Polymer flooding

Master in Petroleum Engineering

Daniel Broseta November 2019 EOR

Principle: to increase the viscosity (i.e., lower the mobility) of the injected water in
order to provide better sweep efficiency (but displacement efficiency is also improved)

This is done by dissolving in an aqueous solution a few hundreds to thousands of

ppm of large-molecular-weight (Mw) water-soluble polymer.

Range of recovery: 5-30% of OOIP

0.7 -1.75 lb of polymer per bbl of additional oil

Main target: unswept zones of the reservoir (not the residual oil saturation in
previously swept zones)
Polymer flooding: outline

What polymers?

Polymer stability at reservoir conditions

Adsorption/retention in the reservoir rock

Rheology

Other issues: preparation, injectivity, etc

A few field cases

 What polymers?

Synthetic polymers: Polyacrylamides with various masses and hydrolysis

degrees The most common EOR polymers:

Molar mass Mw: a few 106 to 107

grams/mole (with large polydispersity)

Anionic: hydrolysis degree (ratio of

acrylamide (M=71 g/mol)
acylate monomers): up to 35%

The effect of acrylate monomers is to

swell the chain & have higher viscosity
flexible chains sensitive to temperature
and prone to hydrolysis
acrylamide acrylate
(M=78 g/mol) Price:$ 1 – 2 /lb
What polymers?

Natural polymers : polysaccharides (xanthan)

Less common EOR polymers

Mw: a few 106 to 107 grams/mole

(large polydispersity)

Anionic

Rigid

Rigid polymers less sensitive to salt content and temperature than HPAM

They tend to be replaced by HPAMs with sulfonate groups (e.g., AMPS=2-acrylamido-2-methyl propane
sulfonic acid) and associative polymers (mostly derived from HPAM) with hydrophobic groups: still an area of
research!
What polymers?

In the following, only flexible polymers (i.e., of the HPAM type) are
considered.

Physical picture of an anionic flexible polymer :

The negative charges make

the polymer expand and
render the solution more
viscous,

But: high salinity screens

electrostatic (repulsive)
interactions and can even lead
to precipitation (in the case of
divalent & trivalent salts)
What polymers?

Effects of salts on the behavior of anionic flexible polymers:

Large viscosity Small viscosity

Low adsorption (on Precipitation when divalents are
negatively-charged minerals) present
Large adsorption
Stability at reservoir conditionsns

HPAMs are subject to various types of degradation:

Chemical degradation

Hydrolysis at high pH and/or high temperature (-> inject HPAM with lower
hydrolysis degree)
Oxydative attack (-> use oxygen scavengers: sulfide, thiosulfate, sodium
dithonite)

Precipitation (loss of solubility), especially at high T and when divalent

ions (Ca++, Mg++, ..) are present
Stability at reservoir conditions

HPAMs are subject to various types of degradation:

Thermal degradation
Hydrolysis at high temperature.
Loss of solubility if divalent ions are present

Bacterial degradation (more of concern for natural polymers) -> use

a bactericide.

Mechanical degradation: where strong elongational flows are

present (in chokes, valves, in the reserv. near the wellbore: see next
subsection)
Adsorption/retention in the reservoir rock

Adsorption: irreversible

(hydrodynamic)
retention:
reversible

flow direction

Polymer adsorption has for effect to decrease rock permeability

when it is flooded again with the solvent (see below « Rheology »).
Adsorption/retention in the reservoir rock
Adsorption on the reservoir rock: measured on crushed rock or by
chromatographic methods on cores
polymer concentration front

delay

1 PV

It is often necessary to inject an aqueous solution behind the polymer,

And then a 2nd polymer front (to account for excluded/inaccessible volume effects) .

Hydrodynamic or mechanical retention (in strictions, dead ends)

Adsorption/retention in the reservoir rock

Orders of magnitude: a few µg/g of rock (ok!) to hundreds of µg/g of rock (not
acceptable)

Is minimized with anionic polymers in sandstones

Decreases with increasing anionicity degree

Increases with clay content and increasing salinity

Decreases with increasing permeability

Decreases the reservoir permeability (by reducing the effective pore size), see
next section (Rheology)
Rheology

Flow in a porous medium is complex and is locally the combination of

shear flow

elongational flow

The effective mobility l of a complex fluid (here: the polymer solution) moving at
Darcy velocity u and generating a pressure drop DP in a porous medium of length l is
defined as:

l =u/(DP/L)
Rheology

This mobility is indeed lower than the mobility l0 of the solvent

(with a Newtonian viscosity µ0), equal to k/µ0, (k is the absolute
permeability of the rock) moving at the same velocity u:

l0 =u/(DP0/L)
Rheology: Resistance factors

The resistance factor Rf (sometimes referred to as mobility ratio Rm) is

the ratio of the mobility of the aqueous solvent to the mobility of the
polymer solution:

Rf =l0/lp=DP/DP0 (see previous slide)

Rf (or Rm) is obtained from the measured pressure drops when the rock is
flushed (at the same constant rate) by the solvent (DP0) and then by the
polymer solution (DP).
 Rheology: Resistance factors

When flushed again by the solvent, the pressure drop does not
decrease down to DP0 but to a higher value DP0p which defines
the residual resistance factor:

Rrf= DP0p /DP0 = k/kp

where kp is the (lower) rock permeability due to irreversible polymer

adsorption.
Rheology

The rheology of flexible polymer solution in a porous rock is highly non-

newtonian (it strongly depends on flow rate):

Resistance factor of a polyacrylamide solution in a rock vs. Darcy

velocity (Martischius et al., 1985)
shear-thickening
Newtonian plateau shear-thinning behavior
behavior
Rheology of flexible polymer solutions:

Viscosity m(c) as a fonction of concentration c:

Rheology of flexible polymer solutions:

dilute regime (c<c*) c=c* (overlap concentration)

for c<c* µ(c)/µ (c=0) = 1+ [µ] c +..

[µ] is the polymer intrinsic viscosity, in the

order of liters/gram for EOR polymers

for c>c* µ (c) increases with c much more

strongly than linearly

overlap concentration c*  1/ [µ ]

semi-dilute regime (c>c*)

Rheology of flexible polymer solutions:

In shear flows : shear thinning

(from Green & Willhite’s book)

Rheogram of 1500 mg/L solutions of Pusher

In elongational flows: shear thickening, breaking of chains (mechanical

degradation) above a certain threshold

coil-stretch transition
Rheological measurements:

Conventional shear rheometers are not representative or at least

are not sufficient.

«Screen factor» (SF) viscometers are more representative of flow

in pores, where elongational flow is an important component of
flow.
SF=tp/ts

SF very sensitive to the high-Mw end of the Mw distribution.

Five 100-
mesh
tp and ts: times needed for an equal volume of polymer screens
0,25 in, in
solution and solvent to flow through the screen viscometer diameter

Screen viscometer
Non-newtonian rheology might be responsible for some subtle
effects favoring displacement efficiency
Non-newtonian rheology of polymer solutions is now recognized to improve
microscopic (or displacement) efficiency

Normal stress effect

« plug flow »
Other issues: preparation, injectivity, etc.

Handling of polymer (mixing with solvent containing the appropriate

additive), available as powder or concentrated liquid

Presence of microgels frequent: necessity to eliminate them (by filtration)

Minimize mechanical degradation in the mixing and flow lines

Injectivity in the reservoir rock needs to be checked carefully.

Polymer molecular weight has to be tailored to rock permeability

(if k> 100 mD Mw=12-16 106 g/mol, if k>300 mD, Mw = 17-25 106 g/mol)
A few field cases:

Daqing, China: by far the largest polymer flood project in the world (73 MMbbl/year)
Sandstone, 45°C (1000 m depth), oil viscosity=6-9 cp, low salinity (3000-7000 mg/L)

Heavy oils (with viscosity a few 103 cp): Pelican Lake, Canada

Offshore conditions: Dalia/Camelia oil field, offshore Angola, Doba field (Tchad)
In conclusions; favorable characteristics for polymer flooding:

Low waterflood residual oil saturation

High remaining oil saturation (i.e., unswept zones in the reservoir)

High permeability and porosity

Sufficient vertical permeability to induce crossflow, good geological continuity

High injectivity

Salinity not too high

Reservoir temperature less than 220 F