracterizacin de fluidos
Los 5 fluidos del reservorio
P C7+ < 0.7% Reservoir initial
condition
Dry 1%<C7+ < 4%

Wet 4%< C7+ < 12.5%

Gas
Gas 12.5% < C7+ < 20%
Gas&
Cond Volat
Oil
20%< C7+
Reservoir Black
fluid path Oil

Separator
condition

Reservoir
Temperature T
Clasificacin de yacimientos
Composicin Quimica
 Clasificacin de yacimientos
Segn McCain

RGP API Color

Petrleo Negro < 90 m3/m3 < 30

Petrleo Voltil < 1400m3/m3 > 30

Gas-condensado < 12500m3/m3 < 60

Gas-Hmedo < 18000m3/m3 > 60

Gas-Seco > 18000m3/m3 > 60

RGP : Relacin Gas - Petroleo

 Fsico - Qumica del Petrleo

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 Mtodos de muestreo

Para que tomar muestras de fluido del

Reservorio ?

Cual es la aplicacin de los anlisis de

laboratorio ?

Representatividad de la muestra.

Tipos De Muestras : fondo y Superficie

 Mtodos de muestreo

Para que tomar muestras de fluido del Reservorio?

Permiten determinar las propiedades de los fluidos en

condiciones de Presin y Temperatura de reservorio y
superficie bajo diferentes condiciones de explotacin.

Cual es la aplicacin de los anlisis de laboratorio?

Clculos de Volmenes In Situ,
Definir Estrategias de Produccin,
Interpretar ensayos de pozos.
Ajustar simuladores composicionales,
Optimizar equipos de tratamiento, etc
 Mtodos de muestreo
Representatividad de la muestra.

El fluido recolectado debe ser lo ms cercano posible en

composicin al fluido que se encuentra en el reservorio.

Si las muestras analizadas no son representativas, los

anlisis resultan errneos, aunque estn hechos con las
mejores prcticas de laboratorio.
P A
Critical Point
Mixture
Crincondentherm
Pc
L Point
e
lin
le
bb
Bu

L+V
%

G
100

e
lin
ew
75
%
%
D
V
50 0%
T
T1 Mixture Tc
 Mtodos de muestreo

El mtodo de muestreo depender de:

Tipo de fluido (Gas, Petrleo, Petroleo Voltil, etc.)
Condiciones de produccin del pozo : Caudal,
Relacin Gas Petrleo, Presin de fluencia, instalacin
de produccin, etc

Tipos De Muestras :
Muestras de fondo
Muestras de Superficie
 Mtodos de muestreo

Tipo de Estado del Posibilidad Posibilidad

Reservorio Fluido Muestra de Fondo Muestra de Superficie

Petrleo Saturado Si Si
( Pb = Pefi )

Subsaturado Si Si
( Pb < Pefi )

Gasifero ---------------- No Si, bajo condiciones

estabilizadas
( Variacin de RGP menor al 6% )

Volatil Ol ---------------- No Si, bajo condiciones

estabilizadas
( Variacin de RGP menor al 6% )

Pb = Presin de burbuja ; Pefi = Presin esttica fondo inicial Pef = Presin esttica de fondo
 Caracterizacin de fluidos
Muestreo de Superficie (SS)
Surface Sampling & Sampling points

Separator Gas sampling

point: 20 lts bottle capacity

Separator Gas
Well stream stream
Tank
Separator Oil stream

Separator

Separator Oil sampling point:

600 cm3 bottle capacity
 Mtodos de muestreo
Company : xxxxxxxx
Field : Campo X
Well : Pozo x-1

DATA and VALUES TAKEN FROM SAMPLING REPORT

FORMATION CHARACTERISTICS
Formation Name SPRINGHILL
Static Reservoir Pressure 4484.31 psia
Reservoir Temperature 321 F

WELL CHARACTERISTICS
Producing Interval 3105/3110 mts.
Packer _

SAMPLING CONDITIONS
(Surface Sample)
Sample number 1 2 3
Choke 14 mm 14 mm
Liquid Bottle id. JM 007 22478-65
Transfer fluid Mercury Mercury
Gas Bottle id. A-10040 A-10970
Transfer fluid Vacuum Vacuum
Sampling Date 14/05/1995 14/05/1995
Sampling initial Time 17:00 18:00
Sampling end Time 17:45 18:45
Bottom Hole Pressure [psia] 3745 3748
Bottom Hole Temperature [F] 318 318
Well Head Pressure [psig] 2249 2259
Well Head Temperature [F] 179 182
Separator Pressure [psig] 520 500
Separator Temperature [F] 129 132
Ambient Temperature [F] _ _
Gas Rate [M m3/da] 396.064 393.340
Gas Gravity (Aire=1) 0.650 0.650
Std Oil Rate (Tank) [m3/da] 42.060 42.761
Separator Oil Rate [m3/da] 50.670 51.209
Oil Gravity (@ 60 F) [g/cm3] 0.779 0.779
B.S.W. 1% 1%
Gas-Oil Ratio (GOR) STD [m3/m3] 9,417 9,199
Fpv Factor 1.033 1.032

LABORATORY MEASSUREMENTS
Gas bottle Pressure @ 60.0C [PSIG] 520 510
Sp. Gas Gravity [air=1] 0.686 _
Caracterizacin de fluidos
Muestreo de fondo (BHS)
 Caracterizacin de fluidos
Muestreo de fondo (BHS)

a single phase fluid, oil plus its dissolved gas, is flowing in the wellbore
 Fsico - Qumica del Petrleo

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Diagramas de Fases
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de laboratorio
Relacin con las determinaciones volumtricas
 Ensayos de Laboratorio

Celda de Ensayo PVT

Ensayos a Temperatura controlada : T reservorio

 Ensayos de Laboratorio
Caracterizacin de fluidos
Flujo trabajo lab muestreo de fondo

Bottom Hole Sample

Sample selection

Compositional analysis via Flash experiment

CCE: Constant Composition Expansion

DL: Differential Liberation

Separator train experiments perform

 Ensayos de Laboratorio
Caracterizacin de fluidos
Expansin a Masa Constante (CCE)
One phase expansion Two phase expansion

P1 > Pb P2< P1 P3 = Pb P4 < P3 P5 < P4 P6 < P5

 Ensayos de Laboratorio
Caracterizacin de fluidos
Liberacin Diferencial (DL)

Gas
withdrawal
Gas
withdrawal Gas
withdrawal

P1 = Pb P2< P1 P3< P2 P4 < P3

 Ensayos de Laboratorio
Caracterizacin de fluidos
Separacin (2 etapas + tanque)
VG1 First stage
Gas volume VG2 Second stage
(Gas withdrawal) Gas volume
(Gas withdrawal)
VGSTD Stock Tank
Oil volume

VOS Liquid VO1 First Stage VO2 Second Stage VOSTD Stock Tank
Saturated volume Liquid volume Liquid volume Oil volume

Pb & Tres P1 & T1 P2 & T2 Patm & 15.5C

 Ensayos de Laboratorio
Propiedades PVT determinadas en Lab.
 Ensayos de Laboratorio
Propiedades PVT determinadas en Lab.

Oil formation volume factor (from DL):

Bo : is the volume in m3 occupied in the reservoir, at the prevailing pressure
and temperature, by one stock tank m3 of oil plus its dissolved gas (units m3
(oil + dissolved gas)/ m3 oil).
Vo( p R ;TR )
Bo =
Vo( std )

Solution Gas Oil Ratio (from DL):

Rs : which is the number of standard cubic meter of gas which will dissolve in
one stock tank cubic meter of oil when both are taken down to the reservoir at
the prevailing reservoir pressure and temperature (units scm. gas/stm3 oil).

Bg The gas formation volume factor, which is the volume in barrels that one
standard cubic meter of gas will occupy as free gas in the reservoir at the
prevailing reservoir pressure and temperature (units rcm free gas/ssf gas).
 Ensayos de Laboratorio

Oil formation volume factor (from DL):

Vo( p R ;TR )
Bo = Bo > 1
Vo( std )
 Ensayos de Laboratorio

Rs : number of standard cubic meter of gas which will dissolve in one stock tank cubic
meter of oil when both are taken down to the reservoir at the prevailing reservoir
pressure and temperature (units scm. gas/stm3 oil).
Ensayos de Laboratorio
 Ensayos de Laboratorio
Caracterizacin de fluidos
Flujo trabajo lab muestreo de sup
Surface Sample
Sample selection

Samples recombination with sampling GOR (Lab corrected )

Compositional analysis via Flash experiment

CCE: Constant Composition Expansion

CVD: Constant Volume Depletion

(sometimes DL is also applied to oil)

For oils: Separator train experiments perform

Surface Sample

RELACION GAS-PETROLEO MEDIDA EN CAMPO

Y CORREGIDA CON DATOS DE LABORATORIO

De la planilla de muestreo se obtiene la

Gas de Separador STD (no corregido)

RELACION ------------------------------------------------------------------- = 26,850 m3/m3
Lquido de Tanque (Condiciones STD)

que en base al factor de Volumen entre Separador y Tanque, determinado en Laboratorio,

Lquido de Separador (Cond. de Separador)

1.147 m /m
3 3
Fact de Vol ------------------------------------------------------------------- =
Lquido de Tanque (Condiciones STD)

conduce a:

Gas de Separador STD (no corregido)

23,413 m /m
3 3
RELACION ------------------------------------------------------------------- =
Lquido de Separador (Cond. de Separador)
 COMPOSICION MOLECULAR DEL FLUIDO DE RESERVORIO CALCULADA
POR RECOMBINACION NUMERICA DE LOS FLUIDOS DE SEPARADOR
CON 'RGP' CORREGIDA EN BASE AL 'Z' Y G. Esp. DEL GAS

GAS DE LIQUIDO DE FLUIDO DE Valores Asignados

COMPONENTE SEPARADOR SEPARADOR RESERVORIO Densidad Peso
Bot: A-10040 Bot: 9209-3 RECOMBINADO
[% Molar] [% Molar] [% Molar] [g/cm3] Molecular
Nitrogeno 2.088 0.269 2.077 0.803 28.020
Dixido de Carbono 0.000 0.000 0.000 0.809 44.010
Metano 91.700 18.656 91.233 0.330 16.040
Etano 3.770 3.414 3.768 0.450 30.070
Propano 1.270 2.894 1.281 0.507 44.090
i-Butano 0.326 1.278 0.332 0.563 58.120
n-Butano 0.338 1.784 0.348 0.584 58.120
i-Pentano 0.139 1.426 0.148 0.624 72.150
n-Pentano 0.083 1.321 0.091 0.631 72.150
Hexanos 0.104 4.110 0.130 0.680 84.000
Heptanos 0.087 8.805 0.143 0.716 96.000
Octanos 0.067 13.985 0.156 0.739 107.000
Nonanos 0.020 8.640 0.075 0.758 121.000
Decanos 0.006 6.517 0.048 0.772 134.000
Undecanos 4.754 0.030 0.783 147.000
Dodecanos 3.573 0.023 0.794 161.000
Tridecanos 3.289 0.021 0.805 175.000
Tetradecanos 2.843 0.018 0.816 190.000
Pentadecanos 1.793 0.011 0.826 206.000
Hexadecanos 1.601 0.010 0.833 222.000
Heptadecanos 1.514 0.010 0.841 237.000
Octadecanos 1.131 0.007 0.845 251.000
Nonadecanos 0.983 0.006 0.850 263.000
Eicosanos y Sup 5.422 0.035 0.858 355.100
100.000 100.000 100.000
PROPIEDADES MEDIAS
G. Esp. (aire=1) 0.614
Densidad @ 15.5C [g/cm3] 0.743
Peso Molecular Medio 17.8 114.6 18.43
PROP. CALCULADAS DE LA FRACCION C7+
Porcentaje Molar 0.180 64.849 0.594
Densidad @ 15.5C [g/cm3] 0.733 0.791 0.777
Peso Molecular Medio 104.1 157.3 141.3

DATOS EMPLEADOS PARA EL CALCULO

3 3
Relacin GAS-PETROLEO: 23,578 m /m en condiciones STD
Fraccin molar de gas 0.9936
Fraccin molar de lquido 0.0064
 Caracterizacin de fluidos
Expansin a Volumen Constante (CVD)

Gas
withdrawal Gas Gas
withdrawal withdrawal

P1 = Pb P2< P1 P3< P2 P4 < P3

Propiedades PVT determinadas en Laboratorio
 DEPLETACIN A VOLUMEN CONSTANTE Y 147.2 C
FACTOR DE VOLUMEN DEL EFLUENTE

F. DE VOLUMEN DEL EFLUENTE

0.038
0.036
0.034
0.032
0.030
0.028
0.026
XBg YBg
### 0.00495 0.00495
0.024
### 0.00562 0.00562
0.022
### 0.00659 0.00659
Bg

0.020
### 0.00812 0.00812
0.018
### 0.01076 0.01076
0.016
### 0.01614 0.01614
0.014 ### 0.03220 0.03220
0.012
0.010
0.008
0.006
0.004
0.002
0 20 40 60 80 100 120 140 160 180 200 220 240 260 280 300 320 340 360
PRESIN [Kg/cm2]abs
 DEPLETACIN A VOLUMEN CONSTANTE Y 147.2 C
FACTOR DE DESVIACIN 'Z' BIFSICO

FACTOR DE DESVIACIN DEL FLUIDO REMANENTE

1.05

1.04

1.03

1.02

1.01

1.00

0.99

0.98

0.97

0.96

0.95

0.94
0 20 40 60 80 100 120 140 160 180 200 220 240 260 280 300 320 340 360
PRESIN [Kg/cm2]abs

The PressureVolumeTemperature relation for a real gas can be uniquely defined by

the simple equation of state
PV = ZnRT
in which the Zfactor, which accounts for the departure from ideal gas behaviour
 DEPLETACIN A VOLUMEN CONSTANTE Y 147.2 C
VISCOSIDAD DEL EFLUENTE

VISCOSIDAD DEL EFLUENTE

0.022

0.021

0.020

0.019
Viscosidad [cp]

0.018

0.017

0.016

0.015

0.014
0 20 40 60 80 100 120 140 160 180 200 220 240 260 280 300 320 340 360
PRESIN [Kg/cm2]abs
 DEPLETACIN A VOLUMEN CONSTANTE Y 147.2 C
VOLUMEN DE LQUIDO ACUMULADO EN PORCIENTO DEL
VOLUMEN DE FLUIDO EN CONDICIONES DE RESERVORIO

LQUIDO ACUMULADO

0.30

0.25
[%] Del Vol. a P. de Reserv.

0.20

0.15

0.10

0.05

0.00
0 20 40 60 80 100 120 140 160 180 200 220 240 260 280 300 320 340 360
PRESIN [Kg/cm2]abs
 DEPLETACIN A VOLUMEN CONSTANTE Y 147.2 C
COMPOSICIN MOLECULAR DEL EFLUENTE
100

N2
CO2
C1
C2
C3
10 i-C4
n-C4
i-C5
Composicin

n-C5
C6
C7
C8
C9
1 C10+

0.1
0 20 40 60 80 100 120 140 160 180 200 220 240 260 280 300 320 340 360
 Fsico - Qumica del Petrleo

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Relacin con las determinaciones volumtricas
 Relacin con las determinaciones volumtricas

Clculos volumtricos

Balance de Materiales

Clculos de Flujo: Ley de Darcy

Clculos Volumtricos
Clculos Volumtricos

Area

Espesor Con
Hidrocarburos
 Porosidad (%)

Saturacin de Petrleo (%)

N= A*H * * So
Bo
Factor de Volumen del
Petroleo (adim)
V= A*H
A : Area (m2)
H: Espesor mineralizado (m)
 Balance de Materiales

A B C

N +mNBoi = Np + Gp (Expans Petroleo +Gas Disuelto)- Expansin Gas Libre

 Clculos de Flujo: Ley de Darcy

Viscosidad
Caudal de Petrleo

Kh = Transmisividad
K : permeabilidad (mD) Factor de Volumen del Petrleo (adim)
h: Espesor permeable