Enhanced Oil Recovery

Optimizing
Molecular
Weight
in Polymer
Flood

07/2006 - This document is the property of SNF. It must not be reproduced or transfered without prior consent

Fluid viscosity in a polymer flood

It is surprising to find that, regardless the initial
molecular weight of the polymer injected, the
molecular weight of the polymer in the produced
water is low, around 4 to 10 million. The questions
that leap to our minds are:

What is the viscosity of the brine inside the reservoir ?

What is the efficiency of the motor fluid ?
Which are the parameters affecting this efficiency ?
How can the polymer flood be optimized ?

07/2006 - This document is the property of SNF. It must not be reproduced or transfered without prior consent

Average molecular weight

Polyacrylamides are formed of very long chain of polymers,
several million Daltons, and the average molecular weight does
not represent the length of the chain. A polymer is a mixture of
long and short chains. In fact, even with very different average
MW, a part of the molecules are the same.
Number
of
molecules

15M

10

15

20M

20

25M

25

30

35

40

Molecular weight (10^6 Daltons)

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Chemical degradation
The mechanism of chemical degradation is the
formation of free radicals that cut the chain
These free radicals are formed by the reaction of an
oxidizer with a reducer (redox)
Oxydizer

Reducer

O2

H 2S

Fe2+, Fe3+

Scavenger

Hydrocarbon

Fe2+

Peroxydes

Sulfato reducing
bacteria
NH3

The high molecular weight chains are more sensitive

to chemical degradation, especially those above 15
million MW
The best polyacrylamide stability is found in a
reducing media
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Example of chemical degradation

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Mechanical degradation
High shear will cut the polymer chains in pieces
High MW giving a certain viscosity with few chains will
be more sensitive to shear than a low MW providing
the same viscosity with more chains
This shear degradation is amplified by the formation
of free radicals as a mechanism of degradation

07/2006 - This document is the property of SNF. It must not be reproduced or transfered without prior consent

Example of mechanical degradation

Low MW polymers are less sensitive to shearing

07/2006 - This document is the property of SNF. It must not be reproduced or transfered without prior consent

Example of mechanical degradation

07/2006 - This document is the property of SNF. It must not be reproduced or transfered without prior consent

Influence of time on shear

The shear at the injection side is normally very
limited in time (seconds to minutes)
It is also dependent, at the beginning of the injection,
on the structure of the reservoir
During injection time, solids come from the injected
water or are precipitated
(CaCO3, MgOH, FeS, S2 or biological molds)

The solids increase the shearing time by forming

channels, where the polymer solution can be under
high degradation conditions for a length of time
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Low stability for high MW

The stability of high molecular weight molecules is
very low
Number
of
molecules

Very high
stability

Poor
stability

stability

Low
stability

15M

10

15

Very low
stability

20M

20

25M

25

30

35

40

Molecular weight (10^6 Daltons)

07/2006 - This document is the property of SNF. It must not be reproduced or transfered without prior consent

Injection time & mechanical degradation

At the beginning of the injection, the shear is given by

The
The
The
The

flow of polymer solution

area of injection
area of the front surface of the reservoir
permeability

Each polymer contains a certain amount of insoluble particles which

swell in the brine about 50 times forming a large amount of gels,
increasing with time and coating the injection surface
There are two types of gels
Soft gels which are degraded to soluble polymers at a certain pressure; and
at this pressure, there is an equilibrium between injected gels and degraded
gels and the injection well is permanently cleaned
Hard gels which are not sensitive to pressure and plug the injection surface

With time, due to coating of the injection surface, the area of injection
decreases till the injection pressure from the gel is achieved, then the
mechanical degradation becomes stable (in the range of 1 to 7 bar)
But the injection pressure increases with the MW as the amount of gel
and hardness of gel increases with MW

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Final viscosity
The mechanical degradation is generated directly at
the injection point
The chemical degradation happens a few hours after
injection and polymer solution is then stable
Viscosity
cps

Factors

Mechanical
degradation
Chemical
degradation

Brine (TDS)
Temperature
Oxydo reduction equilibrium
Oxydo reduction reactions
Flow
Differential pressure, Shear
Permeability
Precipitation (salts, sulfur, SRB, Fe)
Viscosity of injection
Viscosity at different steps of degradation

Stable fluid

Time

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Polymer choice
Choosing the best polymer for polymer flooding is a
very complex question. The efficiency of the polymer
depends on:
The amount of oxygen at the injection and the addition of a
scavenger in large amounts will not correct it. Oxygen and
scavengers form free radicals
The stable pressure of injection which depends on the flow,
permeability, polymer, viscosity
The quality of the polymer
For the same injected viscosity the high MW products will give a
lower viscosity in the reservoir
Harder are the gels, more the pressure of injection is high and
the mechanical degradation
The absorption of the polymer will depend on the anionicity
A copolymer with very narrow distribution of anionicity will absorb
less than a co-hydrolyzed polymer and less than a post hydrolyzed
polymer. The absorption will take place mainly near the injection
points

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How to correct these parameters

There are solutions to improve these parameters
Addition of free radical scavengers. ITW
(isopropylalcohol+thiourea) is presently the best but
expensive and difficult to handle (flash point, volume)
Increase of concentration of high MW products to match the
same viscosity in the reservoir as the medium MW. But this
will decrease injectivity and it is necessary to decrease the
flow to avoid fracturation. It is easier to adapt the MW to the
field conditions
Avoid oxygen in the polymer dissolution system by a very
careful conception of the equipment
Keep all water circuit in reducing status
Decrease to a minimum all chemical injections
Avoid H2S formation by SRB by biological control

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New types of polymers

Many types of polymers are known from the 70s in laboratory
developments. Some of them are now produced in pilot or
industrial quantities. The main ones are:
Thermostable polymers which increase the stability of the
polyacrylamides from 75C to 90C with new monomers
FLOPAAM AN 125-132

Associative polymers with a main polyacrylamide chain and statistic

repartition of hydrophobic groups. There is an association of these
hydrophobic groups in a specific brine to give a high viscosity
SUPERPUSHER

Star polymers with 3 or more branches on a central polymer group.

These polymers are normally associative to have a high viscosity
ST5030

Comb and T shape polymers with a main hydrophobic chain and

end hydrophobic chain
Block associative polymers with multiple hydrophobic groups inside
an hydrophylic chain
Structured polymers with hydrophilic branches in a main hydrophilic
chain
Soft or Movable gels are totally insoluble yet injectable gels mainly
used in profile modification but with high potential in EOR
FLOPERM 2000

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EOR problems solved?

The new polymers bring as many questions as they solve
problems
Size of associative polymers compared with the permeability of the
reservoir
Association with oil
Absorption on the oil wetted parts
Very high variation viscosity against the salinity of the reservoir with
possibility of plugging with salinity increase
Very quick loss of viscosity by dilution
Sensitivity to Calcium, Magnesium and precipitation
Thermal stability
Mechanical stability
Dissolution problems
Very high viscosities before dilution

Today the potential is high and depends on the risks taken

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Thank you for your attention

Optimizing Polymer Molecular Weight
not Maximizing it, to Achieve the
Highest Efficiency in EOR Polymer
Flooding

07/2006 - This document is the property of SNF. It must not be reproduced or transfered without prior consent