Polymer Flooding Topics

POLYMER FLOODING

1. Distinction between polymer floods and gel treatments.

2. Overview of polymer flooding.
3. Potential for polymer flooding viscous oils.
4. Rheology in porous media.
5. Injectivity.
6. Polymer retention.
7. Chemical/oxidative stability of polymers.
8. Polymer flooding versus in-depth gelation.
9. Colloidal dispersion gels.
10. Surface issues for polymer flooding.
11. Other approaches for mobility control.
12. Can polymers reduce Sor below that for waterflooding?
13. Pilot Project Design.

Randy Seright
575-835-5571
[email protected]
http://baervan.nmt.edu/randy/

POLYMER FLOODS VERSUS GEL TREATMENTS

Distinction between a gel treatment

and a polymer flood.

Polymer floods use polymer solutions. Gels add a

crosslinker to the polymer solution.

The Windfall Profits Act of 1980 encouraged

Polymer
solution

grouping the two methods together as polymer

augmented waterfloods.

For a polymer flood, polymer

penetration into low-k zones
should be maximized.

The Oil and Gas Journal does not distinguish the

Gel
For a gel treatment, gelant
penetration into low-k zones
should be minimized.

two methods in their biannual EOR survey.

What is the difference?

3

VISCOUS
POLYMER
SOLUTION

Higher polymer & crosslinker

concentrations yield stronger gels

CROSSLINKED
POLYMER
(GEL)
Crosslink site

If not enough polymer or

crosslinker is present, no gel forms.

Gelant = Polymer + crosslinker solution before gel formation.

Gel = Crosslinked structure after reaction.
5

GEL TREATMENTS ARE NOT POLYMER FLOODS

Crosslinked polymers, gels, gel particles, and
colloidal dispersion gels:

PROPERTIES OF AVAILABLE GELANTS/GELS

1. Early in the gelation process, gelants
penetrate readily into porous rock.

Are not simply viscous polymer solutions.

2. After gelation, gel propagation through

porous rock stops.

Do not flow through porous rock like polymer

solutions.

3. The transition between these two conditions

is usually of short duration.

Do not enter and plug high-k strata first and

progressively less-permeable strata later.

SPERE (Nov. 1993) 299-304; IN SITU 16(1)

(1992) 1-16; and SPEPF (Nov. 1995) 241-248.

Should not be modeled as polymer floods.

7

POLYMER FLOODING is best for improving

sweep in reservoirs where fractures are not
important.
Great for improving the mobility ratio.
Great for overcoming vertical stratification.
Fractures can cause channeling of polymer
solutions and waste of expensive chemical.

UNFRACTURED RESERVOIRS WITH CROSSFLOW

Ideal Near-Wellbore
Treatment

Ideal Far-Wellbore
Treatment

low k

low k

high k

high k

Water

Reality

Oil

GEL TREATMENTS are best treating fractures

and fracture-like features that cause
channeling.
Generally, low volume, low cost.
Once gelation occurs, gels do not flow
through rock.

Gel

low k
high k

10

Waterflood oil recovery, PV

EFFECT OF MOBILITY RATIO (M)

ON WATERFLOOD OIL RECOVERY

OVERVIEW OF
POLYMER FLOODING

0.3

M = 0.5 : FAVORABLE
M = 8 : UNFAVORABLE

0.2

M = water / oil
= (k/)water / (k/)oil

0.1
0
0

10

Pore volumes of water injected

11

12

EFFECT OF MOBILITY RATIO (M) ON

VERTICAL SWEEP EFFICIENCY

EFFECT OF MOBILITY RATIO ON

AERIAL SWEEP EFFICIENCY

M < 1: FAVORABLE
k1
k3
k2
k1 < k2 < k3
k1
k3
k2

M < 1: FAVORABLE

M > 1: UNFAVORABLE

M > 1: UNFAVORABLE

M = (k/)water / (k/)oil

M = (k/)water / (k/)oil
13

POLYMER FLOODING
As the viscosity of the injected fluid increases, sweep
efficiency in the less-permeable layer increases.
http://baervan.nmt.edu/randy/

14

After polymer or gel placement, injected water forms severe

viscous fingers that channel exclusively through the highpermeability layer.
http://baervan.nmt.edu/randy/

16

15

MOBILITY CONTROL
Polymer water
p

Microemulsion
m

Water, w
Oil, o

Favorable displacement at
microemulsion front requires:

m o + w

Favorable displacement at
microemulsion rear requires:

p m

17

18

SELECTION OF POLYMER VISCOSITY

Want to make the water flood mobility ratio favorable.

Want to overcome the permeability contrast.
Water

Water
flood:
M = 9.4

oil
k1/k2= 4

Polymer
flood:
M~1

Polymer,

Polymer
flood:
M ~ 0.25

Polymer,

oil

p/w= 10;

k1/k2= 4
oil

p/w= 40

k1/k2= 4
19

IDEAL PROPERTIES FOR

MOBILITY CONTROL AGENTS
Low cost or high cost-effectiveness.
Allows high injectivity.
Effective when mixed with reservoir brines (up to
20% total dissolved solids).
Resistant to mechanical degradation (up to 1000
m3/m2/d flux when entering porous rock).
5 to 10 year stability at reservoir temperature (up
to 150C).
Resistant to microbial degradation.
Low retention (e.g., adsorption) in porous rock.
Effective in low-permeability rock.
Effective in the presence of oil or gas.
Not sensitive to O2, H2S, pH, or oilfield chemicals.

20

POLYMER PROPERTIES OF INTEREST

Salinity Tolerance
Shear Stability
Rheology and Injectivity
Thermal Stability
Retention
Biostability
Surfactant Compatibility
Cost
21

Both HPAM and xanthan are charged polymers,

but the rod-like xanthan gives higher viscosities
at moderate to high salinities.

1000

22

FLEXIBLE vs SEMI-RIGID ROD POLYMERS

Polyacrylamide or HPAM Polymers

0.06% polymer, 25C

[ - CH2 - CH - ]m - [ - CH2 - CH - ]n

Viscosity, mPa-s

C
100

10

>90% of oil
is in saline
reservoirs

HPAM

-O
acrylate

C
O

NH2

acrylamide

Flexible coil

Xanthan
Double helix, semi-rigid rod.

1
0.01

0.1

Brine salinity, % NaCl

Xanthan
Polysaccharide

10
23

24

RESISTANCE TO MECHANICAL DEGRADATION

MECHANICAL (OR SHEAR) DEGRADATION

% of original viscosity

120

SURFACE FACILITIES
Mixers, pumps, filters, valves, meters.
Degradation generally can be minimized
through good design (avoiding flow
constrictions).

DOWNHOLE
Depends on the nature of the completion.
Increased area at the rock interface
decreases fluid velocity and degradation.

100

XANTHAN
HPAM

80
60
40
20
0
0.1

10

100

1000

10000

Velocity in porous rock, ft/d

25

Velocities in a Five-Spot Pattern (1-layer)

Although both xanthan and HPAM show shear

thinning in viscometers, HPAM shows shear
thickening in porous mediaimportant to injectivity.
0.1% polymer in seawater,
550-md Berea, 25C
Xanthan

SPE 4883:
Parsons

Fresh HPAM

10

HPAM previously forced

through core at 139 ft/d

Open
hole

10

Perforations

70% of the pattern has a velocity

within 50% of the median value.

0.1

1
0.01

Fractured
well

Deep in
reservoir

Apparent viscosity in porous

media

100

26

100

1000

10000

Superficial velocity, ft/d

27

What is the upper temperature limit for

HPAM use in chemical EOR?

STABILITY AT ELEVATED TEMPERATURES

10

Viscosity half-life, yrs

28

SCLEROGLUCAN

HPAM
with Ca2+

form acrylate groups.

HPAM
without
Ca2+

< 2 ppb
dissolved
oxygen

Above 60C, acrylamide groups hydrolyze to

XANTHAN

If the degree of hydrolysis is too high and too

much Ca2+ or Mg2+ is present, HPAM polymers

precipitate.

0
20

40

60

80

100

120

140

Temperature, C
29

Temperature, C:
75
88 96 204
Max Ca2+ + Mg2+, mg/L: 2000 500 270 20
(from Moradi-Araghi and Doe, 1987)

30

THERMAL, CHEMICAL, & BIO-DEGRADATION

Both HPAM and xanthan are very susceptible to
oxidative degradation. Fortunately, most
reservoirs contain no free oxygen.
HPAMs C-C main chain is very resistant to
thermal breaking if O2 or free radicals are absent.
Xanthans C-O main chain is susceptible to
hydrolysis above 70C.
HPAMs amide groups are susceptible to
hydrolysis above 60C, leading to polymer
precipitation if Ca2+ or Mg2+ are present.
HPAM is much more resistant to bio-degradation
than xanthan.

POLYMER RETENTION
(ADSORPTION, MECHANICAL ENTRAPMENT,
PRECIPITATION) CAN VARY WITH
Mineralogy
Permeability & Pore Structure
Polymer Molecular Weight
Polymer Composition
Water Salinity & Hardness
Wettability
Temperature
Residual Saturations
Surfactant Compatibility

31

32

Older Field Projects

SURFACTANT POLYMER INTERACTION

Properties of Successful Polymer Floods

SPERE August 1997, 189-205.
Property

SURFACTANT
+ WATER
+OIL

+ POLYMER

MICROEMULSION
PHASE

Permeability, md
Temperature, C
Oil/water relative viscosity
at reservoir temperature
%OOIP present at project startup
WOR at project startup
Polymer
Polymer concentration, ppm
Polymer injected, lbs/ac-ft
Projected IOR, %OOIP
Projected IOR, bbl/lb polymer
Projected IOR, bbl/ac-ft

POLYMER
PHASE
SINGLE PHASE
MICROEMULSION

Marmul

Oerrel

Courtenay

Daqing

15,000
46
114

2,000
58
39

2,000
30
50

870
45
15

~92
1
HPAM
1,000
373
25*
1.2
27

81.5
4
HPAM
1,500
162
~13
~1.4
~230

78
8
HPAM
900
520
30
0.96
499

71
10
HPAM
1,000
271
11
0.57
155

*IOR over primary production for this case only.

For the others, IOR is incremental over waterflooding.
33

34

Some Recent Polymer Flooding Projects

Daqing: SPE 144294, 77871, 77872, 109682, 99441
Shengli: SPE 169692.
Shuanghe: SPE 50933.
Pelican Lake: SPE165234 166256, 169062
Wainwright: SPE 154050. Other Canadian: 169062
East Bodo: 09-02-55 PETSOC. Rapdan: 27820
Tambaredjo: SPE 154567, 164121, 169027, 138728
Windalia: SPE 165253
Dalia: SPE 116672, 135735
Marmul: SPE 18092, 154465, 154665, 169714
Mangala: SPE 169146, 154159, 155162, 113347
Bockstedt: 169158/169032. Matzen: SPE 169043.
Other German (older): SPE 24118, 24121, 24120
Diadema: SPE 166255

For the most successful and definitive polymerfloods:

T < 60C
k > 800 md
Oils were moderately viscous
Sand or sandstone reservoir
OOIP present at startup > 70%
WOR at startup was not high
Used >1,000-ppm HPAM in fresh water
Formation salinity was low except in one case

35

36

BOTTOM LINE
1. Higher oil prices, modest polymer prices, increased
use of horizontal wells, and controlled injection above
the formation parting pressure all help considerably to
extend the applicability of polymer flooding in
reservoirs with viscous oils.
2. A high mobile oil saturation, degree of heterogeneity,
and relatively free potential for crossflow in reservoirs
also promote the potential for polymer flooding.
3. For existing EOR polymers, viscosity increases
roughly with the square of polymer concentrationa
fact that aids the economics for polymer flooding of
viscous oils.
4. Reduced injectivity may be a greater concern for
polymer flood application than the chemical cost of
viscous polymer solutions.

SPE 129899
POTENTIAL FOR POLYMER
FLOODING VISCOUS OILS

37

38

Thermal methods cant be used for some viscous

oilsbecause of thin zones, ambient cold,
environmental constraints, permafrost, etc.

Even with no heterogeneity (i.e., one layer), reducing the

oil/water viscosity ratio substantially improves oil
displacement efficiency.

Old (1997) screening criteria for polymer flooding:

~150-cp oil was the upper limit because of
(1) polymer costs and (2) injectivity losses.
Changes since the old screening criteria:
Higher oil prices (>$70 versus ~$20/bbl).
Modest polymer prices ($1.50 versus $2/lb).
Greater use of horizontal wells.
Controlled injection above the parting pressure.

Mobile oil recovered, %

100

Is polymer flooding viable for viscous oils?

1 cp oil

90
80
70

krw=0.1 [(Sw-0.12)/(0.76)]4
kro= [(0.88-Sw)/(0.76)]2.5

60
50

10 cp
oil

103 cp

100 cp

1-Sor-Swr = 0.76
1 cp water
Injected

104 cp

40

105 cp oil

30
20

One layer, 1 cp water, linear flow,

no polymer, North Slope case

10
0
0.01

0.1
1
10
Pore volumes of water injected

100

39

40

For cases with crossflow, substantial improvements in

sweep efficiency can occur, especially when using very
viscous polymer solutions.

For cases with no crossflow, a 10-cp polymer solution

provides noticeable sweep improvement.

Mobile oil recovered, %

90
80
70
60
50

1000 cp
polymer

Two layers,
no crossflow,
linear flow,
k1=10k2,
h1=h2,
1000 cp oil,
1 cp water

100

10 cp

1 cp

40
30
20

North Slope case

1-Sor-Swr = 0.76

10
0
0.01

0.1

1000 cp
polymer

90

100 cp

Mobile oil recovered, %

100

10

80
70
60
50
40
30

100 cp polymer

Two layers,
free crossflow,
linear flow,
k1=10k2,
h1=h2,
1000 cp oil,
1 cp water

10 cp polymer

1 cp water

20

North Slope case

1-Sor-Swr = 0.76

10
0
0.01

100

Pore volumes of polymer or water injected

0.1

10

100

Pore volumes of polymer or water injected

41

42

Polymers are more efficient viscosifiers at high

concentrations: ~ C2 (i.e., only 40% more
polymer is needed to double the viscosity).
Viscous oil
polymer floods

1000

Most previous
polymer floods

Relative profit

Viscosity @ 7.3 s-1, cp

10000

polymer in
2.52% TDS
brine, 25C

100

diutan
xanthan
19 million Mw HPAM
7 million Mw HPAM

10

1
100

1000

10000

100000

Polymer concentration, ppm

If polymer could be injected as readily as water, injection

of very viscous polymer solutions would be preferred.
12
Two layers, free crossflow, North Slope case,
11
1,000 cp oil, k1=10k2, h1=h2, linear flow.
10
1000 cp polymer
9
$20/bbl oil
8
$1.50/lb polymer
$0.25/bbl water
7
6
100 cp polymer
10 cp polymer
5
4
3
1 cp
2
water
1
0
0.01
0.1
1
10
100
Pore volumes of polymer or water injected

43

Scheme to Maximize Polymer Injectivity/Productivity

Relative profit

If polymer injectivity varies inversely with polymer viscosity,

injection of less viscous polymer solutions would be preferred.
INJECTIVITY MAY BE MORE IMPORTANT THAN POLYMER COST.

12
Two layers, free crossflow, North Slope case
11
1,000 cp oil, k1=10k2, h1=h2
10
1000 cp
polymer
9
$20/bbl oil
8
$1.50/lb polymer
100 cp
$0.25/bbl water
7
polymer
6
10 cp polymer
5
1 cp water
4
3
2
1
0
0.01
0.1
1
10
100

44

Horizontal
Injector

Injector
Fractures

Minimum
stress
direction
Horizontal
Producer

1000

Relative time

Producer
Fractures

45

Can viscoelastic polymer solutions reduce the

Sor below that for waterflooding?.
1. Daqing says yes; UT Austin says maybe not.
2. Does it matter for viscous oils? (yes)

Does a delay before starting the

polymer flood hurt performance?
100
Mobile oil recovered, %

90
80
70

100 cp polymer

Two-layers,
free crossflow,
k1/k2=10, h1/h2=1,
Base case

60
50
40

0.53
PV

1-Sor-Swr = 0.4

No delay
(polymer flood
from the start)

30
20

1.06
PV

0.26
PV

10
0
0.01

2.7
PV

0.1

46

5.3
PV

Waterflood
only
1000 cp oil,
1 cp water

10

100

Pore volumes of polymer or water injected

47

48

BOTTOM LINE
1. Higher oil prices, modest polymer prices, increased
use of horizontal wells, and controlled injection above
the formation parting pressure all help considerably to
extend the applicability of polymer flooding in
reservoirs with viscous oils.
2. A high mobile oil saturation, degree of heterogeneity,
and relatively free potential for crossflow in reservoirs
also promote the potential for polymer flooding.
3. For existing EOR polymers, viscosity increases
roughly with the square of polymer concentrationa
fact that aids the economics for polymer flooding of
viscous oils.
4. Reduced injectivity may be a greater concern for
polymer flood application than the chemical cost of
viscous polymer solutions.

MODELING RECOVERY EFFICIENCY

1. Fractional flow calculations are just a simple
guide. Certainly, there are things that they cant
do.
2. Simulations can provide much more insight IF
they are set up and performed correctly.
3. Simulations must be benchmarked against known
answers and common sense. Example: I have
witnessed Eclipse, VIP, and UTCHEM indicating
that crossflow and no-crossflow cases giving the
same recovery values regardless of mobility ratio.

49

50

DAQING

DAQING

Why were the fractures apparently wider during

polymer injection than during water injection?
Higher pressures during polymer injection could
have flexed the fractures open wider than
during water injection.

Were fractures present?

YES
Fracture widths:
1.5 to 5 mm from injectivity/productivity
analysis during polymer injection.
0 to 1.8 mm from injectivity/productivity
analysis during water injection.
~0.01 mm from interwell tracer analysis
of polymer breakthrough.

Why were fracture widths from injectivity analysis

greater than from tracers?
Fractures were wider near wells than deep in the
formation.

51

DAQING: DID FRACTURES HURT SWEEP?

Healing the fracture reduces channeling,
but reduces injectivity/productivity, and
reduces sweep within the matrix.

20

20

18

18

16

16

14

14

Pressure, MPa

Pressure, MPa

DAQING: DID FRACTURES HURT SWEEP?

A 1-mm open fracture between two wells
allows high injection/production rates but
also allows severe channeling.

52

12
10
8
6

12
10
8
6
4

4
2

150

0
0

75
75

150
x, m

225

150

0
0

y, m

75
75

150
x, m

300
53

225

y, m

0
300
54

DAQING: DID FRACTURES HURT SWEEP? No.

Restricting the middle third of the fracture
provides the best possibility. Fractures did not
hurt sweep. Gel treatments were not needed.

Moderate-length fractures can substantially

increase injectivity and productivity and
can improve areal sweep efficiency.

20

Moderate-length fractures could have

considerable value for future EOR projects
at Daqing if very viscous fluids must be
injected to maintain mobility control.

18

Pressure, MPa

16
14
12
10
8
6

Utilizing fractures in this way requires a

good understanding of fracture formation,
length, width, height, and orientation.

4
2

150

0
0

75
75

150
x, m

225

y, m

0
300
55

Permeability reduction is greater in lowpermeability rock than in high-permeability rock.

56

If polymer molecular weight is too high, Fr values

increase with decreasing k. (A pore-plugging effect.)
What if Fr1 < Fr2? How does that affect vertical sweep?

This effect could harm vertical sweep efficiency.

Lp2 or rp2

Zone 2, k2,2, Fr2

Zone 1, k1, 1, Fr1

Vela et al. SPE 5102

HPAM
Mw= 5.5 x 106
20% hydrolysis.
Sandstone rock.

Fr = resistance factor (apparent viscosity)

Lp1 or rp1

For radial flow & no crossflow, Fr2 /Fr1 must be < 1.4.
For linear flow & no crossflow, Fr2/Fr1 must be < k1/k2.
For free crossflow, vertical sweep is insensitive to Fr2/Fr1.
57

1.5

No crossflow case,
Radial flow.

1.4

For polymers, Fr values often increase with decreasing k.

What if Fr1 Fr2? If no crossflow, vertical sweep is far
more tolerant to Fr2 / Fr1 for linear flow than for radial flow.
If fluids can crossflow, then Fr2 / Fr1 matters little.
100

k1/k2= 20

1.3

k1/k2= 10

1.2

k1/k2= 5

1.1

k1/k2= 2

Limits for linear flow,

Fr2 /Fr1 = k1 /k2

Resistance factor

Maximum allowable resistance factor in Zone 2

(relative to that in Zone 1) to achieve vertical sweep
no worse than for a water flood

For polymers, Fr values often increase with decreasing k.

What if Fr1 Fr2? For radial flow, Fr2 must be < 1.4 Fr1.

58

Data points: Vela,22

0.06% Pusher 700 HPAM,
13.3% brine, 150F, Sor
10

Limits for radial flow,

Fr2 /Fr1 = 1.4

10

100

Resistance factor in Zone 1

1000

10
59

100

1000

Pre-polymer core permeability (k w at S or ), md

60

10

Rheology: Bottom Line

1. The low-shear-rate viscosity is the best indicator of
resistance factor deep in a formation, if you dont have
good data from corefloods.
2. If your corefloods indicate low-flux resistance factors
that are much higher than low-shear-rate viscosities,
be suspiciousdo more tests.
3. Unless your water is VERY fresh or the polymer
concentration is very high, HPAM shows nearNewtonian behavior at low flux and shear-thickening at
higher flux: This increases the probability that the
polymer must be injected above the fracture pressure.
4. In any realistic reservoir, shear-thinning behavior (e.g.,
xanthan use) is not bad for sweep efficiency.
5. If you want to use non-Newtonian behavior in your
simulator, compare your results with Newtonian
behavior to see if the results make sense.

SPE 129200
Polymer Rheology in
Porous Media

61

When Displacing Viscous Oils,

Viscous Polymer Solutions May Be
Needed to Improve Sweep Efficiency

62

Xanthan shows shear thinning in porous media.

100

High-viscosity oil

Low-viscosity
oil

Resistance factor

water or
polymer
solution

Resistance factors (effective viscosities

in porous media) at low velocities
determine the sweep efficiency during
polymer or chemical floods.

600 ppm xanthan,

2.52% TDS, 25C

55 md
269 md
5120 md
~0.5 ft (14-15 cm)
long cores

10

1
0.01

0.1

10
Flux, ft/d

100

1000

63

64

At low velocities in short cores with low permeability (e.g., 55

md), fresh xanthan solutions show shear thinning, whereas
viscosity data predicts Newtonian behavior.

Xanthan solutions show shear-thinning behavior in

porous media and resistance factors correlate well
using the capillary bundle parameter, u (1-)/(k)0.5.

Shear rate, s-1

Resistance factor or viscosity, cp

Resistance factor

100

55 md

10

269 md

600 ppm xanthan,

2.52% TDS, 25C

5120 md

~0.5 ft (14-15 cm)

long cores

1
0.001

0.01

0.1

10

u (1-)/( k)0.5, ft/d-md0.5

100

65

100

10

100

1000

10000

Is this caused by a high Mw

polymer species that will not
penetrate deep into a reservoir?

55 md
269 md
5120 md
viscosity

10
600 ppm xanthan,
2.52% TDS, 25C
~0.5 ft (14-15 cm)
long cores

1
0.001

0.01

0.1

10

u (1-)/( k)0.5, ft/d-md0.5

100
66

11

If the polymer first flows through a few feet of rock,

resistance-factor-versus-flux data closely follows
expectations from viscosity-versus-shear-rate data.

If the polymer first flows through a few feet of rock,

resistance-factor-versus-flux data closely follows
expectations from viscosity-versus-shear-rate data.

u (1-)/( k)0.5, ft/d-md0.5

0.001

100

0.1

0.01

u (1-)/( k)0.5, ft/d-md0.5

10

100

0.001

100

short core
24-48 cm
48-73 cm
73-98 cm
98-122 cm
viscosity

10
Red circles: at 20 PV
for 14.4-cm, 55-md core.
Other symbols: at 2.5 PV
for 122-cm, 57-md core.

1
0.001

0.01

0.01

0.1

600 ppm xanthan,

2.52% TDS, 25C

0.1

Resistance factor

Resistance factor

600 ppm xanthan,

2.52% TDS, 25C

10

100

10

10

short core
24-48 cm
48-73 cm
73-98 cm
98-122 cm
viscosity

Red circles: at 20 PV
for 14.4-cm, 55-md core.
Other symbols: at 2.5 PV
for 122-cm, 57-md core.

1
0.001

1000

0.01

0.1

Flux, ft/d

100

Suggests that the high Mw

species travels 1/6 to 1/3
the rate of normal xanthan.

10

100

1000

Flux, ft/d
67

1960s Dow HPAM Claim

68

HPAM Behavior in Porous Media

Pye, JPT, August, 1964

HPAM can reduce water

mobility both by increasing
water viscosity and by
reducing permeability:

Resistance factor

100

=k/

Resistance factor (Fr or RF)

Fr = (k / )brine / (k / )polymer
This effect is typically seen in
short laboratory cores using
fresh, gently-handled solutions.

Shear rate, s-1

10
100

1
2500 ppm HPAM,
Mw ~6-8 million,
30% hydrolysis
2.52% TDS, 25C

1000

Is this caused by a high

Mw polymer species
that will not penetrate
deep into a reservoir?

10
55-md core, fresh HPAM
269-md core, fresh HPAM

10-cp
polymer
solution

5120-md core, fresh HPAM

viscosity

1
0.001

Can permeability reduction really

be exploited in a useful way in
a real polymer flood?

0.01

0.1

10

u (1-)/( k)0.5, ft/d-md0.5

69

Shear thinning can be seen for fresh HPAM solutions at low flux,
especially in low-k cores. However, flow through a few feet of
porous media can reduce or eliminate this effect.

Shear thinning can be seen for fresh HPAM solutions at low flux,
especially in low-k cores. However, exposure to high flux or
pressure gradient can reduce or eliminate this effect.
2500 ppm HPAM, Mw ~6-8 million, 30% hydrolysis
2.52% TDS, 25C
Shear degradation
eliminates this effect.

10
55-md core, fresh HPAM
269-md core, fresh HPAM
5120-md core, fresh HPAM
46-md core section, degraded HPAM
17.5-md core section, degraded HPAM
viscosity

1
0.001

0.01

0.1

10-cp
polymer
solution

u (1-)/( k)0.5, ft/d-md0.5

0.01

100

Resistance factor

Resistance factor

100

70

0.1

10

2500 ppm HPAM, Mw ~6-8 million, 30% hydrolysis

2.52% TDS, 25C. 9 PV was first forced through 4
ft (122 cm) of 47-md Berea at 1.6 ft/d flux.
The final effluent was re-injected into a 0.44-ft
long Berea core using a range of flux values.

10
Flow through 4-ft of rock
also eliminates the effect.

1
0.01

10

u (1-)/( k)0.5, ft/d-md0.5

0.1

73 md Section 1
94 md Section 2
81 md Section 3
viscosity
10

100

Flux, ft/d
71

72

12

HPAM Rheology in Porous Rock:

1) Newtonian at low flux,
2) shear thickening at intermediate flux,
3) mechanical degradation at high flux.

For HPAM solutions with a sufficiently low salinity and/or

sufficiently high polymer concentration, shear thinning can be
observed in porous media at moderate to low fluxes.

1000

100

Resistance factor in the second

section

Resistance factor

1000
3830S HPAM:
Mw ~18-20 million,
40% hydrolysis.
5,120-md polyethylene core.
25C

10
900-ppm HPAM in 2.52% TDS brine
1000-ppm HPAM in distilled water
400-ppm HPAM in distilled water
1
0.01

0.1

10

100

From SPE 115142

in 0.3% NaCl

100

in sea water

10

1,000 ppm 3830S HPAM, Mw ~18-20 million,

40% hydrolysis. 573-md Berea core, 25C

1000

1
0.01

Flux, ft/d

0.1

1
Flux, ft/d

10

100

73

Rheology in Porous Media

Effect of Polymer Concentration

on 3830S HPAM in a 5120 md Core
1000

Resistance factor

Mw ~18-20 million,
40% hydrolysis,
2.52% TDS, 25C

HPAM
concentration

100

74

Until recently, most commercial chemical flood

simulators assumed shear thinning behavior
for polymers at moderate to high velocities in
porous media.

2500 ppm
1600 ppm
900 ppm
480 ppm
200 ppm
100 ppm
50 ppm
25 ppm
0 ppm

The assumption is ok for xanthan biopolymers,

but is wrong for HPAM (polyacrylamides)the
main EOR polymer.

10

This incorrect assumption for HPAM results in

overly optimistic injectivity estimates if vertical
wells are not fractured.

1
0.1

10
Flux, ft/d

100

1000
75

Rheology assumed by Alsofi and Blunt

IMPACT OF RHEOLOGY ON SWEEP EFFICIENCY

Based on numerical work, Delshad et al. (U. Texas) and AlSofi and Blunt

With their assumptions, of course shear-thickening will

provide the best sweep efficiency (because it always provides
the highest resistance factor) and shear-thinning will be worst.
100

Unfair comparison
Resistance factor

(Imperial College) suggested that shear-thinning rheology has a

substantial negative impact on sweep efficiency.
In part, their argument is based on work from Jones (1980), where layers
with different permeability were completely filled with polymer. However,
a very different result occurs if polymer is injected to DISPLACE water/oil
from a multilayer system!
Negative assessments of shear-thinning can also be obtained by an
incorrect characterization of polymer rheology: i.e., assuming that a
Newtonian fluid is always more viscous than a shear-thinning fluid.
Our analysis indicates:
Shear-thinning fluids can provide a much worse vertical sweep than
Newtonian or shear-thickening fluids IF (1) no crossflow occurs
between layers AND (2) the injection rates and pressure gradients
are unrealistically high.
However, for realistic reservoir conditions and polymer properties,
rheology has very little impact on vertical sweep, especially for
adjacent layers with free crossflow.
The overall resistance factor at low flux has a greater impact vertical
sweep efficiency.
Experimental verification can be found at:
http://baervan.nmt.edu/randy.

76

10
Newtonian
Shear thinning
Shear thickening
1
0.01

77

0.1

10
Flux, ft/d

100

1000
78

13

For real fluids, the low-flux resistance

factor or zero-shear viscosity increases
with increasing polymer concentration
and with the level of shear thinning.

If polymers are compared at constant

polymer concentration or constant polymer
cost, a different conclusion may be reached.
100

0.1% polymer in seawater,

550-md Berea, 25C

The resistance factor

here is what is most
important to sweep!

10

Fresh HPAM
HPAM previously forced
through core at 139 ft/d

Open
hole

10

10

Perforations

100

1000

10000

1
0.01

Superficial velocity, ft/d

0.1

79

Rheology and Sweep Efficiency

10
Flux, ft/d

100

1000
80

However, a very different result occurs if

polymer is injected to DISPLACE
Crossflow in a two-layer beadpack. SPE 24192
water/oil
from adisplacing
multilayered
Xanthan solutions
water; k 1reservoir!
/k 2 = 11.2.

Some suggest that shear thinning fluids are bad

for vertical sweep efficiency (Jones 1980).
If two zones are completely filled with polymer
solution, the flow profile for a shear-thinning
fluid will be worse than for a Newtonian fluid.
Zone 2, k2,2, Fr2, v2

100 ppm
300 ppm
500 ppm
600 ppm
800 ppm

0.1

1
0.01

Fractured
well

Deep in
reservoir

Resistance factor

Xanthan

Apparent viscosity in porous

media

100

Let (k12,)/(k21)=10

Zone 1, k1, 1, Fr1, v1

v1/v2 ~ (k1/k2) = 10 for a Newtonian fluid (e.g., water).

For a shear-thinning fluid, Fr ~ (v)(n-1) (k/)(1-n)/2
If k1/k2=10 and n=0.5, v1/v2 ~ (k1/k2)1.5 = 32

0-ppm xanthan, 1 cp

Layer 1
Layer 2

200-ppm xanthan, 3 cp

Layer 1
Layer 2

500-ppm xanthan, 8 cp

Layer 1
Layer 2

1000-ppm xanthan, 23 cp

Layer 1
Layer 2

2000-ppm xanthan, 75 cp

Layer 1
Layer 2

Xanthan

Water

81

Rheology: Bottom Line

UNDERSTANDING THE IMPACT OF RHEOLOGY

AND CROSSFLOW ON VERTICAL FLOW PROFILES

1. The low-shear-rate viscosity is the best indicator of

resistance factor deep in a formation, if you dont have
good data from corefloods.
2. If your corefloods indicate low-flux resistance factors
that are much higher than low-shear-rate viscosities,
be suspiciousdo more tests.
3. Unless your water is VERY fresh or the polymer
concentration is very high, HPAM shows nearNewtonian behavior at low flux and shear-thickening at
higher flux: This increases the probability that the
polymer must be injected above the fracture pressure.
4. In any realistic reservoir, shear-thinning behavior (e.g.,
xanthan use) is not bad for sweep efficiency.
5. If you want to use non-Newtonian behavior in your
simulator, compare your results with Newtonian
behavior to see if the results make sense.

p, L

Zone 2, k2, Fr2

Zone 1, k1, Fr1

82

v2 p k2 / ( 2 L)
v1 p k1 / ( Fr1 1 L)

At the front,v2 /v1 Fr1 k2 1 / ( k1 2)

For a shear-thinning fluid, Fr ~ (v)(n-1) (k/)(1-n)/2

Near the well, if n=0.5, v1/v2 ~ (k1/k2)1.5, so the flow

profile appears worse, even though vertical sweep

is as good as it can be.
83

84

14

INJECTIVITY: BOTTOM LINE

1. For most previous polymer floods, injection has
occurred above the formation parting (fracture)
pressureeven though the operators insisted that
they did not.
2. This is not bad, so long as fracture extension is
controlled so that fractures dont (a) let fluids flow
out of zone or (b) extend far enough to cause
channeling.
3. Be realistic. If you cant live with the injectivity
reduction associated with a viscous fluid, dont insist
that you are going to inject below the parting
pressure.
4. If you are willing to inject above the parting pressure,
spend some time understand how the fractures will
extend and the consequences.

SPE 115142
INJECTIVITY CHARACTERISTICS
OF EOR POLYMERS

85

86

Injectivity:

Objectives:
Estimate injectivity losses associated with
polymer solutions if fractures are not open.
Estimate the degree of fracture extension if
fractures are open.

Defined as injection rate divided by pressure

drop from the wellbore into the formation.

Want a high injectivity to allow rapid

displacement and recovery of oil.

Polymers are needed for mobility control for

Factors Affecting Polymer Solution Injectivity:

Debris/microgels/undissolved polymer
Rheology in porous media
Mechanical degradation
Displacement of residual oil (not considered here)

most chemical flooding projects:

The viscous nature of polymer solutions will

necessarily reduce injectivity unless the well

intersects a fracture.
Fractures can cause severe channeling and/or
injection out of zone for expensive EOR fluids.
87

For both xanthan and HPAM solutions, filterability

Plugging of Rock Face During Polymer Injection

varies a lot, depending on polymer source.

~ for unfractured vertical wells.

~ 103 - 104 cm3/cm2 for fractured vertical wells.
cm3/cm2

Filter cake resistance, cmcp/darcy

106

0.13% X US K HV, 75 cp
0.13% X US K K36, 60 cp
0.13% X US K XC, 47 cp
0.1225% X US K K70, 60 cp
0.13% X CH Sh F, 60 cp
0.1% P FR S 38, 9 cp
0.234% P FR S 38, 60 cp
0.2% P CH H K5, 60 cp

10000

Throughput for field EOR projects:

105

88

Previous lab filter tests

Used less than 40 cm3/cm2 throughput.

Typically use filter ratios. [(t500-t400)/ t200-t100)]
Do not correlate with injection into rock.

We developed a new filter test:

Using throughputs over 2,000 cm3/cm2.

That correlates with injection into cores.

1000
100
10

seawater

1
0.1
10

89

100
1000
Throughput, cm3/cm2

10000
90

15

Even with the cleanest polymers, face plugging

will exceed the capacity of unfractured wells
during most chemical EOR projects.

Fracture extension expectations for

polymers that plug at a give throughput.
600
Fracture half length, ft .

10000

Throughput, cm 3/cm2

3000
cm3/cm2

1000

600
cm3/cm2
100
cm3/cm2

100

10

20-ac spacing,
rw=0.375 ft, = 0.2

1
0.0001

0.001

0.01
PV injected

0.1

plugging at
100 cm3/cm2
Severe
extension

500

plugging at
3,000 cm3/cm2
Moderate
extension

400
plugging at
600 cm3/cm2
Substantial
extension

300
200
100

Vertical well, 2-wing fracture,

20-acre 5-spot, =0.2

0
0

0.1

0.2

0.3

0.4

0.5

0.6

0.7

PV injected
91

92

Xanthan rheology in porous media

Xanthan is remarkably resistant to

correlates well with that in a viscometer.

mechanical (shear) degradation.

100

0.1% CP Kelco xanthan in seawater,

551-md Berea core, 25C

Viscosity, cp

Resistance factor or viscosity, cp

100

Viscosity vs
shear rate x 1/20

10

Resistance factor
vs flux

0.1% CP Kelco xanthan in seawater, 25C

10
AOriginal polymer solution
BAfter 2,480 psi/ft through 102-md Berea
CAfter 19,500 psi/ft through 102-md Berea
DAfter 24,600 psi/ft through 102-md Berea

Fr = 2.5 + 20 u-0.5
1
0.01

1
0.1

1
10
100
1000
Flux, ft/d, or shear rate/20, 1/s

10000

10

Shear rate, 1/s

100

1000

93

94

Although HPAM solutions show pseudoplastic

behavior in a viscometer, they show Newtonian
or shear-thickening behavior in porous rock.

100

Shear thickening
or pseudodilatant
Resistance
factor vs flux

100
Resistance factor in the second
section

Resistance factor or viscosity, cp

1000

HPAM Rheology in Porous Rock:

1) Newtonian at low flux,
2) pseudodilatant at intermediate flux,
3) mechanical degradation at high flux.

Mechanical
degradation

Newtonian
10

Viscosity vs
shear rate
0.1% 3830S HPAM
in 0.3% NaCl, 25C
573-md Berea Core

Shear thinning
or pseudoplastic

1
0.01

0.1
1
10
Flux, ft/d, or shear rate/20, 1/s

0.1% P FR S 38 HPAM in seawater,

573-md Berea core, 25C

Fr = 7.9 + u2/5.6
Fresh solution

10

Pre-sheared at 139 ft/d

Fr = 3.7 + u2/1960

100

100

0.1
95

10
Flux, ft/d

1000
96

16

Even without face plugging, the viscous nature of

the solutions investigated requires that injectivity
must be less than 20% that of water if formation
parting is to be avoided (unless Sor is reduced).

HPAM can show an entrance pressure drop

on entering porous rock. Xanthan does not.

0.1% 3830S HPAM,
573-md Berea core, 25C

300
250

Fresh
solution
in seawater

1
Injectivity relative to water

Entrance pressure drop, psi

350

Pre-sheared at 139 ft/d

(938 psi/ft) in seawater

200
150

Fresh solution
in 0.3% NaCl

100
Pre-sheared at 41 ft/d (4640
psi/ft) in 0.3% NaCl

50
0

Vertical well, 20-acre 5-spot, =0.2

3 cp Newtonian
HPAM: Fr = 3.7 + u2/1960
10 cp Newtonian

0.1

0.1

xanthan: Fr = 2.5 + 20 u-0.5

30 cp Newtonian
100 cp Newtonian

HPAM: Fr = 42 + 11 u

0.01

0.1

10
Flux, ft/d

100

1000

0.01
0

0.1

0.2

0.3

0.4

0.5

PV injected
97

98

Fracture extension expectations for

polymers with different rheologies

SIMPLE MODELING OF INJECTIVITY

1. First, for vertical wells, you are looking for a YESNO answer about whether fractures must be open
during polymer injection.
2. Simple radial flow equation (polymer/water
injectivity):

300

Fracture half length, ft

HPAM: Fr = 42 + 11u

I /Io = Ln (re/rw) / [Fr Ln (rp/rw) + Ln (re/rp)]

Assume re=1000 m, rw=0.1 m, rp = 100 m.
Fr

I /Io

0.40

10

0.13

20

0.07

50

0.03

HPAM: Fr = 65 + 90u0.75
xanthan:
Fr = 2.5 + 20u-0.5

200

HPAM:
Fr = 7.9 + u2/5.6

HPAM:
Fr = 3.7 + u2/1960

100

Vertical well, vertical 2-wing fracture

re = 330 ft, rw=0.375 ft. 0.1% polymer
0

3. If you inject above the formation parting pressure,

the fracture(s) will extend to accommodate polymer
injection.

0.1

0.2
0.3
PV injected

0.4

99

0.5
100

STAATSOLIE SURINAME

INJECTIVITY: BOTTOM LINE

1. For most previous polymer floods, injection has
occurred above the formation parting (fracture)
pressureeven though the operators insisted that
they did not.
2. This is not bad, so long as fracture extension is
controlled so that fractures dont (a) let fluids flow
out of zone or (b) extend far enough to cause
channeling.
3. Be realistic. If you cant live with the injectivity
reduction associated with a viscous fluid, dont insist
that you are going to inject below the parting
pressure.
4. If you are willing to inject above the parting pressure,
spend some time understand how the fractures will
extend and the consequences.

Oil viscosity ~1000 cp; Temperature 38C;

Depth: 1000 ft; Thickness ~40 ft; Permeability 4-12 D.
101

102

17

Rheology in Porous Media & Mechanical Degradation

Shear thinning occurs below 1 ft/d.
Shear thickening occurs between 1 and 40 ft/d.
Mechanical degradation occurs above ~40 ft/d.

Rheology in Porous Media & Mechanical Degradation

Mechanical degradation occurs above ~40 ft/d.

100
Effluent viscosity, % of
injected viscosity (at 7.3 1/s)

Effective viscosity in porous media

1000
1000-ppm fresh HPAM
1350-ppm fresh HPAM

100

HPAM in Sarah Maria Water (500-ppm TDS),

25C. 4-darcy porous medium.
0.1

10

100

1000

HPAM in Sarah Maria

Water (500-ppm TDS), 25C.
After passing through 4-darcy
porous medium at given flux.

60
50

100

1000

10000

Flux, ft/d
103

104

INJECTIVITY

Injectivity Test of August, 2008, in Well 1M101

Injectant
water
water
water
water
water
water
1000-ppm
polymer

0.05
1000-ppm HPAM
0.04

1350-ppm HPAM

0.03

Predicted polymer injectivity relative

to water, assuming an open-hole
completion.

0.02

10

10000

Assuming an open-hole completion, polymer injectivity should be

1-2% of water injectivity, with our HPAM rheology.
Actual polymer injectivity was 27-62% that of water.
Fractures were open during polymer injection.

Injectivity relative to water

1350-ppm HPAM
70

40

Flux, ft/d

1000-ppm HPAM

80

10
0.01

90

Injection
rate, BPD
100
650
125
650
175
650

BHP,
psi
553
845
482
737
471
638

Injectivity,
BPD/psi
0.28
1.01
0.44
1.21
0.65
1.48

Fracture
status
closed
open
mostly closed
open
mostly closed
open

175

635

0.40

open

Fractures were open during polymer injection

Radial horizontal fractures are expected at 1000-ft depth.
Calculations indicate the maximum radial fracture extension to be

0.01
0
1

10

100

1000

Radius of polymer front, ft

~20 ft. So polymer injectivity is substantially improved without

compromising sweep efficiency.
Polymer and salinity breakthroughs and production performance
indicated no channeling through fractures.

105

106

CONCLUSIONS
2. A strong shear-thickening rheology was observed for
1000-ppm and 1350-ppm HPAM solutions in porous
media. Injectivity analysis revealed that these
solutions were injected above the formation parting
pressure in the Sarah Maria polymer injection wells.

3. Analysis suggested that the fractures extended only a

short distance (~20 ft) from the injection wells and did
not jeopardize sweep efficiency. In contrast, the short
fractures greatly improved polymer injectivity and
reduced concern about polymer mechanical
degradation.

Injectivity is enhanced without

channeling, so long as the fracture
does not extend to the producer.
107

108

18

A DILEMMA FOR POLYMER FLOODING

Effective permeability of the flow path,

darcys .

1. Injecting above the parting pressure is often

necessary for adequate injectivity.
2. If polymer breaks through early, how can you tell if it
is because of a fracture or viscous fingering?
3. If breakthrough occurs from a fracture, you should
decrease the injection rate and/or polymer viscosity.
4. If breakthrough occurs from viscous fingering, you
should increase the polymer viscosity.

MATRIX OR FRACTURE FLOW?

1000

Transit through fractures that cause severe

channeling should occur fastdays or less.
Transit through viscous fingers typically takes
months.

k ~ re2 /(4t p)

100

Fracture flow
probable

10

Matrix flow
probable
1

=1 cp, p=2000 psi, re=1000 ft.

L~2re, which depends on well spacing
0.1
0.1

10

100

Interwell tracer transit time, days

1000

109

110

BREAKTHROUGH TIME FOR VISCOUS FINGERING AS A

FUNCTION OF OIL/POLYMER VISCOSITY RATIO
(from Ivan Kurnia MS thesis, 2014)

SPE 169027
Field vs Laboratory Polymer Retention
Values for a Polymer Flood in the
Tambaredjo Field
R.N. Manichand, Staatsolie Maatschappij
Suriname N.V. and R.S. Seright, New
Mexico Tech

111

112

Polymer bank delay factors associated with polymer retention.

2
Pore volume delay factor

OUTLINE
1. Importance of polymer retention.
2. Literature review of polymer retention.
3. Literature review of inaccessible pore volume
(IAPV).
4. Review of methods to assess polymer retention.
5. Laboratory polymer retention values In
Tambarejo sand (associated with Sarah Maria
polymer flood pilot).
6. Field polymer retention values associated with
Sarah Maria polymer flood pilot in Suriname.

= 0.3
rock = 2.65 g/cm3
IAPV = 0.

1.5

Polymer
Concentration

200 ppm
500 ppm
1000 ppm
1500 ppm
2000 ppm
3000 ppm

0.5

0
1

10

100

1000

Polymer retention, g/g

113

10 g/g & 1500 ppm polymer: delay = 0.04 PV.

100 g/g & 1500 ppm polymer: delay = 0.41 PV.
200 g/g & 1500 ppm polymer: delay = 0.82 PV.

114

19

LITERATURE REVIEW OF INACCESSIBLE PV (IAPV)

LITERATURE REVIEW OF POLYMER RETENTION

1. Reported IAPV values are VERY inconsistent, especially

with respect to permeability dependence.

1. Clay (high-surface-area materials) and iron in the rock

dominate polymer retention.
2. Polymer retention can increase dramatically with
decreasing permeability, especially below 100 md. Most
current polymer floods are applied in very permeable
formations (> 500 md).
3. Most (but not all) polymer retention data suggests that
use of the Langmuir isotherm is inappropriate. Ironically,
most commercial simulators use the Langmuir isotherm.
4. Retention of xanthan is usually less than that of HPAM.
5. The most reliable current means to measure polymer
retention is the double-polymer/tracer-bank method.
6. Retention in the presence of residual oil is ~1/2 half that
without Sor. Wettability has not been established as a key
factor in polymer retention.

2. The available theories for the IAPV phenomenon cannot

explain the magnitude and odd variations of IAPV with
changes in permeability . Experimental limitations?
3. More work is needed to understand IAPV phenomenon.
4. Most current large polymer floods are in reservoirs with
high-permeability sands or sandstones (Daqing: 800 md;
Pelican Lake: 1-3 darcys; Mangala: 5 darcys; Marmul: 15
darcys; Dalia: >1 darcy; Tambaredjo: 4-12 darcys).
5. A conservative approach to design of a polymer flood
would assume that inaccessible pore volume is zero,
especially in multi-darcy sands
115

116

PREFERRED POLYMER RETENTION METHOD

REVIEW OF POLYMER RETENTION METHODS
1. Mass balance on polymer: Polymer slug followed by water.
a. Unfavorable displacement during water injection after
polymer requiring MANY PV of water.
b. Significant errors accumulate from measuring low
polymer concentrations.

C/Co

2. Static method: Sand mixed with polymer solution.

a. Relies on only two measurements of polymer
concentration.
b. Exposes extra mineral area for crushed rock.
c. Does not account for mechanically entrapped polymer.

3. Double polymer/tracer bank method.

a. Two banks injected.
b. Each bank contains both polymer and tracer (KI).
c. ~100 PV of brine injected between the banks.
d. Only the front part of a given breakout curve is used
thus eliminating problems with unstable displacement.
e. IAPV: from area difference between the polymer and tracer
breakout curves for the 2nd bank.
f. Retention: from the area difference between the polymer
and tracer breakout for the 1st bank, after adding IAPV.

tracer
polymer

Retention
- IAPV

IAPV

PV
117

118

Polymer Retention and IAPV

from Laboratory Studies
Tambaredjo Sands, Sarah Maria
Polymer Flood, Suriname
T1 Sand
T2 Sand

Retention,
g/g
0 20
0 20

IAPV

Laboratory polymer retention measurements

use/represent a VERY small part of the reservoir.
Can field measurements be used to obtain more
representative polymer retention values?
Data would be helpful for scale up to a larger project.
1N11
1M10

0 10%
1M09

0 10%

1N061

1M101

What is the best source of reservoir sand?

a. Coring?
b. From the shale shaker during drilling?
c. Sand production from a production well?
d. Synthetic sand?

1N062

1N08

1N06
1N01

1M051
1M04

I
1M052
1I25

119

1M05

~600 cp oil
4-12 darcy sand

The Sarah Maria

Polymer Flood Pilot
Tambaredjo Field,
Suriname
120

20

Injected salinity: 500-ppm TDS.

Formation water salinity: 4700-ppm TDS.
Polymer flood started right after primary production.
Produced water salinity can act as a tracer.

900
800
Produced polymer, ppm

6000
Produced water salinity, ppm TDS

Injected 1000-ppm HPAM from 9/2008 11/2011.

Inected 1350-ppm HPAM from 11/2011 2/2013.
Recommend more frequent polymer sampling.

1N11
1I25
1N06
1M05
1M09
1N01

5000
4000
3000
2000

700
600
500
400

1N11
1I25
1N06
1M05
1M09
1N01

300
200
100

1000

0
2008

2009

2010

2011

2012

2013

2008

2014

2009

2010

2011

2012

2013

2014

2015

Year

Year
121

122

Procedure to Estimate Polymer Retention from Field Data

Procedure to Estimate Polymer Retention from Field Data

1. Assume IAPV = 0.
2. For each producer, use the stabilized salinity data to
establish the fraction of water flow coming from a
nearby injector. (fwtrac = B/A).
3. Use salinity to assign a swept volume between an
injector producer pair.

4.Estimate the rock mass in the swept area:

5.Estimate polymer retention:
900

Produced polymer, ppm

Produced water salinity, ppm TDS

5000

4000

1N11

3000
2000

600

Injected polymer
= 1000 ppm

1N11

500

Cpolyo possibilities:
1. Stabilized produced
polymer concentration
2. 1000 ppm x fwtrac

400
300
200

0
2008

0
2009

700

100

1000

2008

800

6000

2010

2011

2012

2013

2014

2009

2010

2011

2012

2013

2014

2015

Year

Year

123

Parameters for Estimation of

Polymer Retention from Field Data

124

CONCLUSIONS

Production well

1N11

1I25

1N06

1M05

1M09

1N01

Starting salinity,
ppm TDS

4737

4686

4657

4432

4707

3998

Ending salinity,
ppm TDS

1291

1692

1684

2531

2281

1769

Ending polymer,
ppm

634

550

375

226

216

395

fwtrac

0.813

0.708

0.715

0.483

0.577

0.637

Range of
retention values,
g/g

160-517

129-247

53-125

14-337

45-99

50-168

1. A review of the polymer-retention literature revealed that

iron and high-surface-area minerals (e.g., clays)
dominate polymer retention measurements in permeable
rock and sand (>100 md).
2. A review of the literature on inaccessible pore volume
revealed inconsistent and unexplained behavior. A
conservative approach to design of a polymer flood in
high-permeability (>1 darcy) sands would assume that
inaccessible pore volume is zero.
3. Laboratory measurements using fluids and sands
associated with the Sarah Maria polymer flood in
Suriname suggested polymer retention and inaccessible
pore volume values near zero.

Most retention values fall between 50 and 250 g/g

125

126

21

CONCLUSIONS

SPE 164121

4. A procedure was developed using salinity-tracer and

polymer concentrations from production wells to
estimate polymer retention during the Sarah Maria
polymer flood in the Tambaredjo reservoir.
5. Field calculations indicated much higher polymer
retention values than lab tests, typically ranging from ~50
to 250 g/g.

Effective Propagation of HPAM Solutions

through the Tambaredjo Reservoir during
a Polymer Flood

6. Field cores necessarily represent an extremely small

fraction of the reservoir. Because of the importance of
polymer retention, there is considerable value in deriving
polymer retention from field results, so that information
can be used in the design of project expansions.
127

128

Substantial improvements in sweep efficiency can

occur, especially when using very viscous polymer
solutions.

EFFECT OF MOBILITY RATIO ON

AERIAL SWEEP EFFICIENCY

100

1000 cp
polymer

Mobile oil recovered, %

90

M < 1: FAVORABLE

M > 1: UNFAVORABLE

80

100 cp polymer

Two layers,
free crossflow,
linear flow,
k1=10k2,
h1=h2,
1000 cp oil,
1 cp water

70
60
50
40
30

10 cp polymer

1 cp water

20

1-Sor-Swr = 0.76

10
0
0.01

M = (k/)water / (k/)oil

0.1

10

100

Pore volumes of polymer or water injected

129

130

Polyacrylamide or HPAM Polymers

When Displacing Viscous Oils,

Viscous Polymer Solutions May Be
Needed to Improve Sweep Efficiency

[ - CH2 - CH - ]m - [ - CH2 - CH - ]n
C
-O

C
O

acrylate

Viscosity @ 7.3 s-1, cp

1000

100

NH2

acrylamide

High-viscosity
oil

Polymers are more efficient

viscosifiers at high concentrations:
~ C2 (i.e., only 40% more polymer
is needed to double the viscosity).

polymer
solution
degraded
polymer
solution

10

Polymer must remain stable during most

of the transit through the reservoir.

19 million Mw HPAM

1
100

High-viscosity oil

1000
Polymer concentration, ppm

10000

131

132

22

Where does the degradation occur? If polymer

degradation occurs during the first part of the
flood, the polymer flood could be jeopardized.
Our hypothesis:
1. Iron minerals strip any dissolved oxygen from
solution soon after injection (Seright 2010).
2. Fe2+ enters the polymer solution during transit
through the reservoir.
3. Dissolved Fe2+ does not harm HPAM
effectiveness if no dissolved O2 is present.
4. Degradation occurs when HPAM solutions mix
with air during sampling at the producer.
5. Better sampling methods are needed.
133

134

Depletion of dissolved oxygen by

run
reaction withGeochemistry
sand containing
1% pyrite

If both dissolved oxygen and iron are

present, severe polymer degradation
can occur.

5000

Dissolved oxygen,
ppb

Fe2+ + O2 + HPAM

125C
105C
85C
75C
35C
25C

Initial level:
5000 ppb O2

4000
3000
2000
1000
0

0.01

0.1 Time, days

10

Dissolved O2 that entered the reservoir prior to polymer injection will have
been consumed and will not aggravate polymer degradation.
If an O2 leak develops during the course of polymer injection, that O2 will not
compromise the stability of the polymer that was injected before the leak
developed or after the leak is fixed.
Polymer that is injected while the leak is active will be susceptible to
oxidative degradation. OXYGEN REMOVAL IS NECESSARY!
(But O2 can be removed without use of expensive chemicals).

Fe3+ + H2O + degraded HPAM

135

MODELING O2 TRANSPORT THROUGH A RESERVOIR

What if some O2 is present? How long will it take for
reaction with the oil to deplete the O2?

Radius at which dissolved oxygen

is depleted by reaction with oil
1,000 BWPD/ft pay injected,
Sor = 0.3, = 0.3

1000
Exposure time before oxygen
depletion, hrs

Radius of the oxygen front, ft

1000

100
5000 ppb O2
50 ppb O2

10

5 ppb O2

1
50

100

150

136

5000 ppb O2

100
50 ppb O2

10
1,000 BWPD/ft pay injected,
Sor = 0.3, = 0.3

5 ppb O2

200

50

Temperature, C

100

150

200

Temperature, C
137

138

23

New Anaerobic Sampling Method

1. Point the outlet end of the sample cylinder up during
collection at the wellhead.
2. In the lab, if needed, pressurize the sample cylinder
with N2.
3. Flow anaerobic solution into the bottom of the
viscometer cup (and overflow out the top).

139

140

CONCLUSIONS

Improved Sampling Method Results

1. A new method was developed for anaerobically sampling

polymer solutions from production wells in the Sarah
Maria polymer flood pilot project in Suriname. Whereas
previous methods indicated severe polymer degradation,
the improved methods revealed that the polymer
propagated intact over 300 ft through the Tambaredjo
formation. This finding substantially reduces concerns
about HPAM stability and propagation through low- and
moderate-temperature reservoirs.

Well 1N11 1N06

Polymer, ppm 896
465
cp @ 7.3 s-1
Direct aerobic sampling
6
5
New method

32

14

KEY POINT: Minimum HPAM

degradation after flowing >300
feet through the reservoir.
141

142

OXIDATIVE DEGRADATION OF HPAM

SPE 169030

If O2 is present, HPAM degradation depends on

T, pH, EH, and concentrations of Fe2+, O2
scavenger, polymerization impurities, and
carbonate.

If O2 is not present (and divalent cations are

not present), HPAM stability is good,
regardless of the above impurities.

If O2 is re-introduced after a chemical oxygen

scavenger is applied, a redox couple can form
and degrade the polymer.

Effect of Dissolved Iron and Oxygen on

Stability of HPAM Polymers
R.S. Seright, New Mexico Tech
Ingun Skjevrak, Statoil ASA

143

144

24

APPROACHES TO MINIMIZE OXIDATIVE

DEGRADATION IN FIELD APPLICATIONS
1. Do nothing if the temperature is low and no iron is
present in the injection water.
2. Remove any existing O2; dont let O2 enter the flow
stream.
3. Use an anti-oxidant package, including O2 scavenger.
4. Intentionally oxygenate the water to precipitate iron.
Then try to balance EH, pH, and water composition to
prevent formation of a redox couple.

Polymers and Conditions Tested

1. Two polymers: HPAM and HPAM-ATBS.
2. Two salinities: 11%-TDS and 2.85%-TDS.
3. Two temperatures: 23C and 90C.
4. Dissolved O2 concentrations from 0 to 8000 ppb.
5. Dissolved Fe2+ concentrations from 0 to 220 ppm.
6. Dissolved Fe3+ concentrations from 0 to 172 ppm.
7. Storage periods: 7-11 days.
a. Iron minerals in the reservoir will remove any
injected dissolved oxygen within days.
b. Short storage period eliminates complications
from hydrolysis/precipitation with Ca2+.

WHAT IS THE BEST APPROACH?

If iron is present, how much
dissolved O2 is acceptable?
145

O2 depletion increases with higher Fe exposure.

At the end, Fe2+ and O2 appear to co-exist.
Perhaps the polymer chelates Fe2+?

Polymer degradation is low and not sensitive

to Fe2+ if O2 < 200 ppb and temperature is low.

20

Dissolved oxygen after 11 days at

23C, ppb

Viscosity after 11 days at 23C, cp

146

15

Starting Fe2+

10

0 ppm
10 ppm
30 ppm
Nail

2000-ppm HPAM-ATBS,
11%-TDS brine

0
1

10

100

1000

10000

2000-ppm HPAM-ATBS,
11%-TDS brine

1000

Starting Fe2+
0 ppm
10 ppm
30 ppm
Nail

100

10

10000

Starting dissolved oxygen, ppb

10

100

1000

10000

Starting dissolved oxygen, ppb

147

148

The onset of polymer degradation coincided

The onset of polymer degradation coincided

However, the stoichiometry of iron oxidation

with the onset of a rise in Eh.

However, the magnitude of degradation did not
correlate with Eh.

with the onset of a decrease in pH.

predicts an increase in pH.
8

2000-ppm HPAM-ATBS,
11%-TDS brine

-100

pH after 11 days at 23C

Eh after 11 days at 23C, mV

Starting Fe2+

-200

0 ppm
10 ppm
30 ppm
Nail

-300
-400
-500
-600

7.5

Starting Fe2+
0 ppm
10 ppm
30 ppm
Nail

6.5

2000-ppm HPAM-ATBS,
11%-TDS brine

6
1

10

100

1000

Starting dissolved oxygen, ppb

10000

1
149

10

100

1000

Starting dissolved oxygen, ppb

10000
150

25

and insensitive to Fe2+ concentration.

25
20

15

15

Fe2+

10

0 ppm
5 ppm
10 ppm
20 ppm
30 ppm

23C
HPAM-ATBS
2000-ppm HPAM-ATBS,
11%-TDS brine

10

100

1000

0 ppm
5 ppm
10 ppm
20 ppm
30 ppm

23C 2.85%-TDS
90C 2.85%-TDS
23C 11%-TDS
90C 11%-TDS

20

10

15

0
0.1

10
Fe

2+

Fe2+

10

100

1000

0 ppm
5 ppm
10 ppm
20 ppm
30 ppm

2000-ppm HPAM-ATBS,
11%-TDS brine

0
1

concentration, ppm

90C
HPAM-ATBS

10

100

1000

Starting dissolved oxygen, ppb

100

1000

10000

Starting dissolved oxygen, ppb

Viscosity after one week at 90C
cp

10

2000-ppm HPAM-ATBS,
10-ppb dissolved O2 at
start.

2000-ppm HPAM,
11-%TDS brine

10000

Starting dissolved oxygen, ppb

15

23C
HPAM

Fe2+

10

Viscosity after one week at 90C

cp

Viscosity after one week, cp

30

20

20

Viscosity after one week at 23C,

cp

Viscosity after one week at 23C,

cp

With low O2 content, polymer was stable

10000

20

15

Fe2+

10

0 ppm
5 ppm
10 ppm
20 ppm
30 ppm

90C
HPAM
2000-ppm HPAM,
11-%TDS brine

0
1

10

100

1000

10000

Starting dissolved oxygen, ppb

151

152

Concentration (in ppm) of Fe3+ added to 2000-ppm HPAM-ATBS in

11%-TDS brine, 10-ppb dissolved oxygen.
0
ppm

0.344
ppm

1.72
ppm

3.44
ppm

17.2
ppm

34.4
ppm

CONCLUSIONS

172
ppm

1. Between 0 and 30 ppm Fe2+, viscosity losses were

insignificant after one week (at either 23C or 90C) if
initial O2 200 ppb. If initial O2 > 200-ppb, significant
viscosity losses occurred.
2. For high O2 content (>200 ppb), polymer degradation
increased with increased iron exposure.

Addition any concentration of

to a polymer solution forms a gel.
No gels formed during any of our studies with polymer and Fe2+.
3+
Therefore, no Fe formed during our studies with polymer and Fe2+.
Fe3+

3. For HPAM-ATBS at 90C with 10-ppb initial O2, contact

with steel caused viscosity losses of 34.4% in 2.85%-TDS
brine and 31.5% in 11%-TDS brine. In contrast at 23C,
contact with steel caused no significant degradation if O2
1000 ppb.

153

154

Implications for Field Applications

CONCLUSIONS

1. If temperature is low and the water contains no Fe2+,

no oxygen removal is needed. Iron minerals in the
formation will quickly (days) remove the oxygen.

4. When anaerobic or low-oxygen solutions were exposed

to atmospheric oxygen, polymer degradation increased
substantially with increased Fe2+ concentration.

2. If Fe2+ is present in the polymer make-up water, the

water is probably oxygen-free at its source. Keeping
the water oxygen free is the recommended
approachby preventing O2 leaks, better design of
fluid transfer, gas blanketing, gas stripping.

5. Orange gels formed when any concentration (down to

0.344 ppm) of Fe3+ was added. No gels formed during our
studies with Fe2+--suggesting that free Fe3+ did not form.

155

156

26

Why bother worrying about degradation?

How much are you spending on polymer? $10

million? $100 million?

In polymer flooding, viscosity is money. The

volume of oil you get is directly related to the
viscosity of your polymer in the reservoir.

If you lose 50%-90% of your viscosity, you are

wasting 50%-90% of your investment. Is it ok
to throw away $5-90 million? Wouldnt it be
better to spend a small fraction of that to
remove O2 from the make-up water or prevent
O2 from entering the flow stream?

CHEMICAL/OXIDATIVE
STABILITY OF POLYMERS

157

What is the upper temperature limit for

HPAM use in chemical EOR?

158

You cant stop hydrolysis of PAM or HPAM. At 80C, hydrolysis

will rise to ~60% after 100 days. (Moradi and Doe, Phillips,
SPERE May 1987). Preventing >50% hydrolysis could be done
by incorporating at least 50% AMPS or NVP (SPE 14233).

Above 60C, acrylamide groups hydrolyze to

form acrylate groups.

If the degree of hydrolysis is too high and too

much Ca2+ or Mg2+ is present, HPAM polymers

precipitate.

Temperature, C:
75
88 96 204
Max Ca2+ + Mg2+, mg/L: 2000 500 270 20
(from Moradi-Araghi and Doe, 1987)
159

160

Approaches to mitigating HPAM precipitation:

1. A few hot reservoirs exist with low hardness.
2. Hydrolysis-resistant monomers (AMPS, NVP) can be
incorporated into PAM polymers (Moradi-Araghi, Doe
1987). Need >50% NVP or AMPS. They tend to be
expensive and less effective as viscosifiers.
3. Fresh water or low-hardness HPAM solutions can
provide efficient sweep with minimum mixing with
saline brines if polymer mobility is sufficiently low
(Maitin 1992). Requires that mixing and cation
exchange be understood and controlled.
4. Complex the hardness with chelating agents
(Albonico and Lockhart, ENI, SPE 25220). Expensive.
Must still prevent mixing with the formation water.
May not provide any benefit over just using seawater.
161

WILL A CO/TER-POLYMER WITH AMPS OR

NVP BE MORE STABLE THAN HPAM?
AMPS or NVP copolymers are more
expensive, give lower Mw, and are less
effective viscosifiers than HPAM.
AMPS or NVP copolymers with <45%
AMPS/NVP will not be more stable (to either
O2 or precipitation) than HPAM. [Doe, SPERE
Nov. 1987; Parker and Lezzi, Polymer 34(23)
1993; Seright SPEJ June 2010].

162

27

If divalent cations are not a problem, what is the

upper temperature limit for HPAM use in EOR?
Maximizing polymer stability requires
minimizing oxygen contact.
Most reservoirs produce water with no
detectable dissolved oxygen.
Oxygen-free EOR solutions can readily be
prepared in the field by (1) preventing leaks,
(2) gas blanketing tanks and mixing facilities,
(3) gas stripping if necessary, (4) adding
chemical oxygen scavengers if necessary.
Lab record to date: Shupe (1981) reported a 13%
viscosity loss after 250 days at 105C when a
chemical oxygen scavenger was used.

Preparing, Storing, and Studying O2-Free Polymer

Solutions in the Laboratory. Our Method:
Prepare solutions in an anaerobic chamber with
10% H2 + 90% N2 circulated through Pd catalyst.
O2 levels measured to <0.001% in the chamber
atmosphere and to <0.1 ppb in solution.
Brine reduced to <0.1 ppb O2 by bubbling
chamber gas into the brine (requires ~ 1 hour).
Polymer stored and mixed in the chamber.
Solutions sealed in 150 ml teflon-lined cylinders.
Solutions stored in 120C-180C baths outside
the anaerobic chamber.
Viscosity at 7.3 s-1, O2, and pH measured inside
the anaerobic chamber (at 25C).

163

164

New Features of Our Method:

Uses a new oxygen meter that measures to 0.1

Anaerobic chamber
CHEMET O2
CHEMET Fe
Temperature baths

parts per billion (ppb) in solution.

Confirmed that our solutions were prepared with

<0.1 ppb O2 and maintained at this level
throughout the study.
No need for chemical oxygen scavengers.

Advantage of our method over previous methods:

Measure viscosity, dissolved O2, and pH on the
SAME sample throughout the study.
Brookfield viscometer
Mettler O2 meter
O2 probe
pH meter
Teflon-lined cylinders
Teflon-wrapped plugs

Disadvantage:

If the storage cylinder leaks, the sample is lost.

165

Time/Temperature Behavior of Polymer Stability

Viscosity decay constant, , is the time for the specific

viscosity to fall to 1/e (0.368) times the original value.

Stability must be studied EITHER at reservoir

temperature for MANY years OR at several

temperatures and use an Arrhenius analysis.
120C
160C
180C with decane

40

100

Specific viscosity, (p-s)/s

Viscosity, cp at 25C, 7.3 s-1

50

140C
160C with decane

30
1,000 mg/L HPAM
0.3% NaCl, < 0.1 ppb O2

20
10
0
0

166

50
100
150
200
250
300
Time stored at given temperature, days
167

120C
160C
180C with decane

= 139 days

10

140C
160C with decane

Projected
= 809 days

=
41 days
=
13 days

1,000 mg/L HPAM

0.3% NaCl,
< 0.1 ppb O2

1
0

50
100
150
200
250
300
Time stored at given temperature, days
168

28

Viscosity decay constant, days

100000

Arrhenius Analysis for HPAM

1/(decay constant), 1/days

0.1

1/ = 9.57x108 e-89140/RT
Rc = -0.967 for 0.1% NaHCO3 or less
0.3% NaCl
0.2% NaCl, 0.1% NaHCO3
3% NaCl
2% NaCl, 1% NaHCO3

0.01

180C

160C

0.0023

140C

0.0024
1/T, 1/K

1/ = 1.425x109 e-91130/RT
Rc = -0.930

100

For either HPAM or PAM-AMPS

in 0.3% NaCl, 3% NaCl, or
0.2% NaCl + 0.1% NaHCO3

10

50

100

150

200

Temperature, C

1/ = 3617 e-47000/RT
Rc = -0.894 for 1% NaHCO3

0.0022

1/ = 8325 e-50200/RT
Rc = -0.925 for
1% NaHCO3

1000

< 0.1 ppb O2

0.001

< 0.1 ppb O2

10000

A given viscosity level can be predicted using: /o = e-t/

Viscosity half-lives for HPAM and PAM-AMPS solutions
0.0025

120C

projected to be > 7 yrs at 100C and ~2 yrs at 120C.

At 105C after 250 days, we predict a 9% viscosity loss,

0.0026

while Shupe (1981) saw a 13% loss.

169

170

CONCLUSIONS

CONCLUSIONS
1. We developed a method to prepare, store, and
test the stability of polymer solutions with <0.1
ppb O2, without using oxygen scavengers.
2. In the absence of dissolved oxygen and
divalent cations, HPAM solution viscosity halflives could be over 7 years at 100C and about
2 years at 120C.
3. Within our experimental error, HPAM stability
was the same with/without oil (decane).
171

CONCLUSIONS
7. By reaction with oil and pyrite, dissolved O2 will be
removed quickly from injected waters and will not
propagate very far into the porous rock of a reservoir.
Any dissolved O2 that entered the reservoir prior to
polymer injection will have been consumed and will
not aggravate polymer degradation. If an O2 leak
develops during the course of polymer injection, that
O2 will not compromise the stability of the polymer
that was injected before the leak developed or the
polymer that is injected after the leak is fixed. Polymer
that is injected while the leak is active will be
susceptible to oxidative degradation. Maintaining
dissolved oxygen at undetectable levels is necessary
to maximize polymer stability. This can readily be
accomplished without the use of chemical oxygen
scavengers or antioxidants.
173

4. A 25% AMPS copolymer showed similar

stability to that for HPAM. Stability results
were similar in brines with 0.3% NaCl, 3%
NaCl, or 0.2% NaCl + 0.1% NaHCO3.
5. At 160C and above, the polymers were more
stable in brine with 2% NaCl + 1% NaHCO3
than in the other brines.
6. Even though no chemical oxygen scavengers
or antioxidants were used in our study, we
observed the highest level of thermal stability
reported to date for these polymers.
172

THERMAL, CHEMICAL, & BIO-DEGRADATION

Both HPAM and xanthan are very susceptible to
oxidative degradation. Fortunately, most
reservoirs contain no free oxygen.
HPAMs C-C main chain is very resistant to
thermal breaking if O2 or free radicals are absent.
Xanthans C-O main chain is susceptible to
hydrolysis above 70C.
HPAMs amide groups are susceptible to
hydrolysis above 60C, leading to polymer
precipitation if Ca2+ or Mg2+ are present.
HPAM is much more resistant to bio-degradation
than xanthan.
174

29

At 80C, xanthan may have sufficient stability if the pH

= 7-9, and O2 = 0. (Seright & Henrici SPERE 1990).

SPE 146087

A COMPARISON OF POLYMER
FLOODING WITH IN-DEPTH
PROFILE MODIFICATION

Xanthan stability at pH = 7-9

is much better than a pH=5.
Xanthan may be worth considering
because you dont have to worry
about mixing in the reservoir.

175

BOTTOM LINE
1. In-depth profile modification is most appropriate for high
permeability contrasts (e.g. 10:1), high thickness ratios
(e.g., less-permeable zones being 10 times thicker than
high-permeability zones), and relatively low oil viscosities.
2. Because of the high cost of the blocking agent (relative to
conventional polymers), economics favor small blockingagent bank sizes (e.g. 5% of the pore volume in the highpermeability layer).
3. Even though short-term economics may favor in-depth
profile modification, ultimate recovery may be considerably
less than from a traditional polymer flood. A longer view
may favor polymer flooding both from a recovery viewpoint
and an economic viewpoint.
4. In-depth profile modification is always more complicated
and risky than polymer flooding.

176

POLYMER FLOODING is best for improving

sweep in reservoirs where fractures are not
important.
Great for improving the mobility ratio.
Great for overcoming vertical stratification.
Fractures can cause channeling of polymer
solutions and waste of expensive chemical.
GEL TREATMENTS are best treating fractures
and fracture-like features that cause
channeling.
Generally, low volume, low cost.
Once gelation occurs, gels do not flow
through rock.

177

POLYMER FLOODING
As the viscosity of the injected fluid increases, sweep
efficiency in the less-permeable layer increases.
http://baervan.nmt.edu/randy/

178

After polymer or gel placement, injected water forms severe

viscous fingers that channel exclusively through the highpermeability layer.
http://baervan.nmt.edu/randy/

179

180

30

ADVANTAGES AND LIMITATIONS

IN-DEPTH PROFILE MODIFICATION

A specialized idea that requires use of a low-viscosity gelant.

ADVANTAGES:
1. Could provide favorable injectivity.
2. Incremental oil from this scheme could be recovered
relatively quickly.

LIMITATIONS:

181

Sophisticated Gel Treatment Idea from BP

In-depth channeling problem, no significant
fractures, no barriers to vertical flow:
BP idea could work but requires sophisticated
characterization and design efforts,
Success is very sensitive to several variables.

1. Will not improve sweep efficiency beyond the greatest

depth of gelant penetration in the reservoir.
2. Control & timing of gel formation may be challenging.
3. Applicability of this scheme depends on the sweep
efficiency in the reservoir prior to the gel treatment.
4. Viscosity and resistance factor of the gelant must not be
too large (ideally, near water-like).
5. Viscosity and resistance factor of the gelant should not
increase much during injection of either the gelant or the
water postflush

BRIGHT WATERA VARIATION ON BPs IDEA

(SPE 84897 and SPE 89391)

Thermal front

high k

low k

Water

Oil

Gelant

182

Gel

Injects small crosslinked polymer particles that

pop or swell by ~10X when the crosslinks break.
Popping is activated primarily by temperature,
although pH can be used.
The particle size and size distribution are such that
the particles will generally penetrate into all zones.
A thermal front appears necessary to make the
idea work.
The process experiences most of the same
advantages and limitations as the original idea.

J. Polym. Sci. & Eng. (April 1992) 7(1-2) 33-43.

183

184

For reservoirs with free crossflow between

strata, which is best to use: Polymer Flooding
or In-Depth Profile Modification?

BRIGHT WATER
Had it origins ~1990.

Using simulation and analytical studies, we examined

oil recovery efficiency for the two processes as a
function of:

Had an early field test by BP in

Alaska.

(1) permeability contrast (up to 10:1),

(2) relative zone thickness (up to 9:1),
(3) oil viscosity (up to 1,000 times more than water),
(4) polymer solution viscosity (up to 100 times more
than water),
(5) polymer or blocking-agent bank size, and
(6) relative costs for polymer versus blocking agent.

Was perfected in a consortium of

Mobil, BP, Texaco, and Chevron in
the mid-1990s.

185

186

31

Polymer Flooding vs. In-Depth Profile Modification

2:1 permeability contrast and thin high-k layer (9h1=h2).
100-cp oil

ASSUMPTIONS
1. Two layers. Layer 1 has high permeability, k1, h1.
Layer 2 has low permeability, k2, h2.
2. Free crossflow between layers.
3. No gravity forces.
4. No capillary forces.
5. Incompressible flow.
6. No dispersion of chemical banks.
7. Water viscosity is 1 cp.
8. 1 PV of water is injected prior to polymer or gelant.
9. Polymer solutions are Newtonian.
10. Retention balances inaccessible pore volume.
11. Gelation occurs instantaneously and reduces k to 0.

10-cp polymer
waterflood
5% HP-PV gel
35% HP-PV gel
90% HP-PV gel

% of mobile oil recovered

95
85
75
65
55

Two layers,
free crossflow,
k1=2k2, 9h1=h2
100-cp oil, 1-cp water.
1 PV waterflood first, followed by polymer
or in-depth profile-modification treatment

45
35
25
15
1

Gel

10

Pore volumes injected

Layer 1, k1 =2k2, 9h1 =h2

Layer 1, k1, h1

Layer 2, k2, h2

Layer 2, k2, h2
187

188

Polymer Flooding vs. In-Depth Profile Modification

5:1 permeability contrast and thin high-k layer (9h1=h2).
100-cp oil
100

85
75

% of mobile oil recovered

10-cp polymer
waterflood
5% HP-PV gel
35% HP-PV gel
90% HP-PV gel

95
% of mobile oil recovered

Polymer Flooding vs. In-Depth Profile Modification

10:1 permeability contrast and h1=h2.
100-cp oil

65
55
Two layers,
free crossflow,
k1=5k2, 9h1=h2
100-cp oil, 1-cp water.
1 PV waterflood first, followed by polymer
or in-depth profile-modification treatment

45
35
25

Pore volumes injected

80
70

k1=10k2, h1=h2,
100-cp oil, 1-cp water.
1 PV waterflood first,
followed by polymer or
profile-modification treatment

60
50
40

15
1

10-cp polymer
waterflood
5% HP-PV gel
35% HP-PV gel
90% HP-PV gel

90

10

Pore volumes injected

Layer 1, k1 =5k2, 9h1 =h2

10

Layer 1, k1 =10k2, h1 =h2

Layer 2, k2, h2

Layer 2, k2, h2
189

190

Polymer Flooding vs. In-Depth Profile Modification

10:1 permeability contrast and 3h1=h2.
100-cp oil
10-cp polymer
waterflood
5% HP-PV gel
35% HP-PV gel
90% HP-PV gel

85
75

95
% of mobile oil recovered

95
% of mobile oil recovered

Polymer Flooding vs. In-Depth Profile Modification

10:1 permeability contrast and thin high-k layer (9h1=h2).
10-cp oil

65
55
k1=10k2, 3h1=h2,
100-cp oil, 1-cp water.
1 PV waterflood first,
followed by polymer or
profile-modification treatment

45
35
25
1

Pore volumes injected

10
Layer 1, k1 =10k2, 3h1 =h2

waterflood
10-cp polymer
40-cp polymer
100-cp polymer
5% HP-PV gel
35% HP-PV gel
90% HP-PV gel

85
75
65
55
45

Two layers,
free crossflow,
k1=10k2, 9h1=h2.
10-cp oil, 1-cp water.

1 PV waterflood first,
followed by polymer or
in-depth profile-modification treatment

35
25

Layer 2, k2, h2
191

Pore volumes injected

10

192

32

Polymer Flooding vs. In-Depth Profile Modification

10:1 permeability contrast and thin high-k layer (9h1=h2).
100-cp oil

Polymer Flooding vs. In-Depth Profile Modification

10:1 permeability contrast and thin high-k layer (9h1=h2).
1000-cp oil

100
waterflood
10-cp polymer
40-cp polymer
100-cp polymer
5% HP-PV gel
35% HP-PV gel
90% HP-PV gel

75
65

k1=10k2, 9h1=h2,
100-cp oil, 1-cp
water.

55
45
35

80
70
60
50

1 PV waterflood first,
followed by polymer
or in-depth profilemodification
treatment

40
30
20
0
1

15
1

Pore volumes injected

193

194

Relative Profit = Oil value Water Cost Polymer/Gel Cost

HPAM cost = $1.50/lb, BW cost = $5.71/lb.

Water cost = $0.25/bbl, Oil price = $50/bbl.
0.1%, 0.2%, & 0.3% HPAM give 10, 40, & 100 cp, respectively.

HPAM cost = $1.50/lb, BW cost = $5.71/lb.

Water cost = $0.25/bbl, Oil price = $50/bbl.
0.1%, 0.2%, & 0.3% HPAM give 10, 40, & 100 cp, respectively.

k1=10k2, h1=9h2,
10-cp oil, 1-cp water.

k1=10k2, h1=9h2,
100-cp oil, 1-cp water.
1 PV waterflood first,
followed by polymer
or in-depth profile
modification
treatment

Relative profit

10
10
recovery@5 PV
75.2%
92.6%
98.5%
99.7%
81.3%
82.2%
83.3%
85.8%

waterflood
10-cp polymer
40-cp polymer
100-cp polymer
5% HP-PV gel
15% HP-PV gel
35% HP-PV gel
90% HP-PV gel

0
0

10

Pore volumes injected

10

Relative Profit = Oil value Water Cost Polymer/Gel Cost

15

1000-cp oil, 1-cp

water. k1=10k2,
9h1=h2.

10

1 PV waterflood first,
followed by polymer or
in-depth profile-modification treatment

25

Relative profit

waterflood
10-cp polymer
40-cp polymer
100-cp polymer
5% HP-PV gel
35% HP-PV gel
90% HP-PV gel

90
% of mobile oil recovered

85

39.2%
64.4%
89.8%
99.7%
Recovery 51.8%
@5 PV 53.1%
55.7%
59.5%

0
10

Pore volumes injected

waterflood
10-cp polymer
40-cp polymer
100-cp polymer
5% HP-PV gel
15% HP-PV gel
35% HP-PV gel
90% HP-PV gel

10

Pore volumes injected

195

196

Relative Profit = Oil value Water Cost Polymer/Gel Cost

HPAM cost = $1.50/lb, BW cost = $5.71/lb.
Water cost = $0.25/bbl, Oil price = $50/bbl.
0.1%, 0.2%, & 0.3% HPAM give 10, 40, & 100 cp, respectively.

If the popping-agent bank size is small (e.g., 5% HP-PV),

performance is not very sensitive to chemical cost.

recovery@5 PV
17.1%
35.7%
63.5%
85.1%
27.5%
28.7%
30.9%
34.5%

10

waterflood
10-cp polymer
40-cp polymer
100-cp polymer
5% HP-PV gel
15% HP-PV gel
35% HP-PV gel
90% HP-PV gel

15

k1=10k2, h1=9h2,
1000-cp oil, 1-cp water.
1 PV waterflood first,
followed by polymer
or in-depth profile
modification treatment

Relative profit

15

Relative profit

% of mobile oil recovered

95

k1=10k2, h1=9h2, 10-cp oil, 1-cp water.

1 PV waterflood first, followed by polymer
or 5% in-depth popping-agent treatment

10

recovery@5 PV
92.6%
75.2%
81.3%
81.3%
81.3%

10-cp polymer
waterflood
5% HP-PV gel, 0.5X cost
5% HP-PV gel, 1X cost
5% HP-PV gel, 1.5X cost

0
0

Pore volumes injected

10

10

Pore volumes injected

197

198

33

INJECTIVITY CONSIDERATIONS

BRIGHT WATERRESULTS (SPE 121761)

BP Milne Point field, North Slope of Alaska.

Injected 112,000 bbl of 0.33% particles.
Recovered 50,000 bbl of incremental oil.
0.39 bbl oil recovered / lb of polymer (compared with
~1 bbl oil / lb polymer for good polymer floods).

199

1. Concern about injectivity losses has been a key motivation

that was given for choosing in-depth profile modification
over polymer flooding.
2. However, most waterflood and polymer flood injectors are
thought to be fractured.
3. Fractures are especially likely to be present in hot
reservoirs with cold-water injectors (Fletcher et al. 1991).
4. Even when injecting viscous polymer solutions (i.e., 200300 cp), injectivity has not been a problem in field
applications (Wang 146473) because fractures extend to
accommodate the viscosity and rate of fluid injected.
5. Concerns when injecting above the parting pressure are to
not allow fractures to (1) extend so far and in a direction
that causes severe channeling and (2) extend out of zone.
6. Under the proper circumstances, injection above the
parting pressure can significantly (1) increase injectivity
and fluid throughput, (2) reduce the risk of mechanical
degradation for HPAM, and (3) increase pattern sweep. 200

ADDITIONAL CONSIDERATIONS
1. For small banks of popping-agent, significant mixing and
dispersion may occur as that bank is placed deep within
the reservoirthus, diluting the bank and potentially
compromising the effectiveness of the blocking agent. .
2. Since the popping material provides a limited permeability
reduction (i.e., 11 to 350) and the popped-material has some
mobility, the blocking bank eventually will be diluted and
compromised by viscous fingering.
3. If re-treatment is attempted for a in-depth profilemodification process, the presence of a block or partial
block in the high-permeability layer will (1) divert new
popping-agent into less-permeable zones during the
placement process and (2) inhibit placement of a new block
that is located deeper in the reservoir than the first block.
These factors may compromise any re-treatment using indepth profile

BOTTOM LINE
1. In-depth profile modification is most appropriate for high
permeability contrasts (e.g. 10:1), high thickness ratios
(e.g., less-permeable zones being 10 times thicker than
high-permeability zones), and relatively low oil viscosities.
2. Because of the high cost of the blocking agent (relative to
conventional polymers), economics favor small blockingagent bank sizes (e.g. 5% of the pore volume in the highpermeability layer).
3. Even though short-term economics may favor in-depth
profile modification, ultimate recovery may be considerably
less than from a traditional polymer flood. A longer view
may favor polymer flooding both from a recovery viewpoint
and an economic viewpoint.
4. In-depth profile modification is always more complicated
and risky than polymer flooding.

201

COLLOIDAL DISPERSION GELS (CDG)

(ALUMINUM-CITRATE-HPAM, but sometimes low
concentration Cr(III)-ACETATE-HPAM)

202

CLAIM 1:

Two central claims have been made over the past 28

years. Two additional claims are more recent:
1. The CDG only enters the high-permeability, watered-out
zonesthus diverting subsequently injected water to
enter and displace oil from less permeable zones.
2. The CDG acts like a super-polymer flooding agentadd
~15-ppm Al to 300-ppm HPAM and make it act like a
much more viscous polymer solution.
3. The CDG mobilizes residual oil.
4. The CDG acts like Bright Water (In depth profile
modification)
203

The CDG only enters the high-permeability, watered-out

zonesthus diverting subsequently injected water to
enter and displace oil from less permeable zones.
Why should the CDG not enter low-permeability zones in
proportion to Darcys law? IT DOES!
Like any gelant, you must ask (1) how far does the gelant
penetrate into ALL zones and (2) once the gel is in
place, how much permeability reduction does it cause
in each and every zone? A positive diversion will ONLY
occur if the high-permeability zone is damaged more
than the low-permeability zones.
Claim 1 is nonsense.

204

34

Al(III)-citrate-HPAM gels act like other gels.

3,000

CLAIM 2:

300-ppm HPAM, 15-ppm Al(III) as citrate,

0.5% KCl, 41C, 707-md Berea sandstone
15.8 ft/d (6.7 PV/hr) injection rate.

Resistance factor

1,000

The CDG acts like a super-polymer flooding agentadd

~15-ppm Al to 300-ppm HPAM and make it act like a
much more viscous polymer solution.
This would be a major advance if it was true.

300

1st core
section

100
30
10

2nd core
section

For all gelants to date, before the gelation time, the fluid
flows into porous rock just like a polymer solution.
After gelation, the gel does not flow through porous
rock or sand at any practical rate or pressure gradient.
Do CDGs act differently?

Pore volumes of gelant injected

10

DOE/BC/14880-10 (March 1995) 51-64.

During first 6 PV of injection, gelant shows the same resistance

factor as polymer solution with no crosslinker.
Gelant is ~ 2 hrs old when gel particles begin being filtered out by
the first core section.

205

206

CLAIM 2:

PROPERTIES OF AVAILABLE GELANTS/GELS

1. Early in the gelation process, gelants
penetrate readily into porous rock.

The CDG acts like a super-polymer flooding agentadd

~15-ppm Al to 300-ppm HPAM and make it act like a
much more viscous polymer solution.

2. After gelation, gel propagation through

porous rock is extremely slow or negligible.

This would be a major advance if it was true.

3. The transition between these two conditions

is usually of short duration.

For all gelants to date, before the gelation time, the fluid
flows into porous rock just like a polymer solution.
After gelation, the gel does not flow through porous
rock or sand at any practical rate or pressure gradient.

SPERE (Nov. 1993) 299-304; IN SITU 16(1)

(1992) 1-16; and SPEPF (Nov. 1995) 241-248.

CDGs DO NOT act differently. ALL objective researchers

who have tested this concur.
207

208

GEL TREATMENTS ARE NOT POLYMER FLOODS

Crosslinked polymers, gels, gel particles, and
colloidal dispersion gels:

Distinction between a blocking agent

And a mobility control agent.

Are not simply viscous polymer solutions.

Do not flow through porous rock like polymer
solutions.

For a mobility control agent,

penetration into low-k zones
should be maximized.

Do not enter and plug high-k strata first and

progressively less-permeable strata later.

For a blocking agent,

penetration into low-k zones
should be minimized.

Should not be modeled as polymer floods.

209

210

35

COLLOIDAL DISPERSION GELS: FIELD RESULTS

CATEGORY A

VENDORS CLAIM THAT FIELD RESULTS

PROVE THE EFFECTIVENESS OF
COLLOIDAL DISPERSION GELS.

The treated wells contained no fractures or linear

flow features.

However, detailed examination of these

For these cases, the aluminum was (fortunately)

field results reveals that alternative

explanations are far more credible.

removed (by adsorption on rock) so the polymer

could propagate through the formation and
provide some benefit as a polymer flood.

The field results fit into one of several

Since the aluminum provided no benefit, the

categories.

money spent on aluminum citrate would have

been more effectively spent on more polymer.

211

COLLOIDAL DISPERSION GELS: FIELD RESULTS

CATEGORY B

212

COLLOIDAL DISPERSION GELS: FIELD RESULTS

CATEGORY C (vendor usually denies this one)

The reported benefits and/or increases in oil

recovery had nothing to do with the colloidal

dispersion gels.

The treated wells contained fractures or fracturelike features (despite claims to the contrary).

In some cases, the reported benefits for particular

For these cases, the gels may have provided some

wells and fields occurred because of other

changes or improvements that were implemented.

benefit from partially plugging the fractures.

For moderate to wide fractures, other types of gels

In other cases, no real benefit occurred. The

would have been more effective.

reported benefit was an artificial result of an overly

pessimistic projection of the pre-treatment decline
curve and/or an overly optimistic assignment of
incremental oil to the gel treatment.
213

214

COLLOIDAL DISPERSION GELS: FIELD RESULTS

CATEGORY D

The treated wells experienced general plugging of

CLAIM 3:

all open zones and flow paths. From an areal view,

these wells were key to water channeling.

The CDG reduces residual oil saturation.

By reducing the flow capacity of the treated wells,

Wang Demin and his group also claim that high Mw HPAM
polymers reduce Sor. If you want to prove that CDG
reduces Sor, you must make the comparison against
polymer with no crosslinker.

areal pressure gradients were altered so water

injected into OTHER (non-treated) wells pushed
incremental oil toward offset production wells.

This benefit could be realized by any means that

reduced the flow capacity of the treated wells.

Well flow capacity can usually be reduced more

cost-effectively using other gels and methods.

215

216

36

CLAIM 4:
The CDG acts like Bright Water (In-depth profile
modification).
As designed by BP, the Bright Water process required a
substantial amount of reservoir characterization,
engineering, product development, and timing. It is a
complex process, but has a legitimate, documented,
tested, science-based application history. Where is this
for CDGs?
Bright Water has specific testing that demonstrates the
conditions and timing for popping of the material.
CDGs reaction time with Al or Cr appears to be hours
even at low temperatures. What is the science/
engineering basis for CDG placement?
Claiming that something is true (without testing the claim)
does not make it true.

COLLOIDAL DISPERSION GELS

Have enjoyed remarkable hype, with claims

of substantial field success.

Would revolutionize chemical flooding if the

claims were true.

Currently, no credible evidence exists that

they flow through porous rock AND provide

an effect more than from just the polymer
alone (without crosslinker).
Considering the incredible claims made for
CDGs, objective labs ought to be able to
verify the claims. So far, they have not.

217

218

PROBLEMS WITH PRODUCED POLYMER

SURFACE ISSUES

Excessive wear for sucker rods (SPE 77496).

Emulsions that are difficult to break.
Fouling of heat exchangers & fire tubes (SPE
14110, SPE 144322).

Efficiency reductions for hydrocyclones and gas

floatation units (SPE 95343).

Plugging filters (SPE 144277).

Inability to reuse produced water for polymer flooding.
POTENTIAL SOLUTION: Improve sweep to delay
polymer breakthrough:
Increase polymer concentration & viscosity.
Gel treatments to reduce severe channeling.
Separate layer injection.
219

Produced water treatment and re-injection

Wang Demin et al. SPEPF

(2004) SPE 77496
Techniques were developed
using modified sucker rods to
reduce pump resistance and
frictional wear. The period of
pump examination can be
increased to 696 days from 277
days.
Produced HPAM solutions (500
ppm) reduced the service life of
centrifugal pumps by 50%.

220

Focus on the polymer content in the produced water, settling

techniques, filtration and de-oiling, with horizontal flow applied
to produced water treatment and re-injection.

Flocculating settlement

centralizer
produced
water

aggravation

natural de-oil

pump with
lower rub
resistance

buffering tank

Water recovery pump

oil pump

oil tank

booster pump

outside pump

water recovery pond

backwash tank

Flow illustration for produced water treatment

221

Part 6: Additional techniques

222
2008 IOR [email protected]

37

Daqing Mixing and Injection (from D.

Wang, SPEREE 2009, SPE 114342)

For the gravity settling tank:

the oil content < 1000 mg/L in the
inlet water, and the oil content and
suspended solids elimination rate
are 30% 50% for the outlet water.

Most viscosity loss occurred

from
the
high
pressure
injection pumps and mixing
system to the near-well bore
amounting to about 70% of the
total loss.

For the coagulation settling tank:

mix station
water

mature tank
dispersion

transfer pump

water injection station

store tank

Injection pump

the oil content and suspended

solids content < 50 mg/L for the
outlet water.

mass

store tank

Injection for individual

pump and well

Injection water pump

water
resource

injectors

223

Flow illustration for polymer injection

Part 6: Additional techniques

224
2008 IOR [email protected]

SPECIAL ISSUES ASSOCIATED WITH USING

VISCOELASTIC HPAM SOLUTIONS
Wang Demin et al. SPEPF (2004) SPE 77496

SPECIAL ISSUES ASSOCIATED WITH USING

VISCOELASTIC HPAM SOLUTIONS
Wang Demin et al. SPEPF (2004) SPE 77496

Problems with triplex pumps with HPAM:

High vibration.
10-15% lower pump efficiency.
15% viscosity loss from shear degradation.

Problem: Pumping 0.5% HPAM solutions

substantially increases vibration, especially
upstream of pumps.

Solution: Re-design the pumps.

Decrease valve seat area.
Adjust the angle of the valve seat.
Increase inner cylinder diameter
Decrease dead-end volume.

Solution: Use large diameter pipes, avoid Ts.

225

226

Daqing Mixing and Injection (from D.

Wang, SPEREE 2009, SPE 114342)

SPECIAL ISSUES ASSOCIATED WITH USING

VISCOELASTIC HPAM SOLUTIONS
Wang Demin et al. SPEPF (2004) SPE 77496

chemical stability :

Problem: Inefficient polymer mixing in tanks.

protective package (chelating agent), stainless steel

pipeline, nonmetal tanks etc.

Solution: Re-designed mixing blades reduced energy

requirements 80% and reduced mixing time by 1.5-2
hours.

mechanical degradation:
pipeline with low flow rate, electrical-magnetic flow meter,
low speed mixer, etc

Problem: 10-30% shear degradation in static mixers.

biological degradation :

Solution: Remove the static mixer.

protective package (bactericide)formaldehyde.

227

228

38

Daqing Mixing and Injection (from D.

Wang, SPEREE 2009, SPE 114342)
Drainage volume of perforating channels can be
increased
with
large
diameter
perforators.
Alternatively, polymer viscosity degradation can be
reduced by reducing the injection pressure drop.
Index of large diameter perforations
Perforator

diameter

density

mm

spm

Concrete target
bullet

diameter

depth

mm

mm

500

83DP25

83

16

DP41RDX-1

10.4

89DP25

89

16

DP41RDX-1

10.2

543

102DP32

102

16

DP44RDX-1

11.6

639

102BH44

102

12

BH64RDX-1

24.4

242
229

230

231

232

ASSOCIATING POLYMERS -- Concepts

Relatively small polymers with associating groups

SOME OTHER APPROACHES
FOR IMPROVED MOBILITY
CONTROL

Associating polymers.
Gel particulates (crosslinked

(e.g., hydrophobes) viscosify solutions like polymers

with much higher molecular weights.
Ideally, lower Mw polymers could improve stability.
Ideally, associating polymers could be more costeffective (i.e., if lower concentrations are needed to
achieve high solution viscosities).
HPAM

polymers). (Could be emulsions

or other particulates, also).
Foams and other non-polymers.
ASSOCIATING
POLYMER
233

234

39

ASSOCIATING POLYMERS -- Problems

As concentration increases, viscosity of solutions of

associating polymers increases much more quickly

than for normal polymers.
Achieving a PARTICULAR viscosity is more difficult.
Small variations in concentration cause large
variations in viscosity.
Performance is sensitive to oil, salt, and temperature.

ASSOCIATING POLYMERS -- Problem

EXCESSIVE SHEAR THICKENING IN POROUS MEDIA.

At low flow rates, some associating groups bond within

Viscosity, mPa-s

1000

100

Associating
polymer

HPAM

a given polymer, while others bond between separate

polymer molecules.
At high flow rates, the polymer stretches out, exposing
more associating groups to other polymers.
If too much bonding occurs between different polymer
molecules, gelation occurs and flow stops.

10

SO PERFORMANCE CAN BE SENSITIVE TO FLOW RATE.

1
0.01

0.1

Polymer concentration, %

1
235

236

USE OF PARTICULATES (as a blocking agent)

One objective is to inject particles that are:
small enough to flow freely into high-k zones,
large enough not to enter low-k zones, and
become immobile to divert water into oil zones.
Low k

Distinction between a blocking agent

And a mobility control agent.

Particles

For a blocking agent,

penetration into low-k zones
should be minimized.

For a mobility control agent,

penetration into low-k zones
should be maximized.

Oil
High k
Water
237

USE OF PARTICULATES (for mobility control)

A different objective is to inject particles that:
deform as they extrude through pore throats,
reduce water mobility, and
Imitate a polymer flood.

USE OF PARTICULATES -- Problems

Particles are not all the same size.
Pores are not all the same size.
Some particles will enter most or all pores.
Permeability reduction may be greater in
low-k pores than in high-k pores.
0.1

0.1
18 m

Oil
High k

low-k

high-k

pore

pore

size

size

Probability density

Particles
Probability density

Low k

238

Water

high-k

pore

pore

size

size

00
0

239

low-k

10
20
Particle size, m

30

40

10
20
Pore size, m

30

40

240

40

1
10

100

initial rock permeability, md

1000
241

IMPERMEABLE BARRIER

Polymer
Surfactant,water,
gas formulation
IMPERMEABLE BARRIER

Foam

oil

Low k
strata

High k
water strata
oil

Low k
strata

High k
water strata

Producer

10

High k
strata

water

Producer

IMPERMEABLE BARRIER

Polymer
Injector

Permeability reduction factor

100

Low k
strata

oil
Injector

Particles tend to block small pores more

than large pores.
This bad for both polymer floods and
blocking agent treatments.

Injector

Producer

If barriers prevent cross flow between strata, foams could

provide better sweep efficiency than polymer solutions.

USE OF PARTICULATES -- Problems

242

PROBLEMS WITH FOAMS

Can Polymers Reduce

Sor Below that for
Waterflooding?

For various reasons, foam stability may

not be sufficient.
Foam may not propagate as desired.
The desired level of mobility reduction
may be difficult to achieve. (If mobility is
too high, sweep is bad. If mobility is too
low, injectivity is bad).

243

244

Can viscoelastic polymer solutions reduce the

Sor below that for waterflooding?.
1. Daqing says yes; UT Austin says maybe not.
2. Does it matter for viscous oils? (yes)

Sor Reduction by Polymers: Bottom Line

1. It does mattereven for viscous oils.
2. Primarily, true Sor reduction has been seen in
non-water wet cores.
3. No agreement exists on the mechanism for the
reduction.

245

246

41

PREVIOUS LITERATURE: Water- Wet Cores

Conventional wisdom within the petroleum industry is

LITERATURE:
Cores not water wet

Wang: Daqing HPAM solutions reduced S

that the ultimate residual oil saturation (Sor) for a

polymer flood is the same as that for a waterflood
(Tabor 1969, Lake 1989).

Polymers have a negligible effect on oil-water

interfacial tension, so no reduction of Sor is expected,

compared with waterflooding.

or from 36.8%
(with waterflooding) to 21.75% (for polymer flooding)
using a constant capillary number under oil-wet,
weakly oil-wet, and mixed-wet conditions.
Schneider and Owens (1982): HPAM reduced Sor in oilwet cores up to 8.4%.

Water-wet cores

Zaitoun and Kohler (1987, 1988): PAM reduced S

Several previous literature reports are consistent with

this view in water-wet cores, especially with Berea and

Bentheim sandstone (Schneider and Owens 1982,
Pusch et al. 1987, Wreath 1989).

or by
3% in water-wet Berea and Vosges sandstones. In
Bentheim sandstone, Pusch et al. (1987) saw 1% to 4%
reductions in Sor with xanthan and a sugar solution.
Differences might not be significant.

247

PREVIOUS LITERATURE: Water- Wet Cores

Huh and Pope View for Water-Wet cores

During polymer flooding, Huh and Pope (2008)

observed Sor reductions (relative to waterflooding)

ranging from 2 to 22 saturation percentage points
using heterogeneous Antolini cores. For
heterogeneous cores, two effects could appear to make
the Sor lower after a polymer flood than after a
waterflood. First, if insufficient water is flushed through
the core to displace mobile oil from less-permeable
pathways, one could be misled by the high water cut to
believe that the core was near Sor. Improved volumetric
sweep during a subsequent polymer flood could
rapidly produce a small spike of mobile oil from the
less-permeable pathways.

248

PREVIOUS LITERATURE: Water- Wet Cores

Huh and Pope View for Water-Wet cores

For polymer flooding in a secondary mode (no prior

waterflood), a lower Sor is reached because oil ganglia

stay connected longer and drain pores of oil more
effectively.

249

Our experiments in homogeneous cores

77-cm long, 10-darcy porous polyethylene

250

HPAM polymer as a tertiary flood:

190-cp North Slope crude. Polyethylene core.

At S initially. All floods at fixed capillary number.
10 PV brine, followed by 11 PV 10-cp HPAM.
S reduced by at least 4 saturation percentage points.

Hydrophobic (oil wet)

Homogeneous (based on tracer results).

wr

or

80
75

1000ml/hr
0.8

Cumulative Crude Oil Recovery, %

Normalizedtracerconcentration(C/C0)

1
0.9

1500ml/hr
2000ml/hr

0.7

500ml/hr

0.6
0.5
0.4
0.3
0.2
0.1
0

70
65
60
55
50
45
40
35

Waterflood (Lab Data)

30

10-cp Polymer Flood (Lab Data)

25

100-cp Polymer Flood (Lab Data)

20

Waterflood (Fractional Flow)

15
10
5

0.5

1.5

2.5

0
0

Porevolumesoftracerinjected
251

10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25

Pore Volumes Injected

252

42

HPAM polymer as a secondary flood:

HPAM polymer as a tertiary flood:

190-cp North Slope crude. Polyethylene core.

At S initially. All floods at fixed capillary number.
Waterflood first. Re-saturate to S . Then 10-cp HPAM.
S reduced by at least 6 saturation percentage points.

190-cp North Slope crude. Dundee sandstone core.

At S initially. All floods at fixed capillary number.
10 PV brine, followed by 10-cp HPAM.
S reduced by ~2 saturation percentage points.

wr

wr

wr

or

or

75

Cumulative Crude Oil Recovery, %

70
65
60
55
50
45
40
35

Waterflood (Lab Data)

30

Waterflood (Fractional Flow)

25

10-cp Polymer Flood (Lab Data)

20

10-cp Polymer Flood (Fractional Flow)

15

100-cp Polymer Flood (Lab Data)

10
5
0
0

10

11

12

13

14

15

Pore Volumes Injected

253

254

Papers on Sor Reduction Using Polymers

1. Wang Demin et al. SPE 153070, 146473, 144294,
127453, 114335, 109228, 101950, 88456, 72123.
2. Huh and Pope. SPE 113417.
3. Cottin et al. SPE 169692.
4. Vermolen et al. SPE 169681, IPTC 17342.
5. Afsharpoor et al. SPE 169037.
6. Urbissionva et al. JCPT 49(12) 2010: 49-56.
7. Schneider and Owens. SPE 9408.
8. Kohler and Zaitoun. SPE 16274, 18085.

Sor Reduction by Polymers: Bottom Line

1. It does mattereven for viscous oils.
2. Primarily, true Sor reduction has been seen in
non-water wet cores.
3. No agreement exists on the mechanism for the
reduction.

Bottom Line: No agreement exists on the

mechanism for the reduction or when it occurs.
255

256

257

258

POLYMER FLOODING is best for improving

sweep in reservoirs where fractures are not
important.
Great for improving the mobility ratio.
Great for overcoming vertical stratification.
Fractures can cause channeling of polymer
solutions and waste of expensive chemical.
GEL TREATMENTS are best treating fractures
and fracture-like features that cause
channeling.
Generally, low volume, low cost.
Once gelation occurs, gels do not flow
through rock.

43

POLYMER FLOOD PILOT DESIGN ISSUES

POLYMER FLOOD PILOT DESIGN

What are the pilot objectives?

Gain experience mixing and injecting polymer.

Enhance reservoir description.
Assess water quality issues.
Test polymer injectivity.
Optimize injection rate and concentration.
Assess polymer degradation issues.
Assess polymer retention.
Assess reservoir sweep and oil recovery.
Assess production problems.
Look for surprises.
???

259

Reservoir description. Fluid properties.

Well spacing? Pattern? Number of wells?
Horizontal or vertical wells? Well completions?
What water source(s) will be used?
Which polymer will be used?
How to achieve adequate water quality?
What injection rate, concentration, & viscosity?
Mixers, tanks, pumps, filters, automation, etc.
Will oxygen be excluded?
Will tracers be used? Pressure transients?
What parameters will be monitored? How often?
Will simulation be used?
???

260

POLYMER FLOOD LAB WORK

Oil viscosity. Water composition(s).

Relative permeability characteristics. Sor. Swr.
Viscosity vs concentration and shear rate in

formation water and the target makeup water for

the polymers under consideration at surface and
reservoir temperatures.
Polymer rheology in rock. Shear degradation.
Polymer oxidative/chemical degradation.
Polymer retention and inaccessible pore volume.
Microbial degradation if using biopolymers.
Polymer compatibility with other chemicals.
???
261

losses into these can radically affect success.

Are fractures present that could cause severe

channellng of the injected chemicals? If so, gel

treatments or pattern realignment may be needed
before polymer flooding.
Can fractures (induced or natural) be exploited to
enhance injectivity and sweep efficiency?
What pressures can be tolerated without
compromising the reservoir seals?
Will the reservoir lithology preclude polymer
propagation? High Mw polymers dont like low
permeability or high clay content.
Layering & k contrast impact needed viscosity. 263

FLUID PROPERTIES & RELATIVE PERMEABILITIES

Need oil & water viscosity at reservoir conditions.

Need Sor and Swr to determine oil target.
Endpoint mobility ratio gives a conservative value
kr curves are desirable but are they reliable?
1

Relative permeability

RESERVOIR DESCRIPTION

Is an aquifer or gas cap present? Polymer and oil

262

End
Point kro

0.1

End
Point krw

M = (krw/w) / (kro/o)

0.01

Possible
Displacement
front krw

0.001

krw
kro

0.0001
0

0.1

0.2

0.3

0.4

0.5

0.6

Water saturation

0.7

0.8

0.9

264

44

 Viscosity depends on shear rate and concentration.

What is the effective shear rate/velocity deep in the

Polymers are more efficient viscosifiers at high

concentrations: ~ C2 (i.e., only 40% more
polymer is needed to double the viscosity).

Viscosity @ 7.3 s-1, cp

10000

reservoir where most oil is displaced?

Viscous oil
polymer floods

1000

Most previous
polymer floods

polymer in
2.52% TDS
brine, 25C

100

diutan
xanthan
19 million Mw HPAM
7 million Mw HPAM

10

1
100

1000

10000

100000

Polymer concentration, ppm

265

Shear thinning can be seen for fresh HPAM solutions at low flux,
especially in low-k cores. However, exposure to high flux or
pressure gradient can reduce or eliminate this effect.

Effect of Polymer Concentration

on 3830S HPAM in a 5120 md Core
HPAM
concentration

Resistance factor

Mw ~18-20 million,
40% hydrolysis,
2.52% TDS, 25C

100

100

2500 ppm
1600 ppm
900 ppm
480 ppm
200 ppm
100 ppm
50 ppm
25 ppm
0 ppm

Resistance factor

1000

10

1
0.1

10
Flux, ft/d

100

2500 ppm HPAM, Mw ~6-8 million, 30% hydrolysis

2.52% TDS, 25C
Shear degradation
eliminates this effect.

10
55-md core, fresh HPAM
269-md core, fresh HPAM
5120-md core, fresh HPAM
46-md core section, degraded HPAM
17.5-md core section, degraded HPAM
viscosity

1
0.001

1000
26
7

HPAM VISCOSITY DECREASES

WITH INCREASED SALINITY

266

0.01

0.1

10-cp
polymer
solution

u (1-)/( k)0.5, ft/d-md0.5

10
26
8

For a given HPAM concentration, HPAM provides 3.5

times the viscosity in 500-ppm-TDS brine than in
5000-ppm-TDS brine.

9X
3X
2X

2.3X

3X

Lee 2009 (SPE 124798).

45

SELECTION OF POLYMER VISCOSITY

Want to make the water flood mobility ratio favorable.

Want to overcome the permeability contrast.
Water

Water
flood:
M = 9.4

Differing Ideas: Inject MORE polymer

Wang Demin (Daqing, China)

oil

Is currently injecting 150-300 cp HPAM solutions

k1/k2= 4

Polymer
flood:
M~1

Polymer, p/w= 10;

Polymer
flood:
M ~ 0.25

Polymer, p/w= 40

in thousands of wells to displace 10-cp oil from

the Daqing reservoir.

oil

HPAM solutions reduced S

or from 36.8% (with

waterflooding) to 21.75% (for polymer flooding)
using a constant capillary number under oil-wet,
weakly oil-wet, and mixed-wet conditions.

k1/k2= 4
oil

Is this effect generally valid?

k1/k2= 4
271

272

INJECTIVITY: BOTTOM LINE

Differing Ideas: Inject LESS polymer

1. For most previous polymer floods with vertical wells,

injection has occurred above the formation parting
(fracture) pressureeven though the operators
insisted that they did not.
2. This is not bad, so long as fracture extension is
controlled so that fractures dont (a) let fluids flow
out of zone or (b) extend far enough to cause
channeling.
3. Be realistic. If you cant live with the injectivity
reduction associated with a viscous fluid, dont insist
that you are going to inject below the parting
pressure.
4. If you are willing to inject above the parting pressure,
spend some time understand how the fractures will
extend and the consequences.

Relative permeability arguments:

Actual displacement mobility ratio is the aqueous

mobility at the displacement front divided by oil
bank mobilitywhich is less than the endpoint
mobility ratio.

Some coreflood work indicates that an efficient

displacement can occur with a surprisingly low

polymer concentration.

Do the coreflood results occur because of an

experimental artifact?

273

Rheology in Porous Media & Mechanical Degradation

Shear thinning occurs below 1 ft/d.
Shear thickening occurs between 1 and 40 ft/d.
Mechanical degradation occurs above ~40 ft/d.

0.1% polymer in seawater,

550-md Berea, 25C
Xanthan

Resistance factor

10

1000

HPAM previously forced

through core at 139 ft/d

Open
hole

10

Perforations

0.1

Fractured
well

Deep in
reservoir

1
0.01

1000-ppm fresh HPAM

1000-ppm reinjected after 41.7 ft/d
1350-ppm fresh HPAM
1350-ppm reinjected after 41.7 ft/d

Fresh HPAM

Apparent viscosity in porous

media

100

274

100

1000

10000

100

HPAM in Sarah Maria Water (500-ppm TDS),

25C. 4-darcy porous medium.

Superficial velocity, ft/d

10
0.01
275

0.1

10
Flux, ft/d

100

1000

10000
276

46

Rheology in Porous Media & Mechanical Degradation

Mechanical degradation occurs above ~40 ft/d.

0.05

90
Injectivity relative to water

Effluent viscosity, % of
injected viscosity (at 7.3 1/s)

100

1000-ppm HPAM

80

1350-ppm HPAM
70

HPAM in Sarah Maria

Water (500-ppm TDS), 25C.
After passing through 4-darcy
porous medium at given flux.

60
50
40
1

10

100

1000

1350-ppm HPAM

0.03

Predicted polymer injectivity relative

to water, assuming an open-hole
completion.

0.02
0.01

Injectivity Test of August, 2008, in Well 1M101

Injection
rate, BPD
100
650
125
650
175
650

BHP,
psi
553
845
482
737
471
638

Injectivity,
BPD/psi
0.28
1.01
0.44
1.21
0.65
1.48

Fracture
status
closed
open
mostly closed
open
mostly closed
open

175

635

0.40

open

Fractures were open during polymer injection

Radial horizontal fractures are expected at 1000-ft depth.
Calculations indicate the maximum radial fracture extension to be
~20 ft. So polymer injectivity is substantially improved without
compromising sweep efficiency.
Polymer and salinity breakthroughs and production performance
indicated no channeling through fractures.

10

100

1000

Radius of polymer front, ft

277

Injectant
water
water
water
water
water
water
1000-ppm
polymer

1000-ppm HPAM
0.04

10000

Flux, ft/d

INJECTIVITY for the Suriname Project

Assuming an open-hole completion, polymer injectivity should be
1-2% of water injectivity, with our HPAM rheology.
Actual polymer injectivity was 27-62% that of water.
Fractures were open during polymer injection.

OXIDATIVE DEGRADATION

If O2 is present, HPAM degradation depends on

T, pH, EH, and concentrations of Fe, O2
scavenger, polymerization impurities, and
carbonate (SPE 9299, SPE 129890).

If O2 is not present (and divalent cations are

not present), HPAM stability is good,
regardless of the above impurities.

If O2 is re-introduced after O2 scavenger is

applied, a redox couple can form and degrade
the polymer.

279

APPROACHES TO MINIMIZE OXIDATIVE

DEGRADATION

278

280

CONCLUSIONS From SPE 164121

1. Do nothing if the temperature is low and no iron is

present in the injection water.
2. Remove any existing O2; dont let O2 enter the flow
stream.
3. Use an anti-oxidant package, including O2 scavenger.
(Expensive? Effective?).
4. Intentionally oxygenate the water to precipitate iron.
Then try to balance EH, pH, and water composition to
prevent formation of a redox couple. (Risky?
Expensive?)
281

Polymer produced from most previous polymer floods

indicated severe polymer degradationI believe
because the samples were collected aerobically.

A simple new method was developed for anaerobically

sampling polymer solutions from production wells in
the Sarah Maria polymer flood pilot project in
Suriname.

The improved method revealed that the polymer

propagated intact over 300 ft through the Tambaredjo
formation. No oxygen scavengers or anti-oxidant
packages were used. No pH or oxidation-reductionpotential adjustments were made.
282

47

Recommended Assumptions when

Simulating Polymer Floods

PROBLEMS WITH PRODUCED POLYMER

Excessive wear for sucker rods (SPE 77496).

Emulsions that are difficult to break.
Fouling of heat exchangers & fire tubes (SPE

Assume that low-velocity resistance factors

are given by low-shear rate viscosities.

14110, SPE 144322).

Efficiency reductions for hydrocyclones and gas

DO NOT assume shear thinning behavior for

HPAM at high (near wellbore) velocities.

Assume that residual resistance factor is 1,

unless permeability is low (e.g., < 100 md).

Assume that inaccessible pore volume is

zero.

floatation units (SPE 95343).

Plugging filters (SPE 144277).

Inability to reuse produced water for polymer flooding.
We need solutions after polymer breakthrough.
Improving sweep can delay polymer breakthrough:
Increase polymer concentration & viscosity.
Gel treatments to reduce severe channeling.
Separate layer injection.
283

C/Co

tracer
polymer

Retention
- IAPV

IAPV

Viscosity decay constant, , is the time for the specific

viscosity to fall to 1/e (0.368) times the original value.
100

Specific viscosity, (p-s)/s

PREFERRED POLYMER RETENTION METHOD

3. Double polymer/tracer bank method.
a. Two banks injected.
b. Each bank contains both polymer and tracer (KI).
c. ~100 PV of brine injected between the banks.
d. Only the front part of a given breakout curve is used
thus eliminating problems with unstable displacement.
e. IAPV: from area difference between the polymer and tracer
breakout curves for the 2nd bank.
f. Retention: from the area difference between the polymer
and tracer breakout for the 1st bank, after adding IAPV.

284

120C
160C
180C with decane

= 139 days

10

140C
160C with decane

Projected
= 809 days

=
41 days
=
13 days

1,000 mg/L HPAM

0.3% NaCl,
< 0.1 ppb O2

1
0

50
100
150
200
250
300
Time stored at given temperature, days

PV
285

Viscosity decay constant, days

100000

What is the upper temperature limit for

HPAM use in chemical EOR?

< 0.1 ppb O2

10000

e-50200/RT

1/ = 8325
Rc = -0.925 for
1% NaHCO3

1000

286

1/ = 1.425x109 e-91130/RT
Rc = -0.930

100

For either HPAM or PAM-AMPS

in 0.3% NaCl, 3% NaCl, or
0.2% NaCl + 0.1% NaHCO3

10

Above 60C, acrylamide groups hydrolyze to

form acrylate groups.

1
50

100

150

If the degree of hydrolysis is too high and too

200

Temperature, C

A given viscosity level can be predicted using: /o = e-t/

Viscosity half-lives for HPAM and PAM-AMPS solutions
projected to be > 7 yrs at 100C and ~2 yrs at 120C.

At 105C after 250 days, we predict a 9% viscosity loss,

while Shupe (1981) saw a 13% loss.

287

much Ca2+ or Mg2+ is present, HPAM polymers

precipitate.

Temperature, C:
75
88 96 204
Max Ca2+ + Mg2+, mg/L: 2000 500 270 20
(from Moradi-Araghi and Doe, 1987)
288

48

You cant stop hydrolysis of PAM or HPAM. At 80C, hydrolysis

will rise to ~60% after 100 days. (Moradi and Doe, Phillips,
SPERE May 1987). Preventing >50% hydrolysis could be done
by incorporating at least 50% AMPS or NVP (SPE 14233).

BIODEGRADATION of BIOPOLYMERS
1. Hire a competent microbiologist.
2. Identify all microorganisms in the
reservoir/brine/polymer system.
3. Identify which combination of
microorganisms degrade the polymer.
4. Identify which biocide prevents the
degradation.
290

289

ESTIMATING FRACTURE CONDUCTIVITY FROM

INJECTIVITY OR PRODUCTIVITY DATA

Does my well have a linear-flow problem?

(e.g., a fracture)

Assume:
Vertical well with a vertical fracture
If multiple fractures are present, the widest fracture
dominates flow.
The fracture has a much greater flow capacity than
the matrix.
The fracture has two wings.

Injectivity or productivity data often

provides a low-cost method for diagnosis.
Radial (matrix) flow probable:
q/p ( k h)/[141.2 ln (re / rw)]
Linear (fracture-like) flow probable:
q/p >> ( k h)/[141.2 ln (re / rw)]

qtotal = qmatrix + qfracture = (p hf /) [km/ln(re/rw) + 2kfwf/Lf]

kfwf = {[qtotal /(p hf)] - [km/ln(re/rw)]} Lf /2
291

292

MATRIX OR FRACTURE FLOW?

1000
Effective permeability of the flow path,
darcys .

ESTIMATING FRACTURE PERMEABILITY FROM

TRACER TRANSIT TIMES
Assume the widest fracture dominates flow.
kf = qL/[hfwf p] = (Lhfwf/t)L/[hfwf p] = (L2 ) /(p t)
Where:
L is fracture length (~distance between wells),
is fluid viscosity (usually of water),
p is the pressure drop between wells,
t is tracer transit time between wells.

k ~ re2 /(4t p)

100

Fracture flow
probable

10

Matrix flow
probable
1

=1 cp, p=2000 psi, re=1000 ft.

L~2re, which depends on well spacing
0.1
0.1

293

10

100

Interwell tracer transit time, days

1000
294

49

THE WIDEST FRACTURE DOMINATES FLOW

10000000

Fracture conductivity, darcy-ft

100000

1000000

10000

100000

1000
100

10000

10

1000

1
0.1

100

0.01

10

0.001

kf wf (darcy-ft) = 1.13x10-5 (kf)1.5, where kf is in darcys.

kf wf (darcy-cm) = 3.44x10-4 (kf)1.5, where kf is in darcys.
wf (ft) = 5.03x10-4 (kfwf)1/3, where kfwf is in darcy-ft.
wf (mm) = 0.153 (kfwf)1/3, where kfwf is in darcy-ft.
wf (mm) = 3.44x10-3 (kf)0.5, where kf is in darcys.

0.0001

0.01

RELATION BETWEEN FRACTURE WIDTH,

PERMEABILITY, AND CONDUCTIVITY

Fracture permeability, darcys

1000000

0.1

10

Fracture width, mm
295

296

50