SPE 168069
Study of Polyacrylamide/Cr (III) Hydrogels for Conformance Control in
Injection Wells to Enhance Chemical Flooding Process
Saleh F. Hassan, Ming Han, Xianmin Zhou, Dimitrios Krinis, and Badr Zahrani, Saudi Aramco
Copyright 2013, Society of Petroleum Engineers
This paper was prepared for presentation at the SPE Saudi Arabia section Annual Technical Symposium and Exhibition held in Khobar, Saudi Arabia, 19–22 May 2013.
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 have not been
reviewed by the Society of Petroleum Engineers and are subject to correction by the author(s). The material does not necessarily reflect any position of the Society of Petroleum Engineers, its
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Abstract
This study is to increase the efficiency of chemical injection by reducing the injectivity in high permeability zone, especially
fractures or super-K zones, which are inevitably encountered in carbonate reservoirs. A chemical gelant system in liquid
composed of polymer and crosslinker will be introduced in injection wells and form semi-solid gels in the formation. This
technique will divert the successively injected fluids (chemical solution) into unswept formation and ensure the success of a
chemical EOR process. A polyacrylamide/Cr (III) gel system was studied in terms of sol/gel diagram, kinetics of the gelation,
viscoelastic properties of gels with the help of oscillatory shear rheometer, and long-term stabilities with a measure of
syneresis. The lab results present excellent performance at the conditions of a carbonate reservoir. A core flooding test was
conducted to identify plugging capacity with disproportionate permeability reduction to brine and to oil. Results confirmed a
successful application of gelant system as conformance control agent for a carbonate reservoir.
Introduction
Polyacrylamide (PAM) in aqueous solution may react with chromium originally in its +3 valence state to form a hydrogel.
The hydrogels formed from polyacrylamide and chromium are among the polymeric gels most commonly used in petroleum
industry to modify the water flooding efficiency. The permeability of Super-K zones is several orders of magnitude greater
than the average matrix permeability. The need for permeability modification requires the injection of gelling polymer into
high permeability zones of the reservoir (Alqam et al, 2001). Gels have been used as blocking and diverting agents to treat
injection and production wells (Nasr-El-Din et al, 1998). The objective of these gel treatments is to reduce flow substantially
through high-permeability channels without damaging hydrocarbon productive zones (Seright, 1997). This gel will divert the
injected fluids in to the less permeability, unwept portions of the formation (Alqam et al, 2001). Such an application involves
the injection of mixture of the polymer and chromium aqueous solution into the desired subterranean formation followed by
in-situ gelation (Han et al, 1995). The controllability of gelation rate by adding the organic complexing agents such as
propionate, acetate, malonate makes the gel system of great interest for the application in petroleum production industry,
especially for reservoir profile modification. The success rate of these chemical treatments depends, among other factors, on
the understanding of gelation kinetics, compatibility with reservoir fluids and gel stability (Al-Muntasheri, 2006).
The gel system provides variable gel strengths, from weak gels to strong gels, to meet the need for the conditions of different
strata. A particular attention is then paid to the mechanical performance in repose to viscoelastic properties that can be
determined by means of oscillatory shear measurement. According to the rheological theory, the storage modulus (G’) and
the loss modulus (G”) vary with excitation frequency (ω). For linear polymer solution, the double logarithmic plot of G’ and
G” is characterized by low frequency slopes of 2 and 1 respectively, whereas for gels, G’ and G” are independent of ω.
Moreover, the magnitude of viscoelastic parameters is closely related to the feature of gel network (Han et al, 1996b). By
controlling the crosslinking reaction, gel consistency can be varied from very weak to very strong. With the gel behaving
repetitively like a viscous solution or like an elastic solid, treatment of injection wells requires this gel. Here, studies are
conducted on the viscoelastic behaviors of polyacrylamide/Cr (III) hydrogels with the help of oscillatory shear rheometer,
which may lead to a good understanding of strength and structure of the hydrogels.
The objective of this work is to increase the efficiency of chemical injection by reducing the injectivity in high permeability
zone, especially fractures or super-K zones, which will be inevitably encountered in carbonate reservoirs. A
2 SPE 168069
polyacrylamide/Cr (III) gel system was studied in terms of sol/gel diagram, kinetics of the gelation, viscoelastic properties of
gels with the help of oscillatory shear rheometer, and long-term stabilities with a measure of syneresis. A core flooding test
was conducted to identify plugging capacity with disproportionate permeability reduction to seawater and to oil. This is part
of our efforts to develop gelant system as conformance control agent to enhance a chemical flooding process in a carbonate
reservoir.
Experimental
Brine
Two types of brines were used in this study. One was the connate water, and another was seawater . The components for both
brines are listed in Table 1. TDS of field connate water and seawater are 213,734 ppm and 57,670 ppm, respectively. The
densities and viscosities of brines were found at room and reservoir temperatures in Table 2.
Table 1: Recipes of Field Connate Water and Seawater
Component Connate Water (g/L) Seawater (g/L)
NaCl 150.446 41.041
.
CaCl2 2HO 69.841 2.384
.
MgCl2 6H2O 20.396 17.645
Na2SO4 0.518 6.343
NaHCO3 0.487 0.165
Crude Oil
A dead crude oil sample was used in this study. The dead crude oil was filtrated with 5 µm filter at room condition. The
density and viscosity of crude oil at room and reservoir condition are listed in Table 2.
Table 2: Properties of Fluids
Room Temperature, 25 oC Reservoir Temperature, 100 oC
Fluids Density (g/cc) Viscosity (cP) Density (g/cc) Viscosity (cP)
Connate Water 1.1462 1.450 1.1083 0.476
Seawater 1.0385 0.966 1.0152 0.299
Crude Oil 0.873 14.590 0.7288 2.238
Polymer and crosslinker
The polymer selected for the tests is a sulfonated polyacrylamide, AN125, produced by SNF Floerger. It is a copolymer of
acrylamide and acrylamide tetra-butyl sulfonate whose chemical structure is shown Figure 1. The molecular weight is about
12 million Daltons. The hydrolysis degree of polyacrylamides is 5% (Han et al, 2012). The polymer content is 25%
Acrylamide Tetra-Butyl Sulfonate (ATBS) and 75% Acrylamide.
The stock polymer solutions were prepared by gentle stirring in sea water. The stock solution of Cr (III) with a concentration
of 1% was prepared for CrCl3.6H2O, chemical grade. The 10-ml samples were prepared by mixing of desired quantities of
polyacrylamide, Cr (III), and solvent. They were stirred and then allowed to rest in oven at 75 and 95°C.The polymer was
dissolved in seawater at concentrations of 0.05 wt%, 0.1 wt%, 0.15 wt.%, 0.2 wt.%, 0.3 wt.%, 0.4 wt %, and 0.5 wt %.
Figure 1: Chemical Structure of Sulfonated Polyacrylamide
SPE 168069 3
Elasticity Measurement
Dynamic viscoelastic properties were measured by MCR 301 Rheometer (Anton Paar) equipped with serrated parallels plates
(2 cm). The excitation frequency of oscillatory shear ranged from 0.01 to 100 rad s-1. The temperature was maintained at
25°C using a thermostat circulating water.
Petrophysical Properties of Reservoir Core Plug
A core plug was selected for coreflooding test. Diameter and length of the plug were 3.80 cm and 3.75 cm, respectively. Gas
permeability, pore volume and porosity of the core plugs were measured by routine core analysis.
The dry plug was vacuumed and saturated with connate water. The saturated plugs were left immersed in connate water to
estibish ionic equilibrium between the rock sonstituents and the brine. The brine was then displaced with about 10 pore
volum of sea water before permeability measurement. Values of porosity, pore volume, gas permeabilkity and brine
permeaibility are listed in Table 3.
Table 3: Petrophysical Properties of Reservoir Rocks
Length, Diameter, Pore Volume, Porosity, Air Permeability,
Core ID
cm cm cc % mD
138 3.75 3.80 9.74 23 3,362
Coreflood Procedure
FDES-645 coreflooding apparatus, made by Coretest System, was used for the coreflooding test. Figure 2 shows the
schematic set-up. Injection pressure, confining pressure, pore pressure, differential pressure and flow rate were recorded
automatically. Experimental procedure to measure the capacity of the plugging agent was as following:
1) Dry the core sample, weigh the sample, and determine gas permeability.
2) Saturate the core plug with connate water to set up initial water saturation (Swi) and determine the porosity of core plug.
3) Load core plug into coreholder at confining pressure of 1300 psi applced initially.
4) Flush core plug about 3 PV connate water to displace aging brine and measure permeability towater with back pressure
of 250 psi at ambient condition.
5) Back pressure of 250 psi and confining pressure of 1600 psi were set up automatically.
6) Heat the system up to 100°C at last 4 hours.
7) Inject dead crude oil to displace connate water at starting flow rate of 0.1 cc/min, and end of 1 cc/min for both initial
water saturation and initial oil saturationi.
8) Run seawater flooding to obtain residual oil saturation.
9) Inject 1 PV of gelant into core plug, keep it for 12 hours to allow the formation of gel, and clean the line of system.
10) Run post seawater flooding until breaking through the gel.
11) Continue to inject seawater and record differential pressure for calculating the residual resistance factor to water.
12) Run post oil flooding, and record differential pressure for calculating the residual resistance factor to oil.
13) Cool down the system to room temperature and clean the system
Figure 2: Schematic Core Flooding Apparatus
4 SPE 168069
Calculation of Residual Resistance Factor
Residual resistance factor (RRF) is used to describe the ability of polymer to reduce the permeability to water. RRF is
defined as (Gogarty, 1967):
RRF = (kw/µw)before / (kw/µw)after
= (kw)before / (kw)after (1)
Under given flow rate in same core flooding system, the pressure drop is ∆Pw during primary water flooding, and the value is
assumed as ∆Pw during post water flooding after polymer injection. RRF to water, RRFWater, is expressed as
RRFWater= (∆Pw)after / (∆Pw)before (2)
While RRF to oil, RRFOil, is expressed as
RRFOil = (∆Ppo)after / (∆Po)before (3)
Results and Discussion
Sol/gel Phase Diagram
Figures 3 and 4 illustrate the sol/gel phase diagram for polyacrylamide/Cr (III) at 95°C after 48 hours and 1 week of the
preparation. For polyacrylamide/Cr (III), it involves the hydrolysis of polyacrylamide at higher temperature (70°C) to
partially hydrolyzed polyacrylamide (part of the acrylamide groups converts to carboxyl groups) and then the interaction
between the carboxyl groups and Cr (III) occurs (Kohler et al, 1993). Two phases can be clearly distinguished in the Figures:
sol and gel. In the zone where the concentrations of polymer and/or crosslinker are quite low, only a sol phase can be
observed. In the zone where polymer and crosslinker concentrations are higher, the gel phases can be obtained. The sol and
gel phases are both homogeneous. It should be noted that when the crosslinker concentration is too high, the de-mixed zone
(a gel phase and a solvent phase) might be observed. This corresponds to the expulsion of pure solvent from the gel network,
due to the swelling equilibrium of the gel in the solvent. The results confirm the existence of a minimum polymer
concentration for gelation, above which the gelation occurs. Conversely, if the crosslinker concentration is too low, the
system remains as a sol (Han et al, 1996a).
Figure 3: Phase Diagram in 48 Hours
SPE 168069 5
Figure 4: Phase Diagram in 1 Week
Viscoelasticity
It was reported by some researchers that the gelatin kinetics could be followed by rheometer equipped with parallel plate or
cone-plate geometries. G’ might augment with gelation process and reach its maximum that indicated the equilibrated state of
hydrogels. However, the measurement of a separately prepared gel seems not accurate using parallel plate or cone-plate
geometries. With our experiences, the occurrence of slop effect makes the value of G’ much small and gives the same value
of G’ for different gels. Therefore, it seems necessary to use serrated parallel plate to characterize this kind of formed
hydrogels (Han et al, 1996b).
The rheological properties of a series of polyacrylamide/Cr(III) hydrogels (0.2, 0.3, 0.4 and 0.5 wt%) were measured at room
temperature (25°C) by means of oscillatory shear rheometer with serrated parallel plate in the frequency range of 0.1 to 100
rad s-1. Figures 4-8 illustrate the dependence of dynamic storage moduli (G’) and loss moduli (G”) on the excitation
frequencies (ω). It can be seen in Figure 5; the elasticity of polymer varies with the crosslinker concentration. When the
crosslinker concentration reaches a certain value, the viscosity of the elasticity augments significantly indicating the
formation of three dimensional network-gels.
6 SPE 168069
Figure 5: Viscoelasticity Measurement for 0.2 wt% Polymer in the Presence of Croslinkers
Figure 6: Viscoelasticity Measurement for 0.3 wt% Polymer in the Presence of Croslinkers
SPE 168069 7
Figure 7: Viscoelasticity Measurement for 0.4 wt% Polymer in the Presence of Croslinkers
Figure 8: Viscoelasticity Measurement for 0.5 wt% Polymer in the Presence of Croslinkrs
8 SPE 168069
Figure 9 shows that the plateau of G’ is superior to the plateau of G”. This phenomenon suggests that the hydrogels be
considered as rubber-like materials. G’, which represents the elasticity of polymer network, is virtually related to the strength
of the hydrogels. Moradi-Araghi et al. indicated that a G’ superior to 100 dyne cm-1 represents a strong gel, whereas a G’
inferior to 10 dyne cm-1 a weak gel (Moradi-Araghi et al, 1988). The strength of a gel is one of the important parameters for
the determination of suitability of the gel for a given application.
Figure 9: Viscoelasticity Measurement for Gel and Polymer Solution
The dependence of G’ on crosslinker concentration for different polymer concentrations was shown in (Figures 5-8). As it
can be seen in Figure 10, G’ increases with increasing polymer and/or crosslinker concentration. The value of G’ ranges from
10-2 to 10 dyne cm-2.
Figure 10: Dependence of G' on Cr (III) Concentration
SPE 168069 9
Long-Term Stability
Long-term stability test was conducted for 3000 ppm (0.3 wt%) polymer concentration and different crosslinker
concentration: 20, 50, 100, 150, and 200 ppm Cr3+. The test was performed at 75 and 95°C and lasted for 31 days (Figures 11
and 12). At the end of test, at 95°C the weight of gels varied between 12 to 84 % for 200 and 50 ppm Cr3+ respectively. While
at 75°C, the weight ranged between 64 to 78 % for 200 and 100 ppm Cr3+ respectively.
Figure 11: Stability Test at 95⁰C
Figure 12: Stability Test for 75⁰C
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Effect of Gel on Post Water Injection
Coreflood ing tests were conducted to evaluate the performance of the gel system for a carbonate rock. A gelant of 0.3% of
polymer and 50 ppm of croslinker was inject to the core plug after setting up of the initial water saturation of core plug of
19.4% and residual oil saturation of 31.3%. Permeability reduction to water and to oil, described in equations (2) and (3) is
calculated. The RRF values are summarized in Table 4.
Table 4: Summary of Raw Data for Conformance Control Test
Differential Pressure (psi)
Flow Post RRFWater RRFOil
Seawater Oil Water Gel Post Oil
Rate Water ∆Ppw/∆Pwf ∆Pof/∆Pwf
Flooding Flooding Flooding Injection Flooding
cc/min Injection
1 0.0370 0.145 0.112 151.28 82.44 24.22 736.07 216.25
2 0.0775 0.260 0.180 - 114.81 27.55 637.83 153.06
It appears that the water permeability reduction is more significant than the oil permeability reduction by a factor of 3.4 at a
flow rate of 1cc/min and a factor of 4.2 at 2 cc/min. This is consistent with the performance of polymers and gels for
sandstone rocks (Liang and Seright, 1995, Zaitoun and Bertin, 1996, and Al-Sarji, et al., 1999)
Conclusions
1) Polyacrylamide/Cr3+ gel system was studied for conformance control in a chemical flooding process.
2) Sol/gel phase diagram was established. Viscoelastic measurements as well as visual observation were used to determine
sol/gel diagram.
3) Gel forms in the concentration ranges of 0.2 to 0.5 wt% polymer cross-linked with 50 to 100 ppm of Cr3+.
4) The rate of gel formation increases with either polymer or cross linker concentration. Temperature accelerates gelation
process.
5) The value of storage modulus G’ ranges from 10-2 to 10 dyne cm-2.
6) Gels formed with concentration higher than 50 ppm Cr3+ exhibit lower long-term stability behavior. The long-term
stability is significantly dependent on the test temperature.
7) Coreflooding experiment results show that the gels reduce water permeability more than oil permeability.
Acknowledgement
The authors would like to thank Saudi Aramco/EXPEC Advanced Research Center for the permission to publish this paper.
Special thanks to Dr. Abdulaziz Al-Kaabi and Dr. Abdulkareem M. AlSofi for their technical input and valuable discussion.
Nomenclature
EOR = Enhanced Oil Recovery
G’ = storage modulus
G” = loss modulus
rad = radian
PAM = Polyacrylamide
PV = Pore Volume
RRF = Residual Resistance Factor
RRFOil = Residual Resistance Factor to Oil
RRFWater = Residual Resistance Factor to Water
ω = excitation frequency
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