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New Generation Silicate Gel System for Casing Repairs and Water Shutoff
Lyle D. Burns and Michael Burns, RTA Systems, Inc. Bartlesville, OK; Paul Wilhite and Stan McCool, University of
Kansas, Lawrence, KS; Ken Oglesby, Impact Technologies, Tulsa, OK; Jim Glass, JAG Enhanced Recovery, Tulsa, OK
Copyright 2008, Society of Petroleum Engineers
This paper was prepared for presentation at the 2008 SPE/DOE Improved Oil Recovery Symposium held in Tulsa, Oklahoma, U.S.A., 1923April2008.
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
officers, or members. Electronic reproduction, distribution, or storage of any part of this paper 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 SPE copyright.
Abstract
The SPI gel system is a low cost, multi-component silicate based gel, mixed at surface and pumped as a single stage with
controlled gel times ranging from a few hours to several days to form a variety of resilient gels from hard, "ringing" to soft,
weak gels. This new environmentally friendly, "green" gel system uses low chemical concentrations and no heavy metals for
a low overall cost. SPI gel systems were developed to solve water conformance problems on injector and producer wells, for
casing leak repairs and other applications.
The SPI pre-gelled system has a low viscosity for deep penetration of leaks and tight formations and it can be designed
for special applications. Well over 1000 lab tests were performed to evaluate the SPI gel system at the RTA Systems
laboratory. Further rheological testing was conducted and is in progress at the Tertiary Oil Recovery Project at the University
of Kansas. Lab tests are continuing to establish a minimum 5-year life of the SPI silicate gels for permitted injection well
repairs for regulatory Mechanical Integrity Testing (MIT) requirements. This paper presents the laboratory discovery work
and the early 3rd party confirmation work. These gels are now being field-tested for waterflood conformance and casing
repairs.
Introduction
Permeability and reservoir heterogeneity variations significantly affect the sweep efficiency or reservoir conformance of oil
recovery processes. Over the last 40 years, several methods
1-4
were proposed for improving reservoir conformance using
crosslinked polymers to mitigate the problems associated with reservoir heterogeneity. Two methods are commercially used
to crosslink polyacrylamides based on the controlled availability of multivalent metal ions (generally chromium) resulting in
the crosslinked polyacrylamide. Key issues with the crosslinked polyacrylamide systems include (1) environmental and
safety issues over the heavy metal crosslinking agent chromium, (2) limited penetration depth, (3) polymer shear
degradation, (4) polymer absorption on the reservoir surface, (4) polymer gel time, (5) polymer precipitation under harsh
reservoir conditions.
Application of silicates in different industrial areas is enormous and well documented. Injection of silicate solutions into
reservoirs with the aim at enhancing the recovery factor through a diverting effect was first proposed in 1922.
5
Acidic gel
systems are the oldest and most commonly employed techniques that employ silicates. These gels are more accurately
described as precipitation type gels since they are extremely brittle with no elasticity. In the early 1960s, sodium silicate and
glyoxal were combined to make various hard cement-like coatings on substrates. At low concentrations, a firm gel was
obtained that lacked cohesiveness and was not as hard as cement. In 1964, Gandon
6
took the mission one step further citing
sodium silicate reactions with other organic compounds to make cement like substances used to create very hard consolidated
soils for constructing bridge and dam structures. In the last 50 years, numerous inventors
7-9
patented various sodium silicate
systems to make gels for use in plugging high permeability areas of oil and gas producing reservoirs. Krumrine and Boyces
paper
10
compiles numerous papers and patents on sodium silicate chemistry as applied to oil field and grouting applications.
They also drew attention to a controversial fact that the silicate use was inequitably neglected in commercial applications in
favor of polymer treatments in practice at the time.
Many chemicals can serve as sodium silicate initiators. An initiator can be defined as a chemical that causes a sodium
silicate solution to gel in a delayed fashion. It should be noted that the gel is not simply a precipitate. Metal ions such as
calcium, can cause immediate precipitation of a water-insoluble metal silicate. Many initiators are acidic, water-soluble
chemicals which lower the pH of the silicate solution to a point at least below about 11. Most ammonium salts of strong acids
such as ammonium sulfate are effective gelants.
11, 12
Methods of delaying rapid reactions in the prior art involve multiple
stage treatments such as pumping alternating slugs of sodium silicate and the initiator separated with inactive slugs of fresh
2 SPE 113490
water when the initiator reacts rapidly. This complexity allows for delayed gelation in the formation after the placement of
the two reactants; however this does not allow for in-depth placement of the silicate gels.
Although the sodium silicate technology was the first plugging and permeability modification technology largely put to
practice, the use of gelled polymers based on polyacrylamide and chromium VI salts with reducing agents or
organochromium compounds became more popular in the 1970s and 1980s because of their unique versatility to make hard
and soft elastic gels rather than the inelastic gels formed using the original sodium silicate chemistry. Phillips Petroleum
Company was the pioneer in this area and later followed by Marathon Oil Company with similar technology using
polyacrylamide-chromium gelled systems. For example, Clampitt, Hessert, and Gall
13-16
are among the many inventors
proposing various gelled cellulose and acrylamide polymers that could be placed in a high permeability formation and
crosslinked into a chromium gel. Mumallah
17
patented the concept of chromium proprionate as a delayed gel complexing
agent for polyacrylamide. Later, Falk
18
at Marathon patented chromium acetate for use in gelling polyacrylamides.
Casing repairs and water reduction are important because they can save well profitability, prevent premature well
plugging, loss of oil and gas reserves and allow regulatory compliance. Casing leaks occur primarily over time from steel
casing exposed to corrosive formation waters. In wells with bad casing, water influx through casing leaks can cause scale
formation and excess water production possibly leading to abandonment or premature plugged. As our oil and gas wells
continue to age, casing leaks will become more of a problem.
Competitive polymer gel systems are used successfully as an alternative to cement, or in combination with cement, to
squeeze casing leaks and improve mechanical well integrity. They also are used instead of mechanical methods of cupped
packers. Hard gels are used to hold a solid pressure in the casing or to block encroachment of foreign water into a producing
well or block pressure leakoff into the formation. Advantages of using gels are two-fold. They can be washed out of the
wellbore after a leak is squeezed, preventing the costly rig time necessary to drill out cement. Second, since such solutions
exert a much lower hydrostatic pressure than cement slurry, there is less possibility of breaking down the formation and
losing the squeeze seal.
In this work, sodium silicate gels made with an organic initiator in the presence of a polymer, such as a polyacrylamide
derivative, were evaluated for conformance control and casing leak plugging. Uniform silicate gels are almost impossible to
prepare because the reaction is rapid between sodium silicate and an acidic setting agent. Most silicates form very rigid, non-
uniform gels subject to fracturing or syneresis with concomitant shrinkage.
Certain organic initiators form delayed gels with sodium silicate. However, these gels are brittle without elasticity and the
gels require high material concentrations. Sodium silicate is a complicated system of various molecular weight silica
polymers in an alkaline solution. Aside from requiring a certain minimum amount of buffered alkalinity, sodium silicate has
no definite chemical combining numbers. When sodium silicate is acidified to a pH of less than about 10, sodium silicate is
converted partially to silicic acid. Silicic acid is a weak acid at these alkaline pH values. Silicic acid remains hydrated and
forms a three-dimensional network in trapping the solvent water instead of precipitating and making silica, SiO
2
. This
network is a gel since both phases are continuous. A slight lowering of the pH brings about radical changes in gel time.
Consequently, gel times are difficult to control, and lumping from local acid concentrations during large scale mixing
frequently occurs.
The problems associated with forming silica gel were over come when partially hydrolyzed polyacrylamide was added to
sodium silicate solutions prior to initiating gelation using an organic initiator. Gels were formed ranging from soft gels to
very hard, ringing gels with gel times of minutes to days. This system is termed the Silica Polymer Initiator (SPI) gel. Gels
formed in this manner are elastic in behavior like a polyacrylamide gel and do not exhibit the characteristic brittleness of
sodium silicate gels with the same initiator.
The presence of the polyacrylamide in the formulation is unique and novel resulting in a more elastic gel. Without
polyacrylamide in the SPI formulation, a delayed silica precipitation occurs to generate a very opaque brittle gel. Neutral pH
polyacrylamide solutions do not react with the organic initiator and sodium silicate does not react with polyacrylamide. The
Initiator provides a source of protons allowing the silica to form a silica hydrogel in the presence of polyacrylamide coils.
The silica hydrogel may be weakly bound by hydrostatic forces to the polyacrylamide molecules. These hydrostatic forces
between the silicate hydrogel and the polymer tend to wrap around the polyacrylamide and also bind two or more polymer
chains together in a weak crosslink. As gelation occurs, the pH drops from approximately 12 to the 10 7 range.
This paper presents data of screening experiments for the selection of polymer and initiator types and for defining the
range of component concentrations suitable for casing leak repair and conformance control in water injection wells and water
shutoff in production wells. Two systems were studied in further detail; one for casing leak repair and one for water shutoff
and conformance applications.
Initial Screening Experiments
Screening experiments were conducted to determine the effect of different polymers and initiators on gel times and gel
characteristics. Screening of polymer and initiator types were studied using high concentrations of sodium silicate. After
selection of polymer and initiator types, limited systems with lower chemical loadings were investigated to identify
compositions for applications of water shutoff/conformance control and casing leak repair. Lower concentrated systems have
longer gel times and are more economical.
SPE 113490 3
Experimental Details. The sodium silicate used in this study was N-Sodium Silicate available from PQ Corporation. N-
Sodium Silicate has 37.85% solids as SiO
2
and Na
2
O and 28.90% as SiO
2
. The pH is approximately 11.3. N-Sodium silicate
has a molar ratio of silicon dioxide to alkali metal oxide of 3.22. Numerous initiators were tested and the results using two
initiators, A and B, are presented. Composition of the initiators is confidential pending patent approvals. Polyacrylamide
polymers were evaluated ranging between high and low molecular weights and varying amounts of levels of hydrolysis
ranging from 0 50%. Polymers used were: Alcoflood 254S (AC 254S), a 250,000 molecular weight polyacrylamide with 7
percent hydrolysis; Superfloc
flocculants with both high and low molecular weight polyacrylamide polymers of various
anionicity; Goodrite
polymers that are polyacrylates; HE