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Improved oil recovery using polymeric gelants: A review

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Indian Journal of Chemical Technology
Vol. 13, March 2006, pp. 162-167

Improved oil recovery using polymeric gelants: A review

G P Karmakar* & Chandrima Chakraborty
Department of Petroleum Engineering, Indian School of Mines, Dhanbad 826 004, India
Email: gpkarmakar @ yahoo.com
Received 8 July 2005; revised received 27 December 2005; accepted 12 January 2006

Oil and gas production from the reservoirs are often accompanied by huge amount of water production. Excessive
water production from the oil and gas reservoirs is one of the major problems faced by the petroleum industries worldwide.
Polymers and gels have been successfully used for many years to control the water production. Most methods involve cross-
linked polyacrylamide gels initiated by metal ions or organic radical formation. Some inorganic compounds, particularly
Fe(III) compounds can be transformed to gels by in-situ hydrolysis, which can be effectively used as the blocking materials.
A new type of organically modified silicate compound, tetramethoxysilane (TMOS) has been supposed to be more effective
in water shut- off jobs. In-situ cross-linking acid diverting agents (ISCADA) is proved to be a better solution to stimulate the
multi-layered reservoirs. Certain biopolymers and foams may also be used successfully to control water production in oil or
gas reservoirs. This paper attempts to review the present status of the gel systems used in the oil industries to control the
water production during oil and gas production.

Keywords: Tetramethoxysilane, Polymeric gelant

IPC Code: C10G21/00

The high water production during the production of
crude oil from oil wells is a serious problem faced by
the petroleum industries as it increases the production
cost and creates water disposal problem. It also
induces operational problems such as fines
production, corrosion and scale formation. In the
United States, where many fields are depleted, the
ratio of water-to-oil production is closer to 9:1. In
some areas around the world, fields remain on
production when the ratio is as high as 50:1 (ref. 1).
So to increase the oil recovery it is necessary to apply
some effective methods for controlling the water
production in wells. One of the solutions to reduce the
production of unwanted water is the placement of full
blocking gel systems in reservoir layers that produce
the water. Most polymer gel systems available in the
industry are placed in the near well bore before cross-
linking takes place. After the injection of the polymer
system in the matrix of a target zone, the components
react and form a three-dimensional polymer structure.
This three-dimensional structure is referred to as a
gel. This gel can reduce or completely block water
flows through the porous medium.
Another method involves injection of a suitable
polymer solution into the production well, along with
a cross linker, initiated by metal ions or organic
radicals2. The polymer solution and the cross linker
then react to form an annulus of gel around the
production well. This gel systems work as the relative
permeability modifiers (RPM), modifying the flow of
two phases, oil and water phases, and the
phenomenon they induce is known as
disproportionate permeability reduction (DPR).
TMOS/water system has a number of advantages
over the conventional cement plugging. However,
there is a scope of further research in this field, which
involves the studies of rheological and thermal
properties of the new type of gel system to be used in
high temperature reservoirs and in harsh environment.
Polymers for water shut-off jobs/enhanced oil
recovery
Polymer gels have been widely used to control the
excess water production during oil and gas recovery.
The use of polymers in Enhanced Oil Recovery is first
suggested in the early 1960s as a means of reducing
mobility ratio (M) by increasing the drive water
viscosity and by reducing the formation permeability
3
to water. The early pioneering work of Pye ,
Sandiford4 , Mungan et al.5 and Gogarty6 and later
7 8
works of Smith and Szabo have shown that
polymers at a very low concentration of a few
hundred ppm can significantly increase the viscosity
of the injected brine. Most of the early workers have
worked with partially hydrolyzed polyacrylamide
 KARMAKAR & CHAKRABORTY: IMPROVED OIL RECOVERY USING POLYMERIC GELANTS: REVIEW
9
(HPAM) gel. Sandvik and Maerker have worked
with the biopolymer xanthan for field polymer
10 11,12
flooding applications. Chang and others have
13
evaluated field applications. Broseta et al. have
made some recommendations of the pertinent
rheological measurements for an efficient gel
screening in water shut-off and conformance
14
improvement treatments. Hill claiming a patent has
first proposed use of silicate gels in enhanced oil
recovery. The idea of water shut-off treatments has
been raised when injection of silicate solutions into
oil producing wells with the aim at in -situ gelation to
form a blocking phase is patented. Robertson and
15
Oefelein are one of the few who have not only
studied, but also tested the silicate gels for water shut-
16
off applications. Later studies by Cole et al. and
17
Sparlin et al. also have suggested that these
materials can be successfully used for Improved Oil
Recovery/Enhanced Oil Recovery purposes.
18
Krumrine and Boyce have confirmed that the
permeability modification with silicate gel based
system is a viable alternative in need. Vinot et al.
19
have suggested the possible reasons of not using the
silicate gels widely in practice; they have also pointed
out the mechanism of silicate gelation under various
20
reservoir conditions. Earlier studies with crosslinked
polyacrylamide gels have been shown that the
permeability of such a gel to water varies as power
21
law function of fluid velocity. Al Sharji et al. have
shown that the permeability of water through the gel
depends also upon the elastic properties of the gel.
22
Recently, Grattoni et al. have shown that TMOS is
an effective oil soluble gelant which can be used as a
RPM to control water production during oil recovery.
23
Karmakar et al. have shown that the gelation time
and the RPM characteristics are function of the
24
TMOS concentration. Hanssen et al. report new
experimental data for gas-blocking foams that appear
to have superior oil tolerance caused by the presence
25
of polymer. Lakatos and Kosztin have explained the
laboratory studies and field results of disproportionate
permeability modification by alcohol containing
polymer solutions. A pilot test on the Hungarian gas
fields has showed satisfactory results by using the
alcoholic polymer solutions. Studies by Chauveteau
26
et al. describe in-depth permeability control by
adsorption of micro-gels and the process to improve
their field characteristics. Recent studies by Halder et
27
al. provide a new solution to stimulate multi-layered
reservoirs by using in-situ cross-linking acid diverting
agent (ISCADA).
163
Polymer gel systems used for water shut-off jobs
Apart from mechanical tools, and the traditional
cement and inorganic gel squeezers frequently used to
isolate water out zones, several types of gelant
systems have been used with some degree of success
to control water production. There are three main
types of chemical gel type treatments:
28
a) Permeability blockers or gelants
b) Disproportionate permeability reducers (DPR)
and or Selective Permeability Blockers (SPB)
c) Relative Permeability Modifiers (RPM)
The two most commonly used polymers in such
applications are partially hydrolyzed polyacrylamide
(HPAM) and the biopolymer, xanthan. Recently,
organically modified silicate compounds have been
found to be effective in water shut-off jobs during oil
production.
Relative permeability modifiers in water shut-off
jobs/Improved oil recovery
Polyacrylamide gels
Polyacrylamide gels have been used to reduce
water cut in production wells and control profiles in
injectors. Formations up to 66°C have been treated
rather routinely. Recently these gels are used at higher
temperature formations containing relatively hard
brines. A number of studies have been done with
these gels cross-linked with trivalent chromium and
aluminium with C-13 NMR29. These cross-linking
ions react with the occasional carboxylate groups
distributed along the polymer chain of
polyacrylamides. When the metal ion-carboxylate
reaction occurs the polymer chains are connected
together in a three-dimensional network extending
throughout the aqueous phase.
Dynamic rheological studies30 have been carried
out with the cross-linked polyacrylamide gel by
varying the gel strengths while keeping the
temperature, salinity and cross-linker concentration
constant. Both the loss and storage moduli increased
with the increase in polymer concentration of this gel
system. Two parameters have been used to
characterize the flow behaviour, one is intrinsic gel
permeability and other is elasticity index.
The velocity -dependent behaviour of the gel’s
permeability to water is due to its elasticity. Its
intrinsic permeability is controlled by the distribution
of dense and dilute domains with in the gel structure,
while movement and deformation of the free polymer
164 INDIAN J. CHEM. TECHNOL., MARCH 2006
molecules existing within the dilute domains govern
its velocity-dependent behaviour.
31
Albonico et al. have reported that polymers or
gels can effectively reduce permeability to water more
than that of oil. Various types of gels that are studied
3+
included resorcinol- formaldehyde, Cr (acetate)-
polyacrylamide and Cr
3+
(chloride)-xanthan and
colloidal silica.
Later studies reveal a new and simple chemical
approach to control the gelation reaction of
3+
Cr /polymer solutions that substantially meets the
gelation delay requirements for in -depth treatments
of high-temperature reservoirs. By screening organic
ligands for their gelation delaying power with
hydrated Cr3+/polymer and Cr(OAc)3/polymer
solutions several powerful retarding ligands have
3+
been identified. Use of the pre-formed Cr
complexes of these ligands together with additional,
uncomplexed ligand in the gelant solution provide
outstanding control over the gelation time over the
temperature range of 60-135°C. With these
compositions gelation times spanning the range from
several hours to one month or more have been
obtained at temperature up to 120°C. Due to low
toxicity of the Cr3+ polymer gels the environmental
problems are notably reduced relative to those
employing hexavalent chromium compounds or
formaldehyde.
Inorganic gel systems in water shut-off jobs
Certain Fe (III) compounds can be transformed into
gel-like precipitate by in-situ hydrolysis, which is
then immobilized by in -situ flocculation or
spontaneous aging. Practical applications of Fe(III)
compounds are restricted due to hydrolysis of such
compounds in formation water. The iron-hydroxide
formed in porous media becomes immobile due to
spontaneous aging. However, its blocking efficiency
is not much affected by temperature as iron-hydroxide
is thermostable up to 150°C. Besides Fe(III), Al(III)
and Cr(III) theoretically fulfill the chemical
requirements for such gel formation. The blocking
materials have excellent stability under field
conditions, but in case of technological failure the gel
32,33
phase can easily be broken up into mobile sols . =(OCH3)3-Si-O-Si-(OCH3)3+H2O …(2)
Internally activated sodium silicates (IAS) make up
one of the most well established types of chemical
sealants. The gelation times of IAS are controlled by
the pH and temperature of the systems. The gelants
form stiff, brittle solids at higher temperature with the
use of same amount of silicates and high temperature
activator (HTA). Silicate gels are generally stable
above 200°C, irrespective of the type of activator
used .
34
Oil soluble silicate gels in water shut-off jobs
Besides polyacrylamide gels and inorganic
silicates, organic silicates have been also used widely
in water-shut -off applications. These gels usually
provide some better results than the others in high
35
temperature reservoirs .
The main advantages and disadvantages of using
silicate gels in enhanced oil recovery can be
summarized as follows:
Advantages
(i) Flexibility in chemical mechanism
(ii) Chemically and thermally stable
(iii) Easy gel breaking in case of technical failures
(iv) Simple and cost effective surface technology
(v) The silicates are environmental friendly
materials
Disadvantages
(i) Rigidity of the gel leads to its fracture
(ii) Gelation kinetics is difficult to control
(iii) Penetration of the treating solutions is short if
the buffer capacity of rock is high
Organically modified silicate compounds for water shut off
jobs
Recently some research has revealed that
organically modified silicate compounds such as
tetramethylorthosilicate (TMOS, also known as
tetramethoxysilane) can be used as relative
permeability modifiers in water shut-off jobs which
form an oil soluble gelant in wells during oil
23
recovery . This alkoxide can be hydrolyzed and
condensed under relatively wide range of conditions
to form a rigid, porous gel as shown by the schemes 1,
2 and 3.
(i) Hydrolysis
Si-(OCH3)4+nH2O = Si-(OCH3)4−n(OH)n+n(CH3OH)
…(1)
(ii) Condensation
(OCH3)3-Si-OH+HO-Si-(OCH3)3
and/or
(OCH3)3-Si-OCH3+HO-Si-(OCH3)3
=(OCH3)3-Si-O-Si-(OCH3)3+CH3OH …(3)
The gel formed is a viscoelastic solid where the gel
strength, loss and storage moduli are function of the
TMOS concentration.
 KARMAKAR & CHAKRABORTY: IMPROVED OIL RECOVERY USING POLYMERIC GELANTS: REVIEW
Biopolymers in enhanced oil recovery
Biopolymers such as starch, xanthan, guar, lignin
and cellulose have been used in oil industry for many
years. The microorganism Xanthomonas campestris
produces xanthan biopolymer. The degradation
mechanism of biopolymer like xanthan which is
widely used during polymer flooding applications has
been explained by Wellington36, Ash et al.37, and
38
Seright and Henrici . Both biopolymer xanthan and
synthetic polymers such as HPAM are susceptible to
free-radical attack, which leads to the degradation of
the macromolecules.
Foams in water shut-off jobs
In recent years, foam treatment 39 has been proved
to be effective in gas shut-off jobs in oil wells having
high gas/oil ratio (GOR). Foams provide highly
attractive alternative over conventional non-
Newtonian fluids for various oil and gas industry
applications because of their high viscosity and low
liquid content. Foams have been successfully used in
well stimulations, drilling, acidizing, cleanout
operations, and enhanced oil recovery.
Cement plugging to control water production
Cement plugging means the operation whereby a
cementing slurry is pumped into a drilled hole and/or
forced behind the casing in order to stop the flow of
water, oil or gas into or out of a geological formation,
group of formations or part of a formation through a
borehole or well penetrating these geologic units. In
cement plugging operations it is a requirement to have
the presence of a workover rig to perform the
operation safely and correctly. With gels there is no
need of the rig, rather it uses coiled tubing. The
penetration depth of polymeric gels is higher
compared to cement, allowing for high effectiveness
of the treatments. Compatibility of the gel system is
better and isolation effectiveness of the gel is not
affected by acid40,41.
Stimulation of multilayered reservoirs by in-situ cross-linking
acid diverting agent (ISCADA)
27
Recently Halder et al. have found out a new
solution to stimulate the multilayered reservoirs by
using the in-situ Cross-linking Acid Diverting Agent
(ISCADA). This new diverting agent, which is pH
and temperature sensitive, can temporary block the
high permeable or undesired layers. Water production
in some wells has come down remarkably by using
ISCADA as diverting agent and substantial
improvement in oil productivity has also been
observed.
165
Conclusion
From the above review it can be seen that different
methods have been proposed and tested for water
controlling jobs in oil producing wells worldwide. We
may conclude that:
• Various types of gels that are studied included
+3
resorcinol formaldehyde, Cr (chloride)-
xanthan, Cr3+ (acetate)-polyacrylamide and
colloidal silica.
• Among these the polymer gels give satisfactory
results in almost all types of reservoirs. These
gels are used as relative permeability modifiers
(RPMs), which reduce the permeability of the
water media more than that of the oil, the exact
reason of which is still unknown.
• Most of the previous researchers worked with
the partially hydrolyzed polyacrylamide gels for
water shut-off applications.
• Later studies showed that these gels cross-linked
with suitable metal ions such as, trivalent
chromium or aluminium give better result in
high temperature conditions.
• Recently a new type of silicate gel, TMOS
(tetramethoxysilane) reveals a better way of
controlling water production during oil recovery.
• Recent studies reveal a new possibility of using
in-situ cross-linking acid diverting agent
(ISCADA) to stimulate the different layers in the
reservoirs and to improve the oil production in
certain wells subsequently.
• Selection of a particular type of gel system will
depend on the thermal and rheological stability
of the gel formed under high
temperature/pressure conditions of the reservoir
along with the specified reservoir rock and fluid
properties.
Acknowledgement
C Chakraborty thanks the Department of Science
and Technology, Government of India, for the
financial assistance for carrying out research work in
the Department of Petroleum Engineering, Indian
School of Mines, Dhanabd.
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