EOR: Polymer Flooding

Week 6

Enhanced Oil Recovery – PTRL 4012

 Chemical Flooding
Process Recovery Mechanisms Issues Typical Recovery

Polymer Improves volumetric Injectivity Stability 5%

sweep by mobility High salinity
reduction
Micellar Same as polymer plus Same as polymer 15 %
Polymer reduces the effect of plus chemical
capillary forces (by availability and
adding surfactants) Retention
Alkaline Same as micellar polymer Same as micellar 5%
Polymer plus wettability alteration polymer plus oil
(high pH (by injecting NaOH, Composition
flooding) Na2CO3)
Foam Uses surfactants to Same as micellar Slightly lower than
Flooding stabilise foams and polymer the polymer flood
thereby reduce gas
phase Mobility
 Polymer Flooding
Add polymer to λw k w µ o
Increased M= = ×
the water of a
waterflood
water viscosity λo ko µ w

Increased Lowered
volumetric sweep mobility ratio

WATER +
WATER POLYMER

High-permeability layer High-permeability layer

Polymer Flooding
Polymer Types
• Xanthan gum
• Hydrolysed polyacrylamide (HPAM)
• Copolymers of acrylic acid and acrylamide
• Copolymers of acrylamide and 2-acrylamide 2-methyl propane
sulphonate (AM/AMPS)
• Hydroxy-ethyl-celulose (HEC)
• Carboxy-methyl-hydroxy-ethylcellulose (CMHEC)
• Polyacrylamide (PAM)
• Polyacrylic acid,
• Glucan
• Dextran polyethlene oxide (PEO), and
• Polyvinyl alcohol.
 Polymer Types: Polyacrylamides
Acrylamide

The primary monomeric unit is the acrylamide molecule

Polyacrylamide

Multiple monomeric units are stringed

together to form a large molecular
weight polymer.

Hydrolyzed Polyacrylamide

Some amine groups are hydrolyzed to

form carboxyl groups. The resulting
polymer is anionic because it has a
negative charge.

Molecular weight and the degree of hydrolysis have been selected to optimize
certain properties such as water solubility, viscosity, and retention.
Polymer Types: Polysaccharides

Xanthan Gum

Polymerization of saccharide molecules à biodegradable.

The polysaccharide molecule is relatively nonionic and

therefore free from ionic-shielding effects.
 Polymer Types

Class I - POLYACRYLAMIDES
• Also called partially hydrolysed polyacrylamides (HPAM) due to the fact
that they undergo partial hydrolysis during polymer flooding.
• The degree of hydrolysis (typically ~ 30%) is selected to optimize
certain properties such as water solubility, viscosity and retention.
• Smaller degree >>> less water solubility
• Larger degree >>> the properties too sensitive to salinity. Only obstacle!
• High molecular weight controls the viscosity. Only a small amount is
sufficient to reduce water viscosity substantially.
• HPAM is inexpensive and relatively resistant to bacterial attack and it
exhibits permanent permeability reduction.
• 95% of the field projects have used HPAM.
Polymer Types

Class II - POLYSACCHARIDES
• They are formed from the polymerisation of saccharide molecules,
a bacterial fermentation process.
• High molecular weight controls the viscosity.
• They are sensitive to bacterial attack and the fermentation
produces a debris in the polymer that must be removed before the
polymer injected.
• However, these polymers are insensitive to brine salinity.
• They do not exhibit any permeability reduction.
• They are relatively expensive; but when compared on a unit
amount of mobility reduction, particularly at high salinities, the costs
are close enough so the polymer choice highly depends on the site.
Ionic Shielding Effects Polymer at Low Salinity

Viscosity decreases with

increasing salinity Polymer molecule is made larger in
solution by the ionic repulsion
between polymer molecules
and between segments on the
same molecule.

Polymer at High Salinity

The repulsion is greatly decreased through ionic

shielding, which allows the polymer
molecules to coil up.
Non-Newtonian Effects

Polymer as an non-Newtonian fluid

“A Fluid is non-Newtonian if its viscosity changes with the
rate at which is flows.”

Polymers are large and have shapes that change with the
stresses that are applied to them.

Viscous effects: Due to the entanglement of the polymer

molecules.

Elastic Effects: Due to the stretching of the polymer

molecule.
Polymer Properties
Viscosity Relations

The Flory-Huggins Equation (1953)

µ w' = µ w [1 + α1C + α 2C 2 + α 3C 3 + ...]

Brine Polymer
viscosity Concentration

Constants

Shear rate:
Low: Newtonian fluids
High: non-Newtonian fluids
Example

For a 1,000 g/m3 xanthan gum solution at

a shear rate of 5 s-1 in 1 wt% NaCl brine at
24oC.

The solution viscosity is 10 mPaS (10 cp)!

Compared to brine at the same

conditions, this is a substantial increase
in viscosity, caused by only 0.1 wt% of
polymer.

Note: 1000 g/m3 = 0.1 wt%

 Polymer Properties
Shear-thinning Non-Newtonian Fluids

Lake (1989)
 Polymer Properties
Shear-thinning Non-Newtonian Fluids

For the bulk of a reservoir’s

volume, the shear rate is
usually low (1-5 s-1), making
possible to obtain the desired
mobility ratio with a minimum
amount of polymer. Around the
well, however, the shear rate is
high, causing the injectivity to
be greater than expected based
on the Newtonian viscosity.

Lake (1989)
Shear Rate
Steady flow through a capillary tube Wall Shear in Capillary Tube

R 4v
γ! =
R
v = average _ tube _ velocity
To define an equivalent permeable-media shear
rate we must make the travel time of a fluid element R = tube _ radius
in the capillary tube equal to that in an REV.

Solve for v and incorporate into “capillary

! Lt $ ! L $ !L $
2
tube” shear rate model
#" &% = #" &% τ = # t & = tortuosity
"L%
v v REV
4vτ 1/2
v Interstitial velocity, i.e. Darcy velocity divided by porosity γ!eq =
Lt Capillary tube length
R
L Distance traveled by a fluid element Permeable-Media Shear
Porous Media Shear Rate
Porous Media Flow
Permeable-Media Shear

4vτ 1/2
γ!eq =
Flow
R
R = Capillary Tube Radius
τ = tortuosity
V = interstitial velocity

Simple Permeability Relationship

φ R2 !φ $ 4q
1/2
k= !
γ eq = 4v # & =
8 " 8k % A 8kφ
Shear rate is dependent on the interstitial velocity of fluids and the rock
structure, i.e. permeability and porosity.
Polymer Injection
Assume a five spot pattern where the injector is 600 meters from the producer.
Injector 1/2
!φ $ 4q
γ!eq = 4v # & =
Producer " 8k % A 8kφ
600 m
eters
Central Injector: 5000 bbl/day à 15.9 m2/day
Porosity: 0.25 (assume average)
Permeability: 500 mD (assume average)
100000
Shear Rate (1/sec)

10000
1000
100
10
1
0.1
0.01 0.1 1 10 100 1000
Distance (m)
Polymer Injection
Viscosity of the polymer solution will significantly decrease near the injector.
Injector
Remember!

Producer

600 m
eters

100000
Shear Rate (1/sec)

10000
1000
100
10
1
0.1
0.01 0.1 1 10 100 1000
Distance (m)
Modeling Viscosity
Polymer-solution viscosity and shear rate can be modeled using a power-law model

n pl −1
µ ' = K pl (γ!) K pl Power-law coefficient

n pl Power-law exponent

This data comes from laboratory tests where polymer

solution flows due to a rotating disc.

For shear-thinning fluids, 0 < npl < 1

For Newtonian fluids, npl = 1 and Kpl becomes the viscosity

When applied to permeable-media flow, the same equation

continues to apply, except that the shear rate within the
porous medium increases and the bulk-fluid viscosity
becomes an effective or apparent viscosity.
Standard Viscometer
Example: Laboratory Core Floods

Viscometer Rheology
Vs.
In Situ Rheology

Shear rate in a viscometer is not

comparable to the equivalent
share rate in porous media.

[Humphry et al. 2013]

-Core floods where conducted with emulsion solution (AS) and

emulsion solution with polymer (ASP).
-Apparent viscosity is determined using Darcy’s Law.
-Solution viscosities are also measured using a viscometer.
Example: Laboratory Core Floods

Viscometer Rheology
Vs.
In Situ Rheology

Shear rate in a viscometer is not

comparable to the equivalent
share rate in porous media.

[Humphry et al. 2013]

-Core floods where conducted with emulsion solution (AS) and

emulsion solution with polymer (ASP).
-Apparent viscosity is determined using Darcy’s Law.
-Solution viscosities are also measured using a viscometer.
Example: Laboratory Core Floods
Apparent viscosities, from in situ measurements, are 1.6 to 6 times greater than
those measured in a conventional shear rheometer.

Why is the apparent viscosity so much larger? Wall exclusion, polymer sorption,
size exclusion, elastic effects,
and etc. are a few potential
in situ measurements effects.

! kA $ ΔP
q =# c & Use Darcy’s law and solve for viscosity (µ)
" µ % L
1/2
!φ $
!
γ eq = 4v # & Shear rate is determined from our previous derivation
" 8k %

Viscometer

n pl −1
µ ' = K pl (γ!) This relationship is directly measured
Issues in Polymer Flooding

• Retention due to adsorption onto solid surface or

trapping within small pores. The retention causes the
loss of polymer from solution which lowers the sweep
efficiency. The degree of retention depends on:
• polymer type,
• molecular weight,
• rock composition,
• brine salinity,
• flow rate, and
• temperature.
Issues in Polymer Flooding

• Inaccessible Pore Volume (IPV) is caused by that the smaller

portions of the pore space will not allow polymer molecules to
enter because of their size. This accelerates the polymer
flooding. IPV depends on:
• polymer molecular weight,
• permeability,
• porosity and
• pore size distribution
and becomes more pronounced as MW increases and the
ratio of permeability to porosity decreases. It can be 30% of
the total pore volume.
Issues in Polymer Flooding

• Permeability Reduction occurs when certain type of polymers

(e.g. HPAM) are used. Besides the polymer type, this also
depends on:
• molecular weight,
• degree of hydrolysis,
• shear rate, and
• pore structure.
The permeability reduction can be caused by polymer
adsorption which decreases the effective pore size. Because
it decreases the mobility ratio, it is therefore good for polymer
flooding. However, on the other hand, an extreme reduction
will cause injectivity impairment.
Issues in Polymer Flooding

Chemical and Biological Degradation. There is a critical

temperature (on the order of 400 °K) above which the polymer
will thermally crack. Since the average residence of polymers in
reservoirs is long (~ a few years), even slow reactions may
potentially degrade the polymer quality. At neutral pH, the
degradation is insignificant, whereas, at very low or very high pH
and at high temperatures, it may be important. As a result the
viscosity can drop sharply. Oxidization or free radical chemical
reactions are the most serious degradations. Therefore oxygen
scavengers and antioxidants are often added to polymers.
Biological degradation can occur with both types of polymers.
Variables affecting biological degradation include the type of
bacteria in the brine, pressure, temperature, salinity, and other
chemicals present.
Issues in Polymer Flooding

Mechanical Degradation occurs when polymer solutions

are exposed to high velocity flows, which can be present, in
surface equipment, downhole conditions or the sandface
itself. Perforations are the main cause for concern as large
amount of polymer solution is forced through small entries
to reservoir. For this reason, most polymer injections are
carried out through open-hole or gravel-pack completions.
On a viscosity-shear rate plot, mechanical degradation
usually begins at shear rates equal to or somewhat less
than the minimum viscosity shear rate.
Polymer Retention

Viscosity + polymer size

E.g. Xantham Gum

à Polymer retention in tight rocks! MWxantham = 2 million

Mark-Houwink Equation à dp is approximately 0.4 mm.

a
[ ]
µ = K ' M w
à Same size as the pore throats in
Where K’ and a are polymer specific constants and Mw is medium to low permeability
the polymer molecular weight. sandstone.

Flory Equation
d p = 8[M w [µ ]]1/3
Where dp is in angstroms and [µ] is in dl/g.

These equations are useful in understanding how very large polymer molecules
propagate through small pore openings of rocks.
 Polymer Flooding Design
1 – Screen the candidate reservoirs
EOR Method API Viscosity Composi Oil Sat. Rock Type Net Avg. Perm Depth T (ºF)
Gravity (º) (cp) tion (%) Thic. (ft) (md) (ft)

Micellar/polymer, >20 <35 Light >35 Sandstone Not >10 <9,000 <200
ASP, Alkaline inter. org preferred critical
Flooding acids for
Alkaline

Polymer flooding >15 <150; >10 Not >50 Sandstone Not >10 <9,000 <200
critical preferred critical

The oil saturation in

the target reservoir
Permeability must Temperature must
must be high
be high enough to be below 200 °F to
enough for project’s
prevent from avoid degradation.
economics.
plugging.
 Polymer Flooding Design
2 – Decide on the correct mode
• mobility control,
• profile control, i.e., improve the permeability profile at the wells, or
• a combination of both.

Profile Control: the aim is to inject an agent (gels, polymers, and

solids) that alters the permeability so that more fluid will go into the
low-permeability region than into the high-permeability region. This
minimizes the heterogeneity effects on flooding. This is commonly
applied when selective perforations are ineffective.
 Polymer Flooding Design
3 – Select the polymer type

• Good thickening.
• High water solubility.
• Low retention.
• Shear stability.
• Chemical stability.
• Biological stability.
• Good transport in permeable media.

In practice, no polymer type addresses all criteria. Thus the polymer

must be tailored for the reservoir rock under study.
Polymer Flooding Design
4 – Estimate the amount of polymer required

m p = S slug × V p × C p ,avg

Slug size Average polymer

Pore volume concentration
In PVs

Optimization of the PVs of the incremental oil and injected polymers.

• estimate the polymer concentration in initial portion of the slug (spike)
• estimate the volume of the polymer slug (spike plus rate of taper).
Polymer Flooding Design
Target mobility ratio

(λ )polymer
MT =
(λ )oil
Spike concentration = picking the value of injected polymer
concentration that gives the correct MT in the
equation.

The major parameter controlling the slug size is viscous fingering

between the chase water and the polymer spike.
Fractional Flow: Water Flood + Polymer Flood

Secondary shock front due

to polymer flood, i.e. the
secondary oil bank.

Initial shock front due to

water flood, i.e. the
primary oil bank.

[Green and Willhite 1998]

Fractional Flow Curves
Slope of tangent = speed of the Slope of tangent = speed of the
Primary shock front secondary shock front
1

0.9 Water flood

0.8

0.7
The polymer shock front
0.6 travels much slower than
Fw (rb/rb)

the primary water flood

0.5 shock front.
0.4
Polymer flood
0.3

0.2

0.1

0
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9
Sw
Distance/Time Diagram of Viscous Water flood
The velocity of each saturation front is given by the
slope of these lines

For water flood followed by

polymer flood – two oil banks
develop and there is a
spreading wave behind the
secondary oil bank.

[Green and Willhite 1998]

Comparison Study
The viscous shock arrives
much later for the polymer
flood than water flood.

At infinite time, the recovery

for both floods are the
same. However, the
amount of water produced
for the normal water flood
is much larger.

Better production curve for the

polymer curve, i.e. more
oil produced with less
water.

Comparison of displacement performance for a viscous water flood at

interstitial water saturation with a normal water flood.

[Green and Willhite 1998]

Polymer Flooding Design
5 – Design polymer injection facilities

The cost of injection facilities is usually small compared to

well and chemical costs.
Mixing facilities, filtration, and injection equipment are three
major units.
The mixing apparatus depends on the polymer type.
Filtration largely depends on the success of mixing.
The injection equipment is the same as for waterflooding.
Polymer Flooding Design
6 – Consider the reservoir

Little is required here beyond the usual water flood

considerations such as the optimal well pattern and
spacing, completion strategy, reservoir characterization and
allowable injection rates.

Optimal values of these quantities imply precise values that

result in the maximum rate of return on investment. Since
multiple parameters involved, it is possible to optimize each
parameter. Hence, some parameters are fixed and the
most sensitive parameters are optimized.
 Definitions
Polymer = a high molecular weight molecule that has repeated units.

Hydrolyzed polyacrylamide (HPAM) = one of the most common polymers used or EOR.

Viscosity = measures a fluids resistance to flow.

Shear Rate = the rate of change of velocity at which one layer of fluid passes over an adjacent layer.

Shear-thinning fluid = a fluid where its viscosity decreases with increasing shear rate.

Retention = caused by adsorption of polymer to the reservoir rocks surface.

Degradation = can be mechanical, biological, or chemical. Polymer length is reduced and thus its ability to
increase a fluids viscosity is reduced.

Interstitial water = water that occurs naturally within the pores of rock.
Test Your Knowledge
1. What is the main mechanism for polymer-based EOR?

2. Name the two main polymer classes. What are the advantage and disadvantages of each?

3. As the injected polymer solution moves radially outward from the injection well the pore
velocity of the fluid decreases. What influence would this have on polymer degradation and the
flooding solutions viscosity?

4. Explain the concept of shear thinning by using the concept of entanglement.

5. By using the concept of entanglement, explain why polymer viscosity is highly dependent on
brine salinity.

6. Using fractional flow theory compare the differences between a water flood versus a polymer
flood.

7. What surface facilities need to be considered for polymer-based EOR?

8. Why is apparent viscosity usually much higher than the conventional laboratory measured
viscosity using a viscometer?
Suggested Reading
James J Sheng et al. (2015), Status of Polymer-Flooding Technology, Journal of Canadian
Petroleum Technology, March.

Wang, D. (2013), Enhanced Oil Recovery: Field Case Studies, Chapter 4: Polymer Flooding
Practice in Daqing, ISBN: 978-0-12-386545-8.
References
Larry W. Lake, Russel T. Johns, William R. Rossen, and Gary A. Pope, Fundamentals of
Enhanced Oil Recovery, Society of petroleum Engineers, ISBN: 978-1-61399-328-6.

Sorbie, K. S. (1991), Polymer-Improved Oil Recovery, Boca Raton, Florida: CRC Press, Inc.

Humphry et al. (2013), SPE 1652, SPE Enhanced Oil Recovery Conference, Kuala Lumpur,
Malaysia, 2-4 July.

Don W. Green and G. Paul Willhite (1998) Enhanced Oil Recovery, SPE Text Book Series, Vol.
6, Society of Petroleum Engineers.