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SPE 84862

Development of a Correlation for Estimating Gelation in Porous Media Using Bottle


Test Measurements
Mariyamni Awang and Goh Meng Seng, University of Technology Malaysia

Copyright 2003, Society of Petroleum Engineers Inc.


This paper was prepared for presentation at the SPE International Improved Oil Recovery
Conference in Asia Pacific held in Kuala Lumpur, Malaysia, 2021 October 2003.
This paper was selected for presentation by an SPE Program Committee following review of
information contained in an abstract submitted by the author(s). Contents of the paper, as
presented, have not been reviewed by the Society of Petroleum Engineers and are subject to
correction by the author(s). The material, as presented, does not necessarily reflect any
position of the Society of Petroleum Engineers, its officers, or members. Papers presented at
SPE meetings are subject to publication review by Editorial Committees of the Society of
Petroleum Engineers. Electronic reproduction, distribution, or storage of any part of this paper
for commercial purposes without the written consent of the Society of Petroleum Engineers is
prohibited. Permission to reproduce in print is restricted to an abstract of not more than 300
words; illustrations may not be copied. The abstract must contain conspicuous
acknowledgment of where and by whom the paper was presented. Write Librarian, SPE, P.O.
Box 833836, Richardson, TX 75083-3836 U.S.A., fax 01-972-952-9435.

Abstract
The bottle test method that is currently used to estimate
gelation only provides a qualitative description and also does
not necessarily reflect what happens in a porous media. This
paper aims to show a relationship between the permeability of
a porous medium that has been injected with a pre gel polymer
and the gelling state given by a bottle test. In this way a better
estimation of the gel strength in the reservoir can be made.
Introduction
Polymer gels have been used in oil field for water shut off and
sweep efficiency improvement. In recent years, the state of a
gel is described qualitatively by the gel strength code, where
code A to code J using bottle testing. Robert D.Sydansk
studied the gelation rate and gel strength by using bottle
testing. However, the bottle testing does not indicate the extent
of plugging that occurs in the porous medium.
The aim of this study is to develop a relationship between
the alphabetic gelation system and the degree of plugging in
the porous medium. The most relevant form of testing for gel
plugging efficiency proved to be the permeability reduction in
porous medium.
Theory
There are several alternatives to overcome water production
problem during the course of oil or gas production. One of
them is cementing technology which is aimed at reducing
channeling problem behind the pipe to isolate water-producing
zone. However, this approach is costly and not entirely
reliable. So, gel polymer is preferable and is gaining wider
acceptance on account of its cost-effectiveness. Moreover, it is
efficient in improving water-oil ratio. Cross-linked polymer
utilizing Al3+ as cross-linker introduced by Needham, et. al
was successfully applied in Minnelusa reservoir in 1979. Since

then, cross-linked polymer technology began to gain


popularity in oil industry. In gel treatment, it is best that crosslinked polymer which forms gel penetrates high permeability
zone with low oil saturation. This ensures that the subsequent
injected fluid be forced to flow to the low permeability zone
with high oil saturation. Thus, oil can be displaced in
this zone.
Metallic cross-linkers can be used to produce gels with
anionic polymers. This is done through formation of the ionic
bonds between multivalent cations and the negative sites of
the polymer. The gels produced through metallic cross-linkers
typically have lower thermal stability. Organic cross-linking
involves the formation of covalent bonds between functional
groups of the polymer, i.e. amides, and the cross-linker,
connecting two or more polymer chains.
The cross linking agent is a chromic carboxylate complex.
The term complex herein as an ion or molecule containing
two or more interassociated ionic, radical or molecular
species. The facts the cross linking in Cr3+ /polymer gels can
be described as discrete complexes of Cr3+ implies that they
will display chemical reactivity characteristic of Cr3+
coordination complexes.7 One such reaction is ligand
exchange, which refers to the substitution of a ligand bonded
to Cr3+ by another, uncomplexed ligand. In the case of Cr3+
/polyacrylamide (PAM) gels, exchange of PAM bonded to
Cr3+ for a non-polymeric ligand, L, present in aqueous
medium would lead to destruction of the Cr3+ cross
link(eq.1).1
-L
+P
+P
Cr(L)3
Cr(L)2
Cr(L)2(P)
+L
-L
Cr(L)(P)2
cross link
eq.1
Figure 1 shows the proposed gelation mechanism of cross
linking between the acrylamide group and phenolformaldehyde. The methylolation of a phenol or an acrylamide
polymer immates resin formation. A phenol reacts with an
aldehyde to form a resin, methylolophenol. Types of bonding,
which can occurs between methylophenol and acylamide
polymer or between methylophenol and phenol include:
1)ether linkages; 2)methylene linkages; and 3)acetylene
linkages. The methylol groups on the methylolated acrylamide
polymer are sites for bonding between methyloted acrylamide
polymer and phenols.6

SPE 84862
Bottle Test Gel Strength Code
A(1)

No detectable gel formed. The gel appears to have the


same viscosity (fluid) as the original polymer solution and
no gel is visually detectable.

B(2)

Highly flowing gel. The gel appears to be only slightly


more viscous than the initial polymer solution.

C(3)

Flowing gel. Most of the obviously detectable gel flows to


the bottle cap upon inversion.

D(4)

Moderately flowing gel. A small portion (about 5 to 15%)


of the gel does not readily flow to the bottle cap upon
inversion usually characterized as a touguing gel (ie.,
after hanging out of the bottle, gel can be made to flow
back into the bottle by slowly turning the bottle upright).

E(5)

Barely flowing gel. The gel slowly flows to the bottle cap
and/ or a significant portion (>15%) of the gel does not
flow upon inversion.

F(6)

Highly deformable non flowing gel. The gel does not flow
to the bottle cap upon inversion (gel flows to just short of
reaching the bottle cap).

G(7)

Moderately deformable non flowing gel. The gel flows


about halfway down the bottle upon inversion.

H(8)

Slightly deformable non-flowing gel. Only the gel surface


deforms slightly upon inversion.

I (9)

Rigid gel. There


upon inversion.

J(10)

Ringing rigid gel. A tuning-fork-like mechanical vibration


can be felt after the bottle is tapped.

Fig1. Gelation Mechanism


Experimental
In this study, bottle testing and displacement of gel solution in
sandpack were run at the same time. The purpose was to study
the correlation between the gel strength codes observed in the
bottle testing and the permeability reduction in the sandpack.
Table 1 defines the gel strength code developed by
Robert D. Sydansk.
During the displacement experiment, a sand pack was
saturated with brine water and then flooded with a gel solution
at constant pressure. The sand pack and gel solution were
placed at room temperature. After the gel solution in the bottle
testing achieved certain gel code in the bottle testing, two-pore
volume brine water were injected into the sandpack to displace
the gel and the breakthrough pressure was measured. Then,
brine water was injected into the sandpack to determine the
final permeability.
Apparatus Fig 2 is a schematic for the apparatus used in the
displacement experiment. The system consisted transfer
cylinders and the gas nitrogen. The gel solution was pumped
into the sandpack through the transfer cylinder.
There were two sandpack holder used in the experiment.
One was 30.5 cm long with an ID of 3 cm. The second holder
was 20.4 cm long with and ID 3.8 cm. Permeability was
determined from the pressure drop with the brine water as a
flowing fluid.
Glass bottles with screwed cap, 4 inch long with ID 0.35
inch were used in the bottle testing.
Materials The polymers used in the experiment were
polyacrylamide polymer (M.W.over 5,000,000) and Xanthan
biopolymer from xanthomonas camperstris (Fluka). Both
polymers are in the dry powder form. Polymer solution was
prepared by using magnetic stirrer. Stirring was run overnight
until the polymer was fully dissolved in brine water.
Chromium (III) acetate hydroxide and phenol
formaldehyde were used as cross linking agent.

is

no

gel

surface

deformation

Table 1.Gel Strength Code


Results and Discussion
Twelve experiments were conducted at room temperature,
27oC. Table 2 shows the initial sandpacks condition. Injection
of gel solution began immediately after the solution
was prepared.
For the sandpack 1, 20,000 ppm PAM and 44:1 ratio
polymer to Cr (III) was prepared. The gel solution was
injected into sandpack 1 with 0.0917 ml/s. After setting 66
hours, the gel strength code observed in bottle test was H, the
gel only deformed slightly at the surface upon inversion. Brine
water was injected into the sandpack to displace the gel
solution. The differential pressure of 400 psi was applied on
the sandpack for 4 hours. The gel did not flowing out along
the experiment. Gel breakdown did not occurred.
Fig.3 shows the permeability reduction of sandpack 2,4
and 11 treated with gel solution that no detacable gel formed.
Gel strength codes for sandpack 2, 4 and 11 (which obtained
through the bottle-testing) were same. There was no gel
formed through the visually observation (code A).
10,000 ppm xanthan with 44:1 ratio polymer to Cr(III) was
injected into sandpack 2. The solution was allowed mature in
the sandpack for two hours. After two hours, less than 10 psi
differential pressure was required to displace the gel solution.
The displacement was fast. Two-pore volume of water brine
was allowed to displace the gel solution in the sandpack. The

SPE 84862

Sandpack

Jar

Length

Permeability

Porosity

(cm)

(cm)

(md)

(%)

3.8

20.4

3,462

0.47

3.8

20.4

1,731

0.43

3.8

20.4

1,587

0.43

3.8

20.4

8,149

0.43

3.8

20.4

5,585

0.41

30.5

3,230

0.5

30.5

29,071

0.47

30.5

19,381

0.43

30.5

31,267

0.43

10

30.5

38,040

0.55

11

30.5

17,579

0.43

12

30.5

11,406

0.42

Pressure gauge
sandpack

Diameter

1
Transfer cylinders

Brine water

Gel solution

Gas Nitrogen

Table 2 Sandpack Conditions


Fig.2 Experimental apparatus for displacement experiment

permeability was measured again after the displacement. Only


permeability reduction of 1.25 % can be achieved.
Gel strength codes for sandpack 2, 4 and 11 (which
obtained through the bottle-testing) were same. There was no
gel formed through the visually observation.
10,000 ppm xanthan with 44:1 ratio polymer to Cr(III) was
injected into sandpack 2. The solution was allowed mature in
the sandpack for two hours. After two hours, less than 10 psi
differential pressure was required to displace the gel solution.
The displacement was fast. Two-pore volumes of water brine
were allowed to displace the gel solution in the sandpack. The
permeability was measured again after the displacement. Only
permeability reduction of 1.25 % can be achieved.
For the sandpack 4, 10,000ppm polyacrylamide with 3,000
ppm phenol formaldehyde was left in the sandpack for one
day. The gel breakdown when a differential pressure of 10 psi
was applied on it. The sanpack had a residual permeability of
5180 mD, which correspond to a permeability reduction
of 36.44 %.
Through the bottle test, gel cannot be formed with the
formulation of xanthan with phenol formaldehyde. This
20000

solution was tested in sandpack 11. The solution was left in


the sandpack for one day. The differential pressure of 20 psi
was required to breakdown the gel. After the displacement of
two-pore volume brine water, the permeability of 17 Darcy
reduced to 5104 mD.
Though three of the gel solutions observed in bottle sample
showed no gel formed, the permeability reduction in
sandpacks were different. We believe that the permeability
reduction has correlation with the time for setting gel solution.
The solution had adsorbed onto the sand and reduced the
permeability.
Fig 4 shows permeability reduction of sandpack 3 and 5.
Sandpack 3 was treated with gel solution containing 10,000
ppm PAM and 1,000 ppm phenol-formaldehyde. Gel solution
containing 5,000 ppm xanthan and 44: 1 weight ratio of
polymer to Cr(III) was injected into sandpack 5. When both of
the gel solutions appeared slightly viscous than the initial
solution in bottle testing (code B), both of the sandpacks were
flushed by brine water. The gel flowed out immediately with
the differential pressure of 10 psi. Brine permeability of
sandpack 3 (1587 mD) decreased to 707 mD after 2PV of
brine injection. While brine permeability of sandpack 5 (5585
mD) decreased to 3648 mD. The gel was washed out from the

5,000 ppm xanthan / 3,000 ppm phenol


formaldehyde

18000

6000
5,000 ppm
xanthan
/44:1 Xanthan: Cr

5000

14000
Permeability (mD)

Permeability (mD)

16000

12000
10000
8000
6000
4000

10,000 ppm PAM / 44:1 PAM :Cr III

10,000 ppm xanthan


/44:1 Xanthan: Cr III

III

4000
3000
2000
10,000 ppm PAM / 1,000 ppm
phenol formaldehyde

1000

2000
0
0

24

Time (hour)
Sandpack 2

Sandpack 4

0
0

24

66

70

Time (hour)

Sandpack 11

Fig.3 Permeability Reduction of Sandpack 2, 4 and 11

Sandpack 3

Sandpack 5

Fig.4 Permeability reduction of Sandpack 3 and 5

71

72

SPE 84862

35000

12000
5,000 ppm xanthan
/44:1 Xanthan: Cr III

10,000 ppm PAM / 44:1 PAM: Cr III


10000

25000

Permeability (mD)

Permeability (mD)

30000

20000
15000
10000

20,000 ppm PAM / 44:1 PAM: Cr III

5000

20,000 ppm PAM / 3,000 ppm phenol formaldehyde


8000
6000
4000
2000

0
0

Time (hour)

24

66

70

71

72

96

Time (hour)
Sandpack 9

Fig.5 Permeability reduction of sandpack 6 and 9

sandpack due to the weak gel structure.


Fig.5 shows the permeability reduction of sandpack 6 and
9. The 20,000 ppm PAM and 44:1 weight ratio of polymer to
Cr(III) gel solution was set in the sandpack 6 for 2 hours.
When the flowing gel (code C) was detected in the bottle test,
a differential pressure of 30 psi was applied on it. The gel
breaks down. The sandpack had a final permeability of 989
mD, which achieved permeability reduction of 69%.
Another gel solution, which also appeared flowing gel in
bottle test, was tested in sandpack 9. The gel solution
contained 5,000ppm xanthan and 44:1 weight ratio of polymer
to Cr(III). The post treatment permeability of 12 Darcy
corresponds to a permeability reduction of 60%.
The gel solution contained 10,000 ppm xanthan and 44:1
weight ratio of polymer to Cr(III) in bottle testing showed
moderately flowing gel (code D) when the gel solution was
placed in the sandpack 10 for 72 hours. The gel did not break
down and washed out when differential pressure of 10psi was
applied on it during the brine injection. However, it broke
down when the differential pressure had increased to 60 psi.
After injection of two-pore volume brine, the brine
permeability reduced to 6990mD from 38D, it showed
permeability recuction of 82%.
Sandpack 12 was treated with gel solution contained
10,000 ppm polyacrylamide with 44:1 weight ratio of polymer
to Cr(III). Sandpack 7 was treated with gel solution contained
20,000ppm
polyacrylamide
and
3,000ppm
phenol
formaldehyde. The brine water injection started when both of
the gel solution appeared moderately deformable gel non
flowing gel (code G). The gel flowed about half way down the
bottle upon inversion. The gel in sandpack 12 did break down
when differential pressure of 50 psi was applied on it. While
the gel in sandpack 7 broke down when differential pressure
had increased to 80 psi. The gel setting time in sandpack 12
was longer than sandpack 7. The permeability reduction in
sandpack 12 showed 88 % and sandpack 7 showed 74%.

Sandpack 12

Sandpack 7

Fig.6 Permeability reduction of sandpack 7 and 12

Fig. 7 summarizes the results of permeability reduction for


the gel solution that prepared by using polyacrylamide
polymer. The highest permeability reduction, 100 % can be
achieved when the gel in the condition code H, where the gel
surface only deform slightly upon inversion in bottle testing.
Results from the treated sandpacks show the permeability
reduction has correlation with the gel code that obtained from
the bottle test samples. Though different concentrations and
cross-linking agents were used in the experiments, however
the Fig.7 shows the permeability reduction trend to increase
when the condition gel had changed form gel code A to code
H. The magnitude of the permeability change was not
consistent than expected.

Permeability reduction (%)

Sandpack 6

100
90
80
70
60
50
40
30
20
10
0
A

Gel Code
20,000 ppm PAM/454 ppm Cr(III)
10,000ppm PAM/3,000 ppm phenol formaldehyde
10,000 ppm PAM/227 ppm Cr(III)
10,000 ppm PAM/1,000 ppm phenol formaldehyde
20,000 ppm/3,000 ppm phenol formaldehyde

Fig.7 Correlation permeability reduction with gel strength codes


using polyacylamide

SPE 84862

100

100

90
Permeability reduction (%)

Permeability reduction (%)

90
80
70
60
50
40
30

80
70
60
50
40
30
20
10

20

10

Gel Code

0
A

10,000ppm PAM/3,000 ppm phenol formaldehyde

Gel Code

10,000 ppm PAM/1,000 ppm phenol formaldehyde


20,000 ppm PAM/454 ppm Cr(III)

20,000 ppm/3,000 ppm phenol formaldehyde

10,000 ppm PAM/227 ppm Cr(III)

Fig.8 Correlation permeability reduction with gel strength codes


using polyacrylamide and chromium

Fig.9 Correlation permeability reduction with gel strength codes


using polyacrylamide and phenol formaldehyde.

Fig.8 and Fig.9 separate the results form Fig.7 by different


crosslinker in polymer polyacrylamide. The graphs show more
clearly the effect of gel strength on the permeability reduction
in sandpack by using different gel system.
Fig.10 shows permeability reduction as a function of gel
strength codes in treated sandpack with xanthan. The general
trend of permeability of sandpack show the permeability of
sandpack had reduced when the gel strength codes had
changed from code A to code D.
These studies demonstrate the permeability reduction
during placement of gel solution in the reservoir. We assume
that laboratory data of bottle testing can be applied directly to
predict the permeability reduction in the field application. For
example, if fully blocking is needed to block the water flow,
the gel strength code H must be obtained from bottle testing in
preparation of gel solution. However, the laboratory results
showed that the permeability reduction is not a linear
correlation with the gel strength code.
The factors influencing the permeability reduction in the
gel treatment in this study are the type of polymer, type of
crosslinker and also the shut-in time of gel solution in the
sandpack. A linear correlation of permeability reduction is
unable to be created with the gel strength code.

Conclusion
1.
When gel strength code H was observed, that is, the
gel surface deformed slightly upon inversion, the permeability
reduction in the sandpack was 100%. Therefore the alphabetic
code can be used to estimate total blocking.
2. Type of polymer and crosslinking agent affected the
permeability reduction in the sandpack. The same gel strength
code
achieved
by
xanthan/crosslinker
and
polyacrylamide/crosslinker
systems
gave
different
permeability reductions in the sandpack.
3. Clear trends were seen between the alphabetic code
and sand pack permeability reduction when the same polymer
and crosslinker were used in both estimations. Consequently,
the gelling time can be estimated using bottle tests specific to
one polymer and crosslinker.
Nomenclature
K = Absolute permeability, L2, mD

= Porosity
ppm = part of million
Q = flow rate, cc/s

= viscosity, cp
A
= area, cm2
dP/dL = atm/cm
K=
Q
A(dP/dL) -------------- Darcys equation

Permeability reduction(%)

90
80
70
60
50
40

Acknowledgements

30
20
10
0
A

Code Gel
5,000 ppm xanthan/113 ppm Cr(II)

10,000 ppm xanthan /227 ppm Cr(II)

Fig.10 Correlation permeability reduction with gel strength codes


using xanthan

Support from the Petroleum Engineering department is


gratefully appreciated, especially from the EOR research
group.
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SPE 84862

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SI Metric Conversion Factors


cp x 1.0*
md x 9.869233
o
F
ml
= cm3
ppm
= 8.34Ib/1,000 gal
*Conversion factor is exact.

E 03 = Pa.s
E 04 = m2
o
( F 32 )/1.8 = oC

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