06 07 08 Chemical EOR

CHEMICAL EOR
Department of Chemical Engineering UPN “Veteran” Yogyakarta

I GUSTI S. BUDIAMAN
Pembahasan Materi Kuliah
• Definisi EOR, konsep dasar fluida dan batuan reservoir
• Jenis dan sifat minyak bumi, kelakuan fasa minyak dan gas
bumi
• Eksplorasi minyak bumi dan eksploitasi minyak bumi
• Mekanisme dan klasifikasi recovery minyak bumi
• Implementasi water flooding, pressure maintenance,
pattern/ pola injeksi/ produksi, Neraca massa air dan
minyak
• Chemical flooding (alkalin, surfaktan, dan polimer)
• Gas/ solvent flooding (HC, CO2, N2, dan flue gas)
• Thermal flooding (steam, udara, dan insitu combustion)
• Microbial injection & others

Chemical EOR
1. Alkalin: dimaksudkan untuk bereaksi dengan asam-asam yang
ada dalam minyak membentuk surfaktan dan merubah
wetabilitas batuan menjadi water wet. Alkalin yang banyak
digunakan al. NaOH dan NaHCO3
2. Polimer: dimaksudkan untuk meningkatkan viskositas air
sehinggan rasio mobilitas air-minyak turun/ kecil dan juga
meningkatkan sweept efficiency. Polimer yang banyak
digunakan al. jenis HPAM, keypam, santan gum, dll
3. Surfactant/ micellar polymer: dimaksudkan untuk menurunkan
tegangan antar muka minyak-air dan bila memungkinkan
reservoir menjadi water wet, sehingga akan terjadi peningkatan
jumlah kapiler yang mampu mengalirkan fluida. Jenis surfaktan
al. anionic, kationik, non ionic, dan ampoterik (zwitzerlan)
Page 4
Page 5
Page 6
Polymer flooding
 Polymer flooding is used under certain reservoir

conditions that lower the efficiency of a regular
waterflood, such as fractures or high-permeability
regions that channel or redirect the flow of injected
water, or heavy oil that is resistant to flow.
 Adding a water-soluble polymer to the waterflood
allows the water to move through more of the
reservoir rock, resulting in a larger percentage of oil
recovery.
 Polymer gel is also used to shut off high-permeability
zones.
Page 7
Chemical Recovery
Page 8
Micellar-polymer or surfactant flooding
 Micellar-polymer flooding uses the injection of a

micellar slug containing a mixture of a surfactant,
cosurfactant, alcohol, and brine that moves
through the oil-bearing formation, releasing much
of the oil trapped in the rock.
 This method is one of the most efficient EOR
methods, but is also one of the most costly to
implement.
Page 9
MICELLAR-POLYMER FLOODING
Page 10
Alkaline flooding
 Alkaline flooding requires the injection of alkaline

chemicals (lye or caustic solutions) into a reservoir that
react with petroleum acids to form surfactants that help
release the oil from the rock by reducing interfacial
tension, changing the rock surface wettability, or
spontaneous emulsification. The oil can then be more
easily moved through the reservoir to production wells.
 A new modification to the process is the addition of
surfactant and polymer to the alkali, giving rise to an
alkaline-surfactant-polymer (ASP) EOR method,
essentially a less costly form of micellar-polymer flooding.
Page 11
Alkaline flooding
Page 12
Perbandingan Kinerja Tiga Proses Chemical
EOR (Taber dan Martin, 1983)
Process Recovery Mechanism Issues Typical Typical agent
recovery utilization*
(%OOIP)
Polymer Improves volumetric Injectivity, stability, and 5 0.3-0.5 lb polymer

sweep by mobility high salinity per bbl oil
reduction produced
Micellar Same as polymer plus Same as polymer plus 15 15-25 lb surfactant

polymer reduces capillary forces chemical availability, per bbl oil
retention, and high salinity produced
Alkaline Same as micellar polymer Same as micellar polymer 5 35-45 lb chemical

polymer plus oil solubilization and plus oil composition per bbl oil
wettability alteration produced
Page 13
Important Factors
in Chemical Floods
 Viscosity of polymer solutions
 Phase behavior of surfactant-oil-water

systems
 Acid number of crude oil
 Optimal salinity
 Capillary desaturation curves
 Retention of chemicals
Chemical Floods
• Increase volumetric sweep efficiency due to reduction of
mobility ratio
• Increase displacement efficiency due to reduction of
residual oil saturation
• Increase imbibition efficiency due to alteration of reservoir
rock wettability
Injector Producer
ASP
Mobility Mobility or Original
Chase Water Pre-flush
Taper Buffer TFSA Reservoir
Chemical Flooding
Page 16
Types of Polymers
Polymers are substances with very large
molecules that result in high solution viscosity
Parameter Bio-polymers Synthetic polymers

Such as Xanthan Polyacrylamides
Made by Fermentation Hydrolysis
Charge Neutral Negatively charged
Effect of salinity Less sensitive More sensitive
Viscosity High Medium
Price Expensive Less expensive
Effect of bacteria Attacked Not attacked
Effect of shear Thinning Thickening
Viscosity of Polymer Solutions
100
1% NaCl Bio-polymer
90
80 Temp. = 25 C
Solution Viscosity, cp
70 Shear rate = 5 s-1
60
50
40
HPAM
30
20
10
0
0 500 1000 1500 2000
Polymer Concentration, ppm
Solution viscosity depends on:

• Polymer type and Concentration
• Salinity
• Shear rate
• Visco-elastic effects
• Inaccessible pore volume (IPV)
Flory-Huggins equation for Newtonian Behavior
At fixed salinity and temperature and low shear rates:
0 = w (1 + a1Cpl + a2Cpl2 + a3Cpl3)
Intrinsic viscosity a1 = Kp (Mwp)n
Where: Kp = characteristic polymer constant
n = exponent with value in the range 0.5 – 1.5
Non-Newtonian Behavior at high shear rates
1 3 p  u
app = Kpl eq(p-1)  eq   
 2 p  2k wS w
u = superficial velocity kw = effective water permeability
 = porosity Sw = water saturation
p = empirical exponent between 0 and 1 (= 1 for Newtonian fluids)
Kpl = empirical coefficient with approximate value equal to 0
At low shear rates: viscosity = 0 (independent of shear rate)

At high shear rates: viscosity =  (independent of shear rate)
  0 
 app    
1 ( eq /  eq )
* ( M 1)
Where:
eq* = shear rate at which app = (0 + ) / 2
M = empirical constant
Example
Given data:
Superficial velocity = 1.2x10-6 m/s Absolute permeability = 236 md
Water saturation = 64% Porosity = 23%
Water relative permeability = 0.26 Empirical exponent p = 0.75
Empirical constant M = 2.2 Empirical coefficient Kpl = 0 = 36 cp
Constant viscosity above critical shear rate  = 4 cp
Shear rate (eq*) at which [app = (0 + ) / 2] = 15 s-1
 1  3x0.75  1.2 x106

Equivalent shear rate  eq    = 19.3 s-1
 2 x0.75  2 x0.26 x236 x1015 x0.23x0.64
36  4
app = 36x(19.3)(0.75 - 1) = 17.2 cp or  app  4  ( 2.2 1)
= 17.6 cp
1 (19.3 / 15)
1000 1000
1000 ppm Bio-polymer Concentration, ppm Bio-polymer
Salinity, ppm
1000 ppm HPAM 2000 HPAM
Salinity = 10000 ppm
1000
Apparent Viscosity, cp
Apparent Viscosity, cp
2000
100 10000 100
1000
30000
1000
500
1000
10 10
10000 500
30000
1 1
0.01 0.1 1 10 100 0.01 0.1 1 10 100
Shear Rate, 1/s Shear Rate, 1/s
Inaccessible Pore Volume (IPV)
Polymer Molecules
Solid
Grains
Thin Layer
without Polymer
Molecules
Solid Pore sizes smaller
Grains than Polymer
Molecules Excluded Volume
Inaccessible
Pores
Inaccessible Pore Volume (IPV)
IPV = Inaccessible pores + Excluded volume

IPV depends on molecular weight, porosity,
permeability and pore size distribution
Polymer molecules show higher velocity
compared to water
Typical IPV values are 10-30% of pore
volume
Permeability Reduction and Visco-Elastic Effects
In capillary flow or laboratory viscometers, all polymers exhibit shear
thinning, non-Newtonian behavior
In porous media at very high shear rates, bio-polymers maintain this
behavior while HPAM shows behaves different than laboratory
viscometers
Viscosity of bio-polymers decrease with shear rate till  but retain
original viscosity if shear rate is decreased back to low values
This behavior (shear thinning) is related to high molecule elasticity
short relaxation time (period required for molecules to retain original
shape after distortion)
Bio-polymers exhibit low apparent viscosity near injection wells and,
consequently; improved injectivity
HPAM polymers exhibit long relaxation time and some permanent
distortion if subjected to very high shear rate and their apparent
viscosity may increase (shear thickening)
Some permeability reduction results from injecting HPAM polymers into
reservoir rocks
Screen Factor (SF)A sample of polymer solution is sucked

into the pipette (through the wire
screens) till its level exceeds upper
timing mark
Solution is allowed to flow freely to
drain downward through wire screens
Timing Marks
Time required for solution level to move
from upper to lower timing marks is
recorded (tdp)
Process is repeated using water (without
5 Wire Screens polymer) at same conditions and time is
(100 Mesh) recorded (tdw)
Screen factor is: SF = tdp / tdw
Higher values of SF indicate longer relaxation times and expected

significant reduction in reservoir permeability
Resistance Factor (RF)

Provides a measure of water injectivity / polymer injectivity
RF = (kwp) / (kpw)
Measure either:
Flow rates (qw and qp) under constant pressure drop conditions: RF = qw / qp
Pressure drops (Pw and Pp) under constant flow rate conditions:
RF = Pp / Pw
Permeability reduction factor

Rk = (kw / kp) = (w / p) RF
Residual Resistance Factor (RRF)

Provides a measure of water injectivity before polymer / water
injectivity after
Indicator of permanent permeability reduction due to polymer
RRF = kw / kwafter
Estimating RF and RRF from SF
25
Resistance Factor y = 0.4971x + 3.114
Residual Resistance Factor- Calculated
20 Residual Resistance Factor - Measured
Resistance Factors
15
10
y = 0.2281x + 2.4053
5
0
0 5 10 15 20 25 30 35 40
Screen factor
Example
Given data:
Original rock permeability = 276 md
Water viscosity = 0.6 cp
Polymer solution viscosity = 19 cp
Screen factor = 23
Water relative permeability before polymer injection = 0.35
Water relative permeability after polymer injection = 0.28
From correlation: Resistance factor RF = 0.4971x23 + 3.114 = 14.55

Hence; Permeability reduction factor = (0.6 / 19)x14.55 = 0.46
From correlation: Residual resistance factor RRF = 0.2281x23 + 2.4053 = 7.65

Hence; Effective permeability to water after polymer injection is:
kwafter = (0.35x276) / 7.65 = 12.62 md
Rock permeability after polymer injection kafter = 12.62 / 0.28 = 45 md
Polymer Retention
Permanent Permeability Reduction Due to Retention of

HPAM Polymer
100
90 Polymer Injection Water Injection

80
Permeability, % of Initial
70
60
50
40
30
20
10
0
0.01 0.1 1 10 100
Pore Volumes Injected
Polymer Retention
Polymer adsorption is the main form of retention
Can be measured in laboratory using representative core and
fluid samples
Usually expressed as:
Mass of polymer per unit mass of rock solid
Mass of polymer per unit surface area of rock solid
Mass of polymer per unit bulk volume
Mass of polymer per unit pore volume
Volume of polymer solution per unit of pore volume
Langmuir Isotherm (adsorption):

p = ap Cpl / (1 + bp Cpl) in g/kg rock solid
Polymer Frontal Advance Loss Dpl = p r (1 - ) / ( Cpl) in FPV

Polymer Degradation
Temperatures in the range 120-130C, could cause most polymer
solutions to crack and lose their viscosity
Temperature level influences other degradation mechanisms
Hydrolysis, specially at high temperature, can reduce viscosity of all

polymers
Low pH environment increases the effect of hydrolysis
Presence of oxygen, even in very low concentrations; can prompt
chemical reactions that lead to polymer loss
Some types of bacteria in the system can attack and break polymer
molecules (especially bio-polymers)
High shear rates (in surface pipes, valves, well perforations and near
injection wellbore) can break polymer molecules into smaller segments
Polymer pre-shearing tends to strengthen it against this effect
HPAM polymers are also influenced by elongational stress when they are
stretched during flow through small pore spaces
Selecting the Right Polymer
Good viscosity characteristics

High water solubility and easy mixing
Low retention in reservoir rock
Shear, temperature, chemical and biological stability
Ability to flow in the reservoir rock
Reasonable injectivity
Acceptable resistance and residual resistance

Relatively low values are desirable for mobility control
High values are desirable for plugging and profile control
Estimating Polymer Concentration
Polymer concentration depends on type and required viscosity

Viscosity is estimated from mobility ratio and shear rate
[(k rp /  p )  (k rw /  w )]behind
M PF

[(k ro / o )  (k rw /  w )]min imum
Required Polymer Slug Size
Required polymer slug size is calculated based on:
Supplying enough polymer to satisfy retention
Acceleration factor for polymer flow (inaccessible pore volume)
Maintain slug stability under viscous fingering from chase water
(retardation factor against the flood front)
V ps  Dpl IPV VF (1 Sor )(1 H K1 [0.78  0.22( p /  w ) 0.25 ]4 )
0.2
log( H K )  VDP (1VDP )
VF = adjustment factor for applicability of viscous fingering effects
For preliminary calculations: VF = 0.5 – 0.75
If experimental data is available, it could be used to provide an
estimate of VF
Required Polymer Slug Size
Example
Given data:
Porosity = 23% Inaccessible pore volume = 15% of porosity
Residual oil saturation = 28% Rock solid density = 2650 kg/m3
Polymer concentration = 700 g/m3 Polymer adsorption = 0.031 g/kg rock solid
VDP = 0.65 Polymer viscosity = 9 cp
Reservoir water viscosity = 0.5 cp Adjustment factor VF = 0.6
0.031x 2650 x(1 0.23)

Frontal advance loss D pl  = 0.393
0.23x700
log(Hk) = 0.65/(1 – 0.65)0.2 which yields: HK = 6.34
Kval = 6.34x[0.78 + 0.22x(9/0.5)0.25]4 = 14.66
Additional slug volume due to viscous fingering = 0.6x(1–0.28)x[1–(1/14.66)] = 0.403

Hence;Required slug size Vps = 0.393 – 0.15 + 0.403 = 0.646 of floodable pore volume
Required Polymer Mass
Polymer mass = 10-3Vb n  Ev Vps Cpl in kg

Where Ev = estimated volumetric sweep efficiency
Example
Given data:
Flood area = 2.1 km2 Gross reservoir thickness = 24 m
Net-to-gross ratio = 0.87 Porosity = 23%
Volumetric sweep efficiency = 82% Polymer slug size = 0.72 floodable PV
Polymer concentration = 700 g/m3
Bulk volume = 2.1x106x24 = 5.04x107 m3

Polymer mass = 10-3x5.04x107x0.87x0.23x0.82x0.72x700 = 4.17 MMkg
Surfactant Characteristics
Surface active agents that act on fluid interfaces and
reduce interfacial tension and reduce capillary forces
A typical surfactant monomer consists of a non-polar

part (lypophile) and a polar part (hydrophile) and may or
may not exhibit a charge:
Anionic exhibit a (-)ive charge and yield anions when

dissolved in water
Cationic exhibit (+)ive charge and yield cations when

dissolved in water
Non-ionic neutral and do not ionize in water but

provide characteristics similar to surfactants
All surfactant molecules are neutral before ionizing in water
- +
[Sodium cation] [Inorganic anion]
Anionic Surfactant Cationic Surfactant Non-ionic Surfactant

Tail represents non-polar part and head represents the
polar part
Anionic, synthetic petroleum sulfonates made by sulfonating
intermediate molecular weight petroleum products or crude oil are
most commonly used for EOR due to their resistance to adsorption,
stability and relatively-low cost compared to other types
Individual Micelles
Monomers
Surfactant Concentration  CMC Surfactant Concentration > CMC
At concentrations above critical value, anions form micelles

Surfactant floods are also called micellar floods
Surfactant-Oil-Water Phase Behavior
Cation content of the water, specially di-valents such as calcium and
magnesium; play an important role in the mechanism by which the surfactant
reduces interfacial tension
Oil
Excess Oil
Water
Water
Surfactant
Surfactant
Single
Single Phase
Phase
Oil-continuous
Plait Micro-emulsion
Water-continuous Plait Point
Micro-emulsion Point Excess Oil Excess Water Two Phase
Two Phase
Water Oil
Water Oil
Overall composition
Overall composition
Low salinity, Winsor type I (lower phase) High salinity, Winsor type II (upper phase)
Oil
Water
Surfactant
Surfactant-rich
micro-emulsion
Single
Phase
Invariant
Plait Point Plait
Point Point Excess Oil
Excess Water
Three Phase
Water Oil
Overall composition
Overall composition
Optimal salinity, Winsor type III (middle phase)

At optimal salinity, a third phase (Winsor type III or middle phase)
develops containing most of the surfactant and in equilibrium with
both oil and water phases
Within this micro-emulsion, both water and oil are unlimitedly
soluble in each other through the action of surfactant micelles
This condition corresponds to minimum height of bi-nodal curve
and the invariant point located on the line of equal water and oil
contents
Water and oil in this micro-emulsion are at their maximum and
surfactant at its minimum with equal solubility in both oil and
water
Cwe Coe
S sol
w  and S sol
o 
Cse Cse
Cwe, Coe and Cse are volume fractions of water, oil and surfactants in micro-
emulsion
1.E-01
Sw sol = Cwe / Cse
So sol = Coe / Cse
Interfacial Tension, mN/m 1.E-02
1.E-03
1.E-04
1.E-05
0 5 10 15
Solubilization Parameters
As solubilization parameters increase, interfacial tension decrease

Optimal Salinity
1.E-01 22
Salinity Increasing
20
Salinity Decreasing
Interfacial Tension, mN/m
Solubilization Parameters
18
Salinity Increasing
Salinity Decreasing 16
1.E-02
14
12
10
8
1.E-03
6
4
2
1.E-04 0
0 0.4 0.8 1.2 1.6 2 2.4 2.8 3.2 0 0.4 0.8 1.2 1.6 2 2.4 2.8 3.2
Salinity, % NaCl Salinity, % NaCl
At optimal salinity:
Solubilization parameters are equal and maximum
Interfacial tensions are equal and minimum
Optimal Salinity
1.E-01 100
90
Interfacial Tension, mN/m
Displacement Efficiency
80
70
1.E-02 Salinity
Increasing 60
Salinity
50
Decreasing
40
1.E-03
30
20
10
1.E-04 0
0 0.4 0.8 1.2 1.6 2 2.4 2.8 3.2 0 0.4 0.8 1.2 1.6 2 2.4 2.8 3.2
Salinity, % NaCl Salinity, % NaCl
Experiments show that displacement efficiency

is maximum at optimal salinity
Surfactant Retention
Surfactant anions get retained in reservoir rocks due to:
Adsorption on positively-charged surfaces
Reaction with divalent cations
Trapping of oil-continuous micro-emulsions
Use of co-surfactants can reduce surfactant retention
48
10% Co-surfactant
44 6% Co-surfactant
40 2% Co-surfactant
Adsorption, micro g-mole/g clay

Langmuir Isotherm
No Co-surfactant
36
32
as Csl 28
s  24
1 bs Csl 20
16
12
8
4
0
0 0.2 0.4 0.6 0.8 1 1.2 1.4 1.6 1.8 2
Equilibrium Concentration, g-mole/m3
Many studies relate surfactant retention in reservoir rocks to clay content
and water salinity
Laboratory and field tests can provide reliable retention values
0.7 1.1
Field data
1
0.6
Surfactant Retention, mg/g of Rock

Surfactant Retention, mg/g of Rock
0.9 Lab Data

Effect of Phase Trapping
Field Data
0.5 0.8
0.7 Lab data

0.4
0.6
0.5
0.3
0.4
0.2 0.3
0.2
0.1
0.1
0 0
0 0.5 1 1.5 2 2.5 3 3.5 0 4 8 12 16 20 24
Salinity, % NaCl Clay Content, % wt
Laboratory and field tests can provide reliable values of surfactant retention
(a) Static Adsorption Test

A known mass (m) of solid grains (from a crushed core sample) is submersed in a
known volume (Vs) of the surfactant solution (of concentration Csli) at reservoir
temperature
Surfactant concentration is measured after several time periods till it stabilizes at a
constant value (Cslr) .
Static surfactant retention is: ss = (Csli - Cslr) Vs / m
Example
Given data: Mass of solid grains = 25 g
Volume of surfactant solution = 30 cm3
Initial surfactant concentration = 2.4 g/lit
Remaining surfactant concentration = 1.95 g/lit
ss = 1000x(2.4 – 1.95)x(30/1000) / 25 = 0.54 mg/g of rock

(b) Dynamic Adsorption Test
 A clean, dry core sample of known mass (m) and pore volume (Vp) is placed in
the test holder at reservoir temperature and saturated with formation water
 A waterflood is conducted at constant rate till the inlet pressure is stabilized
 A known volume of the surfactant solution Vsi (usually around 0.6Vp), of known
concentration Csli; is injected into the core sample and followed by waterflood.
 The concentration of surfactant in the produced fluid is measured and
recorded every 2 cm3 and the test is concluded when this concentration drops
below 2 mg/lit
 The concentration data is plotted versus injected volume and the resulting
curve (which resembles a Gaussian distribution curve) is used to calculate the
dynamic surfactant retention (sd)
sd = (Vsi Csli – A) / m
Where A is area under the concentration versus injected volume curve
(b) Dynamic Adsorption Test, Example
Given data:
Mass of solid grains = 54.8 g; Pore volume of core sample = 5.84 cm3
Volume of surfactant solution = 0.6 PV; Initial concentration = 5.2 g/lit
PV injected 0.66 0.89 1.17 1.46 1.74 1.99 2.28 2.59 2.91 3.24 3.59 3.89 4.17 4.46
Conc., mg/l 0 5.5 9.8 15.7 25.6 34.5 32.4 26.7 20.1 15.9 10.2 6.7 3.2 1.7
40
36
Surfactant Concentration, mg/lit
32
28
sd = (0.6x5.84x10-3x5.2x103–
358x10-3)
24
20
16
/ 54.8 = 0.326 mg/g of rock
12
Area under curve = 358
8
0
0 4 8 12 16 20 24 28
Injected Volume, ml
Thin Film Spreading Agents
Some surfactants (especially non-ionic and cationic types) can alter rock
wettability towards more water-wet in addition to reducing interfacial tension
These surfactants are called thin film spreading agents (TFSA) since they form
a thin film that spreads over and wets the solid surface
Contact angle () is reduced and could become close to zero (very strong
water-wet)
Wettability alteration provides additional EOR mechanisms especially in oil-wet
or intermediately-wet reservoirs and those that exhibit low permeability and
contain significant amount of oil in tight rock matrix
Displacement Direction Displacement Direction
 
 cos  cos
 
2r 2r
Water Oil Oil Water
Drainage Process Imbibition Process

Improved Imbibition Efficiency
60 60
TFSA concentration, ppm Surfactant Type
2000
Concentration = 1000 ppm
Imbibition Efficiency, % of OIP
Imbibition Efficiency, % of OIP

1000 Cationic
50 50
750
600 Non-ionic
40 40
400
30 30
Anionic
0
20 20
10 10
0 0
0 1 2 3 4 5 6 7 8 9 10 0 1 2 3 4 5 6 7 8 9 10
Time, day Time, day
Improved Relative Permeability Characteristics
1
Water-wet
Oil-wet
Oil
kr
Water
0
0 1
Water Saturation, Sw
Capillary De-saturation Curves
Experimental CDC Curves
N vc  u / [ cos {(k rw
0
/  w )  (k ro0 /  o )}]
Other
N vcforms
 0.565of
q wcapillary
/(h Ap ) number
or 0.N vc q w /(h Ap )
565
u
Laboratory Nvc 
 [(krw / w )  (kro / o )]
0 0
uo uw uw

Nvc  N vc  Nvc 
 kro
0
 krw
0

0.565 q w 0.565 q w
Field N vc  N vc 
h Ap h Ap
Given data:
Example Porosity = 24%

Water viscosity = 0.5 cp
Laboratory injection rate = 1.6 ml/hr
Core sample diameter = 3.6 cm
Field injection rate = 1900 Bbl/day/pattern
Pattern size = 18 acre
Net reservoir thickness = 28 m
Maximum Sor = 32%
Interfacial tension for waterflood = 3.1x10-2 N/m
Interfacial tension for surfactant flood = 4.2x10-5 N/m
110
100
90
N vc  0.565 qw /(h Ap ) or

Sor, % of Maximum
80
70
 0.565 qw /(h Ap )

60
50
40
30
20
10
0
1.E-06 1.E-05 1.E-04 1.E-03 1.E-02 1.E-01 1.E+00
Capillary Number
Selecting Suitable Surfactant
N vc  0.565 q w /(h Ap ) or 0.565 q w /(h Ap )
Possible candidate reservoirs for surfactant flood applications:

Medium to high oil gravity
Reasonably low salinity and hardness of formation water
Temperatures less than 100 C
Relatively high residual oil saturation
Relatively low clay content with low cation exchange capacity
Select several surfactants based on preliminary screening

Conduct preliminary lab tests for further screening
Select 2 – 3 surfactants for detail lab tests
Find the right formulation and additives
Conduct core floods
Make final selection and design field pilot test
Surfactant slug Size
Vss  Dsl  s  r (1   ) / ( Csl )

If estimated slug size is too large due to severe surfactant
retention, consider conducting a pre-flush and/or adding cheaper
co-surfactants to the slug
Example
Given data:
Porosity = 26% Surfactant concentration = 5500 g/m3 (0.55% wt)
Rock solid density = 2650 kg/m3 Surfactant retention = 0.22 g/kg of rock solid
0.22 x2650 x(1 0.26)

Vss = Frontal advance loss Dsl  = 0.3 floodable pore volume
0.26 x5500
Required Surfactant Mass
Surfactant mass = 10-3Vb n  Ev Vss Csl in kg
Example
Given data:
Flood area = 2.1 km2
Gross reservoir thickness = 24 m
Net-to-gross ratio = 0.87
Porosity = 26%
Volumetric sweep efficiency = 74%
Surfactant slug size = 0.3 floodable PV
Surfactant concentration = 5300 g/m3
Bulk volume = 2.1x106x24 = 5.04x107 m3

Surfactant mass = 10-3x5.04x107x0.87x0.26x0.74x0.3x5300 = 13.4 MMkg
Alkaline Floods
Generate in-situ surfactants by reacting with acids in reservoir oil
NaOH = Na+ + (OH)-
Na2CO3 = 2Na+ + (CO3)- -
(CO3)- - + 2H2O = H2CO3 + 2(OH)-
Then (OH)- + HA = H2O + A-
Requires reservoir oil with acid number greater than 0.5
Acid number = grams KOH that neutralize 1 kg oil
35
Acid numbers for
% of Tested Crude Oils
30
160 crude oils
25
20
15
10
0
0.5 1.0 1.5 2.0 2.5 3.0 3.5 4.0 4.5 5.0
Acid Number Range
Page 64
Alkaline Floods
EOR Mechanisms
• Reduction of Interfacial Tension.
• Alteration of Reservoir Rock Wettability
• Generation of Emulsions
• Higher volumetric sweep efficiency due to reduced
mobility ratio that results from high emulsion viscosity
compared to water viscosity
• Solubilization and entrainment of oil globules in the
flowing emulsion
• Improving Properties of ASP Slugs
Alkaline Floods
Optimal salinity and concentration are

determined from laboratory tests
Effect of Polymers on
Fractional Flow Curves
1
Waterflood
Polymer flood
Water Fractional Flow, fw
0.8
0.6
0.4
Swp = IPV - Dpl
0.2
Swp Swi
0
0 0.2 0.4 0.6 0.8 1
Effect of Surfactants on
Fractional Flow Curves
1
Waterflood
Surfactant flood
Water Fractional Flow, fw
0.8
0.6
0.4
Sws = - Dsl
0.2
Swi
0
Sws 0 0.2 0.4 0.6 0.8 1
Estimating Oil recovery Factors
Reservoir simulation is the most accurate and reliable methods for

predicting performance and oil recovery from chemical floods
Simulation studies require significant amounts of data, engineering
time and detailed geologic models
Most simulation input data parameters require detailed laboratory tests
for their evaluation
Simulation should be used for final dsign and prediction
Simple Method
Oil recovery factor Er = Ed Ev EMB as % of OIP at flood start
Ed = 1 – (SorBoi)/(SoiBo)
EMB = 0.71 – 0.6VDP + (0.29 + 0.6VDP)[1 – exp(-0.4Vps / Ev1.2)]
Volumetric sweep efficiency Ev

100
VDP 0
Volumetric Sweep Efficiency, %
0.25
90
0.5
80
0.65
0.75
70
0.8
60
50
40
30
20
10
0
0 0.5 1 1.5 2 2.5 3 3.5 4
Slug Size, Multiples of frontal advance loss
Example
Given data:
Residual oil saturation with surfactant = 5% Initial oil saturation = 69%
Dykstra-Parsons coefficient = 0.6 Porosity = 27%
Surfactant retention = 0.2 g/kg of rock solid Rock solid density = 2650 kg/m3
Surfactant concentration = 6400 g/m3 Surfactant slug = 0.5 FPV
Mobility buffer-taper slug size = 0.8 FPV
Ed = 1 – (0.05 / 0.69) = 92.8%

0.2 x 2650 x(1 0.27)
Frontal advance loss Dsl  = 0.224 FPV
0.27 x6400
Hence; Vss / Dsl = 0.5 / 0.224 = 2.23
From correlation in Figure (VII.30): Ev = 90%
EMB = 0.71 – 0.6x0.6 + (0.29 + 0.6x0.6)[1 – exp(-0.4x0.8 / 0.91.2)] = 54.8%
Hence; Er = 0.928x0.9x0.567 = 45.8%
Page 72

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CHEMICAL EOR

Department of Chemical Engineering UPN “Veteran” Yogyakarta

• Microbial injection & others

 Polymer flooding is used under certain reservoir

 Micellar-polymer flooding uses the injection of a

 Alkaline flooding requires the injection of alkaline

Polymer Improves volumetric Injectivity, stability, and 5 0.3-0.5 lb polymer

Micellar Same as polymer plus Same as polymer plus 15 15-25 lb surfactant

Alkaline Same as micellar polymer Same as micellar polymer 5 35-45 lb chemical

 Viscosity of polymer solutions

 Phase behavior of surfactant-oil-water

 Acid number of crude oil

 Capillary desaturation curves

Parameter Bio-polymers Synthetic polymers

70 Shear rate = 5 s-1

Solution viscosity depends on:

Non-Newtonian Behavior at high shear rates

At low shear rates: viscosity = 0 (independent of shear rate)

 1  3x0.75  1.2 x106

IPV = Inaccessible pores + Excluded volume

Screen Factor (SF)A sample of polymer solution is sucked

Higher values of SF indicate longer relaxation times and expected

Resistance Factor (RF)

Permeability reduction factor

Residual Resistance Factor (RRF)

Estimating RF and RRF from SF

From correlation: Resistance factor RF = 0.4971x23 + 3.114 = 14.55

From correlation: Residual resistance factor RRF = 0.2281x23 + 2.4053 = 7.65

Permanent Permeability Reduction Due to Retention of

90 Polymer Injection Water Injection

Langmuir Isotherm (adsorption):

Polymer Frontal Advance Loss Dpl = p r (1 - ) / ( Cpl) in FPV

Hydrolysis, specially at high temperature, can reduce viscosity of all

Good viscosity characteristics

Acceptable resistance and residual resistance

Polymer concentration depends on type and required viscosity

0.031x 2650 x(1 0.23)

Additional slug volume due to viscous fingering = 0.6x(1–0.28)x[1–(1/14.66)] = 0.403

Polymer mass = 10-3Vb n  Ev Vps Cpl in kg

Bulk volume = 2.1x106x24 = 5.04x107 m3

A typical surfactant monomer consists of a non-polar

Anionic exhibit a (-)ive charge and yield anions when

Cationic exhibit (+)ive charge and yield cations when

Non-ionic neutral and do not ionize in water but

All surfactant molecules are neutral before ionizing in water

Anionic Surfactant Cationic Surfactant Non-ionic Surfactant

Surfactant Concentration  CMC Surfactant Concentration > CMC

At concentrations above critical value, anions form micelles

Optimal salinity, Winsor type III (middle phase)

Interfacial Tension, mN/m 1.E-02

As solubilization parameters increase, interfacial tension decrease

Experiments show that displacement efficiency

Adsorption, micro g-mole/g clay

Surfactant Retention, mg/g of Rock

0.9 Lab Data

0.7 Lab data

(a) Static Adsorption Test

ss = 1000x(2.4 – 1.95)x(30/1000) / 25 = 0.54 mg/g of rock

Displacement Direction Displacement Direction

Drainage Process Imbibition Process

Improved Imbibition Efficiency

Imbibition Efficiency, % of OIP

Experimental CDC Curves