4/4/2014 1

Termodinamica de
Hydrocarburos

(Phase Behavior of Hydrocarbon Fluids)


Fall, 2006
4/4/2014 2

Phase Behavior
Fundamentals and Review
of Thermodynamics

Bucaramanga
Diciembre, 18-22, 2006
Instructor: Dr. Maria A. Barrufet


4/4/2014 3
Welcome Discussion
Class starts at 8:00 A.M
Class ends 5:00 p.m+
?
Lunch from 12:00 to
12:30?
Coffee/tea breaks in
the morning and in the
afternoon
10 Minute breaks every
50 minutes of class
A mix of lectures,
discussions, and
exercises morning and
afternoon
4/4/2014 4
Welcome Discussion
Informal class - ask
questions at any time
Autobiographical
sketch
Objectives of Course
Rules
Disable all cell phones
Be in class ON TIME
Avoid talking to
neighbors (public
discussions only)
4/4/2014 5
Maria A. Barrufet
Education
University National of Salta
(Argentina) B.S. Chemical Engineering
University National of Sur (Argentina)
M.S. Chemical Engineering
Texas A&M University Ph.D. Chemical
Engineering
Professor in the Petroleum and
Chemical Engineering Departments of
Texas A&M University
4/4/2014 6
Teaching Experience
Numerical Physics Of Reservoir Simulation
Enhanced Oil Recovery Processes
Thermal
Chemical
Miscible
PVT/Phase Behavior
Engineering Near Critical Reservoirs
(compositional reservoir simulation)
Reservoir Engineering
Thermal Recovery Processes (detailed)
Applied Reservoir Simulation
Waterflood Management



4/4/2014 7
Class Materials
Power Point Presentations
Selected SPE papers and
bibliography in day-by-day folder
Excel files and useful software
Digitizer
Steam Properties
Fluid Property Calculator
Excel Exercises
Ternary diagram
Homework practices
Etc.

4/4/2014 8
Schedule Day 1
Course Introduction:
Thermodynamic Concepts and
Definitions. Mathematics and
Programming Tools
Basic Phase Behavior.
Single Component Systems.
Two-Component Systems.
Three-Component Systems.
Multi-Component Systems
4/4/2014 9
Schedule Day 1 (more)
Phase Diagrams: Volumetric and
phase behavior of pure substances,
binary and multicomponent
systems. Phase diagrams (P-V, P-T,
P-x, y-x).
Hydrocarbon Phase Behavior.
Classification of Reservoir Fluids
Based Upon Phase Diagrams, Fluid
Compositions, and Production Data
Ternary Diagrams. Phase Equilibria
Representation

4/4/2014 10
Schedule Day 1.
Examples & Homework.

4/4/2014 11
References
Lecture Notes from Maria Barrufet (MAB)
The Properties of Petroleum Fluids William
McCain Jr. Pennwell (1990) (WM)
Properties of Oils and Natural Gases Pedersen
et al. (PFT)
Phase Behavior SPE Monograph 20 Curtis
Whitson and Michael Brule (CW)
Hydrocarbon Phase Behavior Tarek Ahmed
Gulf Publishing Co. (1989). (TA)
Selected Papers from the SPE and other Journals.
Selected Internet sites to be announced. (I)
4/4/2014 12
Additional References

Power point presentations
Other library papers (AIChe,
Journal of Fluid Phase
Equilibria, Journal of
Petroleum Engineering Science
and Technology)

4/4/2014 13
Grading Police

30% HW & Discussions
35% Exam 1 in class
35% Exam 2 take home
4/4/2014 14
Graphical, Analytical,
Math Skills Required
Understand 3-D plots and 2-D
projections (slices)
Derivatives (analytical, numerical &
graphical)
Partial Derivatives (numerical &
analytical)
Integration (analytical and numerical)
Solution of non linear equations
Root finding routines
4/4/2014 15
Graphical, Analytical,
Math Skills Required
Units and conversions (dimensional
analysis)
Numerical analysis
Dependent and independent variables
Solution of simultaneous equations
4/4/2014 16
Learning Objectives
After completing this section you
will be able to:
Understand pure component phase
behavior as a function of pressure,
temperature, and molecular size.
Understand the behavior of binary
and multicomponent mixtures.
4/4/2014 17
Learning Objectives
After completing this section you
will be able to:
Construct single (pure) component
phase diagrams (PT), (PV)
Construct temperature
composition diagrams for a fixed
pressure or pressure composition
diagrams for a fixed temperature.
Construct ternary phase diagrams
(fixed P & T)
4/4/2014 18
The Need to Understand
Phase Behavior

As oil and gas are produced from the
reservoir, they are subjected to a
series of pressure, temperature, and
compositional changes.
Such changes affect the volumetric
and transport behavior of these
reservoir fluids and, consequently,
the produced oil and gas volumes.
4/4/2014 19
The Need to Understand
Phase Behavior
Type of reservoir fluid determines
depletion and production strategies
and the design of surface facilities
Except polymer flooding, all of EOR
methods rely on the phase behavior of
reservoir fluids and fluids injected
into the reservoir.
This behavior is used to classify the
recovery method (i.e., thermal,
miscible, chemical, etc.), and to
design the recovery process.

4/4/2014 20
Major Definitions
System: A body of matter with
finite boundaries (physical or
virtual)
Closed System: Does not exchange
matter with surroundings but may
exchange energy (heat).
Open System: Does exchange
matter and energy with
surroundings.

4/4/2014 21
Major Definitions
Homogeneous System: Intensive
properties change continuously and
uniformly (smoothly)

Heterogeneous System: System
made up of two or more phases in
which the intensive properties
change abruptly at phase-contact
surfaces
4/4/2014 22
Major Definitions
Phase: A portion of the
system which has
homogeneous intensive
properties and it is bounded by
a physical surface.
Interface: Separates two or
more phases. These phases are
solid, liquid(s), and gas.
4/4/2014 23
Major Definitions
Intensive Properties:
Independent of system
mass (i.e density)
Extensive Properties:
Dependent of system mass
(i.e volume)


4/4/2014 24
Major Definitions
Properties: Characteristics of a system
(phase) that may be evaluated
quantitatively, i.e.
Phase density (liquid, gas, solid)
Phase compositions
Isothermal compressibility
Surface tension
Viscosity
Heat capacity
Thermal conductivity
4/4/2014 25
Major Definitions
Component: A molecular
species, defined or hypothetical.

Defined: C
l
, C
2
, H
2
O, etc.

Hypothetical: lumped defined (i.e.
C
2
-C
6
), or undefined C
7
+
, C
20
+
4/4/2014 26
Major Definitions
State: Condition of a system
at a particular time determined
when all intensive properties
are fixed
4/4/2014 27
Phase Diagrams
The most common types of
phase diagrams are

Single: (PT), (PV), (TV)
Binary: (PT)
zi
, (PV)
zi
, (P,x,y)
T
,
(T,x,y)
P


4/4/2014 28
Single Component Phase
Diagram (PT)
P
r
e
s
s
u
r
e


P
c
Temperature
T
c
Liquid
(1 phase)
Vapor (1 phase)
Solid
(1 phase)
Sublimation Curve (2 phases)
Triple Point
(3 phases)
Vapor Pressure
Curve (2 phases)
Critical
Point
Fusion Curve
2 phases
4/4/2014 29
Vapor Pressure Curve
P
r
e
s
s
u
r
e

Temperature
Vapor
Liquid
Critical Point

l

v
P
c
T
c
4/4/2014 30
Pressure vs Specific
Volume Pure Component
T
c
2-phase
T
Specific Volume (ft
3
/ lbm)
P
r
e
s
s
u
r
e

(

p
s
i
a

)

V
v
V
L
CP
4/4/2014 31
Tabulated critical properties
(notes)
Pure Component
Properties

4/4/2014 32
Hydrocarbon Families
Physical Properties
4/4/2014 33
Heat Effects
Accompanying Phase
Changes of Pure
Substances

Clapeyron & Clausius
Clapeyron Equations
4/4/2014 34
Heat Effects from Phase
Changes of Pure
Substances


AH
vap
= TAV
dP
sat
dT

( )
l
M
g
M
V V V = A
4/4/2014 35
Heat Effects from Phase
Changes of Pure
Substances


AH
vap
= TAV
dP
sat
dT

dP
sat
dT
=
AH
vap
RT
2
P
sat
Approximate relation (Clausius - Clapeyron Equation)
4/4/2014 36
COX - Vapor Pressure
Charts
(normal paraffins)

P
r
e
s
s
u
r
e

Temperature
heavier
Non-linear scale
Log scale
4/4/2014 37
Two Component Systems
Phase Diagrams
4/4/2014 38
Pressure Composition
Diagrams - Binary
Systems

Temperature
x
1
, y
1


P
r
e
s
s
u
r
e

P
2
v
T
a
CP
1
2-phases
Liquid
Vapor
P
1
v
P
1
v
CP
2
P
2
v
T
a
0
1
4/4/2014 39
Hydrocarbon Composition
The hydrocarbon composition
may be expressed on a weight
basis or on a molar basis.
i
i
i
Mw
M
n
4/4/2014 40
Hydrocarbon Composition
By convention liquid compositions
(mole fractions) are indicated with
an x and gas compositions with a y.







liquid
n n
n
x
|
|
.
|

\
|
+
=
2 1
1
1
gas
n n
n
y
|
|
.
|

\
|
+
=
2 1
1
1
4/4/2014 41


with


In general
Mathematical
Relationships
v l
f y f x z
1 1 1
+ =
v v
f y f x z
1 1 1
1 + = ) (
( ) ( )
l v
v
v
n n n n
n n
f
2 1 2 1
2 1
+ + +
+
=
) (
1 1
1
1
x y
x z
f
v

=
i i
i i
v
x y
x z
f

=
4/4/2014 42
Temperature vs.
Composition Diagrams
Binary Systems

Temperature
P
r
e
s
s
u
r
e

2-phases
x
1
, y
1
P
a
P
a
CP
1
CP
2
T
1
s
T
2
s
T
2
s
T
1
s
0
1
4/4/2014 43
3-D Phase
Diagram
(P,x)
T

(T,x)
P

4/4/2014 44
Quantitative Phase
Equilibrium Exercise
P-xy Diagram
0
400
800
1200
1600
2000
0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8
Composition (%C1)
P
r
e
s
s
u
r
e

(
p
s
i
a
)
T=160F
4/4/2014 45
Phase Equilibria Methane/n-Decane
0
1000
2000
3000
4000
5000
6000
0.00 0.20 0.40 0.60 0.80 1.00
x
1
, y
1
, z
1
, (1 = Methane)
P
r
e
s
s
u
r
e

(
p
s
i
a
)
BP (200)
DP (200)
Gas cap
composition
Black Oil Composition
Typical Black-Oil System
4/4/2014 46
Supercritical Conditions
Binary Mixture
T
a
T
b
T
g
Temperature
x
1
, y
1
T
a
T
b
T
g
[1]
[2]
P
1
P
2
v

4/4/2014 47
Depletion Path
Isothermal Reservoir Depletion Process for a
Reservoir Oil with 2 Components
Temperature
P
r
e
s
s
u
r
e

P
D
P
B
T = T
a
T
a
CP
M
z
1
= fix ed
z
1
y
1 x
1
1
0
A
B
C
z
1
=overall mole fraction of [1], y
1
=vapor mole fraction of [1], x
1
=liquid mole fraction of [1]
4/4/2014 48
Pressure-Temperature
Diagram for
Multicomponent Systems
R
e
s
e
r
v
o
i
r

P
r
e
s
s
u
r
e

Reservoir Temperature
60%
20%
0%
2-Phase
1-Phase 1-Phase
CP
4/4/2014 49
Quantitative Phase
Equilibrium Exercise
P-xy Diagram
0
400
800
1200
1600
2000
0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8
Composition (%C1)
P
r
e
s
s
u
r
e

(
p
s
i
a
)T=160F
4/4/2014 50
Quantitative Phase
Equilibrium Exercise
P-xy Diagram
0
400
800
1200
1600
2000
2400
0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0
Composition (%C1)
P
r
e
s
s
u
r
e

(
p
s
i
a
)
T=100F
T=160F
T=220F
4/4/2014 51
Changes During
Production and Injection
Temperature
t
1
P
r
e
s
s
u
r
e

t
3
t
2
Gas
Injection
Production
t
t
3
2
Gas
Injection
Production
4/4/2014 52
Ternary Diagrams: Review
.9
.8
.7
.6
.5
.4
.3
.2
.1
.1
.2
.3
.4
.5
.6
.7
.8
.9
1
.1 .2 .3 .4 .5 .6 .7 .8 .9
0
0
1
L
H
I
4/4/2014 53
Ternary Diagrams: Review
Pressure Effect
C
3

C
3

nC
5
C
3

C
1

Gas
p=14.7 psia
C
1

nC
5

2-phase
Liquid
p=380 psia
C
3
nC
5

C
1

C
3

2-phase
Liquid
p=500 psia
C
1

2-phase
Liquid
nC
5

p=1500 psia
2-phase
Liquid
C
1

nC
5

p=2000 psia
C
1

nC
5
C
3

Liquid
p=2350 psia
4/4/2014 54
Dilution Lines
Ternary Diagrams: Review
.9
.8
.7
.6
.5
.4
.3
.2
.1
.1
.2
.3
.4
.5
.6
.7
.8
.9
1
.1 .2 .3 .4 .5 .6 .7 .8 .9 0
0
1
C
1
C
10
n-C
4
x
4/4/2014 55
Ternary Diagrams: Review
Quantitative Representation of
Phase Equilibria - Tie (or
equilibrium) lines

Tie lines join equilibrium conditions
of the gas and liquid at a given
pressure and temperature.
- Dew point curve gives the gas
composition.
- Bubble point curve gives the liquid
composition.

4/4/2014 56
Ternary Diagrams: Review
Quantitative Representation of Phase
Equilibria - Tie (or equilibrium) lines

All mixtures whose overall composition
(z
i
) is along a tie line have the SAME
equilibrium gas (y
i
) and liquid
composition (x
i
), but the relative
amounts on a molar basis of gas and
liquid (f
v
and f
l
) change linearly (0
vapor at B.P., 1 liquid at B.P.).
4/4/2014 57
Illustration of Phase
Envelope and Tie Lines
.9
.8
.7
.6
.5
.4
.3
.2
.1
.1
.2
.3
.4
.5
.6
.7
.8
.9
1
.1 .2 .3 .4 .5 .6 .7 .8 .9 0
0
1
C
1
C
10
n-C
4
CP
4/4/2014 58
Uses of Ternary Diagrams
Representation of Multi-
Component Phase Behavior with a
Pseudoternary Diagram
Ternary diagrams may approximate
phase behavior of multi-component
mixtures by grouping them into 3
pseudocomponents

heavy (C
7
+
)
intermediate (C
2
-C
6
)
light (C
1
, CO
2 ,
N
2
- C
1,
CO
2
-C
2
, ...)
4/4/2014 59
Compositional
Distribution of
Reservoir Fluids
4/4/2014 60
Uses of Ternary Diagrams

Phase behavior of
solvent/reservoir fluid mixtures
Pre-design of miscible processes

4/4/2014 61
Uses of Ternary Diagrams
First Contact Miscible Recovery
Processes (FCM)
.9
.8
.7
.6
.5
.4
.3
.2
.1
.1
.2
.3
.4
.5
.6
.7
.8
.9
1
.1 .2 .3 .4 .5 .6 .7 .8 .9 0
0
1
C
1
C
2
-C
6
C
7
+
A
O
solvent mixes
completely with
the reservoir oil
in all
proportions,
such
4/4/2014 62
Exercise
Find overall composition of mixture
made with 300 moles oil "O" + 50
moles of mixture "A".
__________________________
________________________
_______________________
_____________________
___________________
_________________
.9
.8
.7
.6
.5
.4
.3
.2
.1
.1
.2
.3
.4
.5
.6
.7
.8
.9
1
.1 .2 .3 .4 .5 .6 .7 .8 .9 0
0
1
C
1
C
2
-C
6
C
7
+
A
O
4/4/2014 63
Practice Ternary
Diagrams
Pressure Effect
T=180F
P=14.7 psia
Pressure Effect
O
T=180F
P=200 psia
C1-C3-C10
Pressure Effect
O
T=180F
P=400 psia
Pressure Effect
O
T=180F
P=600 psia
Pressure Effect
O
4/4/2014 64
Practice Ternary Diagrams
Pressure Effect
T=180F
P=1000 psia
Pressure Effect
O
T=180F
P=1500 psia
Pressure Effect
O
T=180F
P=2000 psia
O
T=180F
P=3000 psia
O
T=180F
P=4000 psia
O
4/4/2014 65
Practice Ternary Diagrams
Temperature Effect
T=100F
P=2000 psia
Temperature Effect
O
T=150F
P=2000 psia
Temperature Effect
O
T=200F
P=2000 psia
Temperature Effect
O
T=300F
P=2000 psia
Temperature Effect
O
4/4/2014 66
Practice Ternary Diagrams
Temperature Effect
T=350F
P=2000 psia
Temperature Effect
O
T=400F
P=2000 psia
Temperature Effect
O
T=450F
P=2000 psia
Temperature Effect
O