PEGN424

PEGN424
Petroleum Reservoir Engineering II Luis Zerpa, PhD
PEGN 424 – Petroleum Reservoir Engineering II

Spring 2017
Chemical and Miscible

Enhanced Oil Recovery
Dr. Luis Zerpa
Learning Outcomes
1.  Identify physics behind supplementary/enhanced oil recovery methods and fluid
displacement processes, by describing effects of fluid and rock properties and their
interactions on fluid displacement efficiency
2.  Apply mathematical models for the operational design of supplementary oil recovery
methods (waterflooding), to estimate overall displacement efficiency
3.  Describe fundamentals of numerical reservoir simulation technology, by explaining the

physical processes represented in governing equations of fluid flow in porous media and
describing the components of a numerical reservoir simulator
4.  Describe different numerical approaches to solve governing equations of fluid flow in
porous media and identify limitations of these approaches
5.  Apply numerical reservoir simulation to evaluate flow and displacement processes during
supplementary oil recovery operations, and analyze the results obtained from the
numerical simulation
6.  Classify enhanced oil recovery processes
7.  Apply screening methodologies for the selection of enhanced oil recovery methods
8.  Describe modeling techniques for unconventional reservoirs
Colorado School of Mines 1

PEGN424 Petroleum Reservoir Engineering II Luis Zerpa, PhD
ENHANCED OIL RECOVERY

METHODS
Recovery methods
Primary Secondary Enhanced
Solution gas
drive Waterflood
Thermal Miscible Chemical
Gas cap drive Steam Hydrocarbon Polymer

injection gas injection injection
Gas injection
Natural water
drive Cyclic Nitrogen or Polymer/
Steam flue gas Surfactant
Water injection injection injection
Compaction Alternated Gas
drive injection (WAG)
SAGD CO2 Alkali

Gravity injection injection
drainage
In-situ
Combinations combustion ASP
drive injection

During primary/secondary recovery oil is

immiscibly displaced by water and/or gas
•  Efficiency of the immiscible displacement process is

affected by:
–  Relative permeability
–  Wettability of rock
–  Capillary pressure
–  Mobility ratio between displaced and displacing

fluids
Enhanced oil recovery (EOR) methods: are based on

injection of gases or liquid chemicals and/or use of thermal
energy to supplement reservoir natural energy
•  Three classes of EOR methods:
1.  Thermal: different configurations of steam injection

and in-situ combustion
2.  Miscible: injection of hydrocarbon gases, carbon

dioxide (CO2), nitrogen or flue gases
3.  Chemical: injection of aqueous mixtures of

polymer, surfactants and/or alkali

Injected fluids interact with reservoir rock/oil

system enhancing oil recovery
•  EOR methods are •  Key parameters that
based on these affect EOR methods:
physical mechanisms:
–  Oil viscosity
–  Decrease displacing fluid
mobility –  Oil composition
–  Increase oil mobility –  Rock composition
–  Miscibility
–  Beginning of injection
–  Decrease interfacial
tension between oil and –  Formation lithology
water
CHEMICAL EOR

Principles of chemical recovery methods
•  Mobility control of displacing fluid by:

–  Increase viscosity of displacing fluid
•  Decrease residual oil saturation by:

–  Decrease interfacial tension between oil and water
•  Types of chemical recovery methods:

–  Polymer injection
–  Polymer/Surfactant injection
–  Alkali injection
–  Combination of chemicals (ASP)
Capillary forces act against viscous forces

#1 1&
•  Capillary forces generate a ΔpLaplace = 2σ % − (
$ R1 R2 '
pressure drop inside the
trapped oil droplet
–  For a droplet flowing into a

narrow pore throat, this
pressure drop is opposite
to the direction of flow
•  When capillary forces balance

with viscous forces, the oil
droplet stops flowing 8µ Lv
ΔpPoiseuille =
R2
–  Residual oil saturation
10

Capillary forces act against viscous forces

#1 1&
•  Using typical values: ΔpLaplace = 2σ % − ( = −1600 Pa
$ R1 R2 '
–  R1 = 50 µm
–  R2 = 10 µm
–  µ = 1 cP
–  v = 1 m/day
–  σ = 10 dynes/cm
–  L = 100 µm
–  R = 10 µm
•  Capillary forces are several

orders of magnitude greater
than viscous forces
–  Responsible for residual oil 8µ Lv
saturation ΔpPoiseuille = = 0.1 Pa
R2
11
Capillary number is the ratio of viscous forces to

capillary forces
#1 1&
ΔpLaplace = 2σ % − ( = −1600 Pa
µv $ R1 R2 '
Nc =
σ
•  Increasing fluid velocity is limited
by fracture gradient and
pumping capacity
•  Viscosity could be increased by
one order of magnitude, so
injectivity is not severely
reduced
•  Interfacial tension can be 8µ Lv
reduced to the order of 10-3 –
ΔpPoiseuille = = 0.1 Pa
R2
10-4 dynes/cm
12

There is a critical capillary number where the

residual saturation decreases (i.e., more oil is
recovered)
µv
Nc =
σ
Lake et al., (2014) Fundamentals of EOR
13
Polymer injection: add polymers to water

increasing viscosity and reducing mobility
•  Limitations:
Injector Producer
well well
–  Not applicable to high
viscosity oils
–  Not applicable to
reservoirs with high
clay content
(adsorption problem)
–  Low injectivity at
beginning of project
Chase Polymer Oil
water solution bank
14

Polymers are long chain of smaller molecules,

called monomers, with a high molecular weight
Partially hydrolyzed polyacrylamide
Polysaccharides
15
Polymer solutions are non-Newtonian, since its

viscosity is not constant
•  Polymer solutions are consider
pseudoplastic, because its
viscosity decreases with
increase shear rate
•  At high flow rates the viscosity

increases with further increase
in shear rate (viscoelastic
behavior)
16

Polymers can be adsorbed onto solid surfaces or

trapped in pore throats
•  Polymer retention results in:
–  Reduced mobility control

Water
–  Delay in polymer
propagation and displaced
oil bank
Solid
17
Polymer performance can be affected by chemical,

biological or mechanical degradation
•  Chemical degradation consists of thermal oxidation, free radicals

substitution, or hydrolysis
–  Chemical additives can be added to prevent chemical

degradation
•  Mechanical degradation occurs at high shear rates, where large

polymer molecules are broken
–  Reduces molecular weight and viscosity
–  Open-hole completions or gravel packs are used to prevent

mechanical degradation
18

Polymer/Surfactant injection: inject surface

active agents to reduce oil/water interfacial tension
•  Surfactant solution in •  Limitations:

water is injected to
reduced residual oil
saturation –  Chemical degradation by
high reservoir temperatures
•  Followed by a polymer
solution for mobility –  Chemical adsorption
control
–  High chemicals cost

•  Chemical bank is usually
displace by water
injection
19
Surface active agents have affinity for surfaces

and interfaces
•  SURFACTANS, are molecules with two functional parts, a
hydrophilic polar group (soluble in water) and a hydrophobic or
lipophilic non-polar group (soluble in oil)
Surfactants tend to adsorb at interfaces

lipophilic hydrophilic
Sodium Dodecil Sulfate
20

Surfactants are classified according to the

dissociation of the hydrophilic group in water
+ - +
-
Anionic Cationic No-ionic Amphoteric

Alcohols
Organic Alkylphenol
Sulfonates quaternary polyethoxylates
Sulfates ammonium, Alquil-, alquil- Polycarboxylic
Carboxilates imidazoline, aril, acil-amine acids
Phosphates piperidine, y polyglycol,
sulfonium ether polyol
Alkanolamides
21
Molecular aggregates - Self-assembly of surfactant

molecules
22 22

Critical Micelle Concentration (CMC)
OIL
WATER
CRITICAL MICELLE
CONCENTRATION (CMC)
Depends upon surfactant structure

and physicochemical conditions (T, pH, salt)
23
Phase behavior of water/oil/surfactant systems

Winsor (1954) suggested a qualitative relationship Surfactant affinity to oil phase
R=
between the interaction energies at the interface Surfactant affinity to water phase
R<1 R=1 R >1

WINSOR I WINSOR III WINSOR II
Lower microemulsion Intermediate microemulsion Upper microemulsion
TYPE II(-) TYPE III TYPE II(+)
(optimum formulation)
24

Optimum formulation is obtained when the surfactant

affinity is equal to the oil and water phases
•  At the optimum formulation

I III II
–  Interfacial tension is
minimum
–  Viscosity is minimum
–  Emulsion stability is
minimum
–  Residual oil saturation is

minimum
25
Wetting of solid surfaces is determined by the

contact angle
Young’s equation Spreading coefficient
σ SV − σ SL SL/S = σ SV − σ LV − σ SL
cosθ =
σ LV
Spontaneous spreading
occurs when SL/S > 0
σLV σLV
σSL σSV σSL σSV
Solid Solid
Surfactants change wettability!

26

Alkali injection: high pH compounds react with

organic acids in the oil to generate natural
surfactants
•  Promotes wettability •  Limitations:

change of the rock
surface –  Not applicable to high
temperature, or high
•  Chemicals injected: clay content
–  Sodium carbonate –  Not compatible with
(Na2CO3)
carbonate reservoirs
–  Sodium hydroxide (NaOH)
–  Minimum oil acid
number required
27
Chemical reaction during alkali injection
•  Alkali dissociation in water •  Increased pH promotes

increases pH, by increasing extraction of organic acids
hydroxide (OH-) concentration from oil (HAo) to water phase
(HAw)
•  Organic acids react in water
→ Na + + OH −
NaOH !! phase to generate surfactants
(A-)
→ 2Na + + CO32−
Na2CO3 !!
2H 2O + CO32− ""
→ H 2CO3 + 2OH −
28

Screening criteria for chemical recovery methods
Polymer Polymer/
Alkali
injection surfactant
API gravity 14 – 34 14 – 34 13 – 35
Fluid
Oil viscosity (cP) < 150 < 30 < 200
properties
Temperature (ºF) < 200 < 175 < 200
Oil saturation (% PV) > 10 > 30 > Sorw
Lithology Sandstone Sandstone Sandstone
Reservoir
Permeability (md) > 10 > 20 > 20
properties
Porosity (%) 20 – 30 20 – 30 20 – 30
Depth (ft) < 9000 < 8000 < 9000
29
MISCIBLE GAS INJECTION
30

Principles of miscible gas injection
•  Miscibility between oil and

displacing gas
Interface
–  Conditions at which two fluids can mix
at any proportions without interface
•  Increase oil mobility by: Immiscible

–  Decreasing oil viscosity
–  Decreasing interfacial tension
•  Types of miscible methods:

–  Hydrocarbon gas injection
–  Nitrogen or flue gas injection
–  CO2 injection Miscible
Recovery mechanisms of miscible recovery methods
•  Mass transfer occurs as miscibility is developed between

injected solvent and oil
–  Extraction, dissolution, vaporization, solubilization, and

condensation
–  Phase behavior change
•  Viscosity reduction
•  Oil swelling
•  Solution gas drive
32

Single-contact miscibility vs. multiple-contact

miscibility
•  Single-contact miscibility: injected gas is completely miscible with
the oil
–  Large ultimate displacement efficiency
–  There can be no residual phases
•  Multiple-contact miscibility: injected gas is partially miscible with the

oil
–  Total composition in mixing zone changes to develop miscibility
33
Ternary diagrams are the basis for classifying

miscible EOR processes
•  Solvent/oil mixture is represented
by three components
•  A light component on the top Ternary diagram of CO2 and crude oil
apex
•  An intermediate crude fraction on
the right apex (C6-)
•  A heavy crude fraction on the left
apex (C7+)
•  These are consider
pseudocomponents
•  A ternary diagram is specified at a
constant temperature and
pressure
•  Two-phase region along the light-
heavy axis
34

Ternary diagrams are the basis for classifying

miscible EOR processes
•  Inside the two-phase region there
are tie lines
Ternary diagram of CO2 and crude oil
•  Tie lines represent composition of
equilibrium phases
•  At the plait point the properties of

the two phases are
indistinguishable
•  Critical mixture at this P and T
•  Critical tie line: a fictitious tie line

tangent to the binodal curve at the
plait point
35
Single-contact miscibility: a straight line dilution path

between solvent and oil does not intersect two-phase
region
•  The displacement will consist of a

single hydrocarbon phase that will
change composition from crude oil
to undiluted solvent through the
solvent/oil mixing zone
36

Multiple-contact miscibility: vaporizing-gas drive

•  Miscibility is not achieved instantaneously
because dilution path passes through two-
phase region
•  Miscibility is developed after multiple
contacts
•  Mixing oil and solvent results in overall
composition M1
•  Which at equilibrium splits into two
phases: gas G1 and liquid L1
•  Gas G1 has larger mobility than L1, and
moves contacting more oil to form mixture
M2
•  M2 splits into gas G2 and liquid L2
•  Eventually, the process develops miscibility
Miscibility will develop as long as
•  The solvent is enriched with intermediate the injected solvent and oil are on
components that are vaporized from the oil opposite sides of the critical tie line
37
Multiple-contact miscibility: rich-gas drive (condensing

gas drive)
•  Miscibility is not achieved

instantaneously because dilution
path passes through two-phase
region
•  Miscibility is developed after multiple

contacts
•  Mixing oil and solvent results in

overall composition M1, which splits
into gas G1 and liquid L1
•  Gas G1 has larger mobility than L1,

and moves, liquid L1 mixes with
fresh solvent form mixture M2
•  Eventually, the process develops miscibility
•  M2 splits into gas G2 and liquid L2, at rear of solvent/oil mixing zone
and L2 mixes with fresh solvent •  The liquid phase is enriched with
intermediate components that are
condensed from the solvent
38

Summary of classification of miscible

displacements for ternary diagrams
Dilution
Type
path
I1 – J1 Immiscible
I1 – J2 Multiple-contact, rich gas
I2 – J1 Multiple-contact, vaporizing
gas
I2 – J3 Single-contact miscible
Miscibility will develop as long as

the injected solvent and oil are on
opposite sides of the critical tie line
39
Hydrocarbon gas injection: inject light

hydrocarbons to develop miscible conditions
•  Three types of miscibility •  Limitations:
processes:
–  Minimum miscibility pressure
–  Instantaneous miscibility: propane depends on gas and oil
(C3) or liquefied petroleum gas (C2 composition, and reservoir
– C4) temperature
–  Condensing-gas drive: condense –  Rigorous control of injected gas

gas components in the oil phase,
composition
enriched gas injection (C2 – C6)
–  Vaporizing-gas drive: vaporizes –  Unfavorable mobility ratio

light components from oil phase,
high pressure injection (methane or –  High cost of injection gases
natural gas)

Nitrogen or flue gas injection: injects gas at

miscible or quasi-miscible conditions
•  Miscible conditions depends •  Limitations:
on reservoir pressure and oil
composition –  Requires rigorous compositional
analysis
•  Key physical mechanisms:
–  Minimum miscibility pressure
depends on gas and oil
–  Gas absorption into oil phase,
composition, and reservoir
increasing oil volume
temperature
–  Gas enrichment by vaporization

–  Unfavorable mobility ratio
of oil light components
–  Nitrogen injection requires on-

–  Decrease of interfacial tension
site separation facilities
and viscosity
CO2 injection: pure CO2 is injected to increase oil

mobility and displace residual oil
•  Miscibility is attained by •  Limitations:
multiple contact between oil
and injected fluid –  Unfavorable mobility ratio.
Usually CO2 is injected as a
WAG process with water
•  Contact between CO2 and oil
promotes vaporization of –  Density difference promotes gas
medium and high molecular overriding and by passing oil
weight hydrocarbons column
–  CO2 availability
•  At appropriate conditions the
enriched CO2 phase achieve
miscibility with oil

Screening criteria for miscible recovery methods
Nitrogen or
Hydrocarbon CO2
flue gas
gas injection injection
injection
API gravity 21 – 57 > 30 28 – 44
Fluid
Oil viscosity (cP) 0.1 – 1.3 < 0.5 0.4 – 3.0
properties
Temperature (ºF) 136 – 290 > 250 100 – 250
Oil saturation (% PV) 30 – 98 > 50 25 – 90
Carbonate or Carbonate or Carbonate or
Lithology
Reservoir sandstone sandstone sandstone
properties Permeability (md) 10 – 5000 > 30 2 – 500
Porosity (%) 4 – 26 > 10 4 – 26
Depth (ft) 4000 – 14500 > 7000 2000 - 12000

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Petroleum Reservoir Engineering II Luis Zerpa, PhD

PEGN 424 – Petroleum Reservoir Engineering II

Chemical and Miscible

Dr. Luis Zerpa

3. Describe fundamentals of numerical reservoir simulation technology, by explaining the

6. Classify enhanced oil recovery processes

8. Describe modeling techniques for unconventional reservoirs

Colorado School of Mines 1

ENHANCED OIL RECOVERY

Primary Secondary Enhanced

Gas cap drive Steam Hydrocarbon Polymer

SAGD CO2 Alkali

Colorado School of Mines 2

During primary/secondary recovery oil is

• Efficiency of the immiscible displacement process is

– Mobility ratio between displaced and displacing

Enhanced oil recovery (EOR) methods: are based on

• Three classes of EOR methods:

1. Thermal: different configurations of steam injection

2. Miscible: injection of hydrocarbon gases, carbon

3. Chemical: injection of aqueous mixtures of

Colorado School of Mines 3

Injected fluids interact with reservoir rock/oil

Colorado School of Mines 4

Principles of chemical recovery methods

• Mobility control of displacing fluid by:

• Decrease residual oil saturation by:

• Types of chemical recovery methods:

Capillary forces act against viscous forces

– For a droplet flowing into a

• When capillary forces balance

Colorado School of Mines 5

Capillary forces act against viscous forces

• Capillary forces are several

Capillary number is the ratio of viscous forces to

Colorado School of Mines 6

There is a critical capillary number where the

Polymer injection: add polymers to water

Colorado School of Mines 7

Polymers are long chain of smaller molecules,

Polymer solutions are non-Newtonian, since its

• At high flow rates the viscosity

Colorado School of Mines 8

Polymers can be adsorbed onto solid surfaces or

– Reduced mobility control

Polymer performance can be affected by chemical,

• Chemical degradation consists of thermal oxidation, free radicals

– Chemical additives can be added to prevent chemical

• Mechanical degradation occurs at high shear rates, where large

– Reduces molecular weight and viscosity

– Open-hole completions or gravel packs are used to prevent

Colorado School of Mines 9

Polymer/Surfactant injection: inject surface

• Surfactant solution in • Limitations:

– High chemicals cost

Surface active agents have affinity for surfaces

Surfactants tend to adsorb at interfaces

Sodium Dodecil Sulfate

Colorado School of Mines 10

Surfactants are classified according to the

Anionic Cationic No-ionic Amphoteric

Molecular aggregates - Self-assembly of surfactant

Colorado School of Mines 11

3.  Describe fundamentals of numerical reservoir simulation technology, by explaining the

6.  Classify enhanced oil recovery processes

8.  Describe modeling techniques for unconventional reservoirs

•  Efficiency of the immiscible displacement process is

–  Mobility ratio between displaced and displacing

•  Three classes of EOR methods:

1.  Thermal: different configurations of steam injection

2.  Miscible: injection of hydrocarbon gases, carbon

3.  Chemical: injection of aqueous mixtures of

•  Mobility control of displacing fluid by:

•  Decrease residual oil saturation by:

•  Types of chemical recovery methods:

–  For a droplet flowing into a

•  When capillary forces balance

•  Capillary forces are several

•  At high flow rates the viscosity

–  Reduced mobility control

•  Chemical degradation consists of thermal oxidation, free radicals

–  Chemical additives can be added to prevent chemical

•  Mechanical degradation occurs at high shear rates, where large

–  Reduces molecular weight and viscosity

–  Open-hole completions or gravel packs are used to prevent

•  Surfactant solution in •  Limitations:

–  High chemicals cost

•  At the optimum formulation

–  Residual oil saturation is

•  Promotes wettability •  Limitations:

•  Alkali dissociation in water •  Increased pH promotes

•  Miscibility between oil and

•  Increase oil mobility by: Immiscible

•  Types of miscible methods:

•  Mass transfer occurs as miscibility is developed between

–  Extraction, dissolution, vaporization, solubilization, and

–  Phase behavior change

•  Solution gas drive

–  Large ultimate displacement efficiency

–  There can be no residual phases

•  Multiple-contact miscibility: injected gas is partially miscible with the

–  Total composition in mixing zone changes to develop miscibility

•  At the plait point the properties of

•  Critical mixture at this P and T

•  Critical tie line: a fictitious tie line

•  The displacement will consist of a

•  Miscibility is not achieved

•  Miscibility is developed after multiple

•  Mixing oil and solvent results in

•  Gas G1 has larger mobility than L1,

–  Condensing-gas drive: condense –  Rigorous control of injected gas

–  Vaporizing-gas drive: vaporizes –  Unfavorable mobility ratio

–  Gas enrichment by vaporization

–  Nitrogen injection requires on-