Abstract
Understanding the behavior and responses of shale to shale inhibitor additives of drilling and completion fluids has been a
challenge for many years because of the numerous and complex chemical and physical variations present in these type of
formations. This paper presents the results of laboratory experiments that show how the integration of the geological aspects
can help to understand the different responses of the shale to fluids and improve the selection of chemical additives for clay
inhibition.
Many of the chemical inhibitor additives have been developed in the laboratory through systematic methods with the use
of standard clay-rich rock samples. These rock samples have relatively simple geologic characteristics and predictable
behaviors. The responses of these types of rock samples tend to be consistent and appropriate for evaluations where
chemistry of the additives is manipulated constantly. However, the application of these additives goes beyond this approach.
In the field, applications target formations that can vary significantly in composition and structure, and simplicity is an
uncommon condition. Therefore the challenge for clay stabilization is to integrate many more aspects that can influence the
response of the shale formation to fluids.
The paper will present the preliminary process of analysis and understanding of the geologic characteristics of the rock
samples and the importance of this fundamental step to achieve the chemical clay stabilization objectives. The paper will
include various cases of the inhibitor selection process for shale samples with different characteristics. Chemistry and
geology perspectives will be used to analyze the results of the experiments including cases with typical and atypical
responses of shale samples. This approach is used to provide a more comprehensive and meaningful interpretation of the rock
structural failures due to rock/fluid chemical interactions and, in the same manner, explain how chemical solutions can be
used to minimize and control rock instability.
Introduction
Extensive work has been done for many years to evaluate and find solutions to mitigate and control the interaction of drilling
fluids and clay-rich formations (shale, mudstone, claystone, and other fine-grained clastic rocks). Significant advances in the
chemistry of clay inhibitors have shown excellent results in problematic shale formations around the world. Conventionally,
different type of salts are added to the drilling fluids or combined in completion brines to control reactive clays. Potassium
chloride (KCl) has been for many years the most recommended type of salt for inhibition purposes. Other inorganic
compounds such as soluble silicates also are recognized for their inhibition capability which uses a combination of chemical
and physical stabilization mechanisms.
Most recent developments in the chemistry of inhibitors concerned organic compounds. Amines compounds are widely
used to provide inhibition properties to water-based drilling fluids and completion fluids. These amine compounds were
developed to replace salts in environmentally sensitive areas and improve the performance of the inhibitor additives. Some
other organic additives are also available to provide a source of potassium in the fluids and stabilize the clays.
Multiple types of other additives are also used to control the invasion of fluids in natural or induce fractures, natural flow
channels, or pores. Most of these additives are inert or non-reactive products that work by creating a physical plug. Different
types of asphaltenes, graphite, calcium carbonate, and other solid products with specific particle sizes are available to create
an effective seal. The latest developments in sealing additives include nano particle products (Ji et al. 2011) and copolymers
(Mehtar et al. 2010). Technological advances with the use of polymers for shale control include different types of polymeric
products to control the dispersion of shale cuttings by encapsulating the clays and preventing contact with water. Most of
these products prevent the invasion of water in the clay structures by an encapsulation mechanism. This paper focuses
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primarily on shale inhibitors that interact chemically with the clay minerals. Additives that act physically to seal or plug the
formations are referenced briefly in some examples.
Although different types of clay inhibitors provide excellent performance in specific formations, there still is not a simple
or general chemical solution to control the instability of shale formations. A specific combination of chemicals for clay
inhibition can be successfully used for a specific shale but not for another shale even though the two formations have the
same amount and type of clays. For this reason, the selection of the inhibitors becomes a customized process where types,
amounts, and combinations of chemical additives are carefully optimized using multiple laboratory experiments using a
single shale sample to represent the problematic formation. This testing optimization process is very effective not only
because the actual shale formation can be used for the experiments but because it can integrate and cover many more aspects
related to the rock material beyond type of clays, amounts, and reactivity. These other aspects are related to the structural
rock properties which can be as important as the chemical interactions between clays and fluids. The structural properties of
the shale formations can vary significantly to the point that in some cases they are more important to the instability
mechanism than the impact of the mineral composition of the rock.
Chemical Inhibition Additives
Water-based drilling fluids systems and completion brines are formulated with inorganic or organic additives, mostly in the
form of salts to enhance the shale inhibition properties. Potassium chloride is a widely used inorganic shale inhibitor while
quaternary amine salts are favored organic shale inhibitors. These shale inhibitors can be classified in two categories:
temporary shale inhibitors, also known as clay-controlling additives, and permanent shale inhibitors, also known as claystabilizers. Both of these classes of shale inhibitors have their pros and cons.
Inorganic Shale Inhibitors
Salts such as sodium chloride, calcium chloride, and potassium chloride are clay-controlling additives and provide temporary
shale inhibition. These salts are only effective as long as the water-based drilling fluids containing these salts are in contact
with the clays. However, as soon as the salts are depleted or the salt-containing fluid is displaced by fresh water, the clay will
again hydrate and swell, destabilizing the drilled formation. The concentrations of salts between 2 and 37% are frequently
used in drilling fluids.
Salts retard the swelling of the clay through a variety of mechanisms. The cation exchange reaction reduces the amount of
water that can be absorbed by hydratable cations on the surface of the swelling clays. This mechanism however becomes
ineffective when clays contain little or no exchangeable cations. Alternatively, a large quantity of salts, such as heavy brines
or other electrolytes, have been used to increase the ionic concentration of the water phase in order to retard osmotic
hydration. This method of shale inhibition becomes very effective in shale formations where Smectite is the predominant
clay mineral.
Inorganic salts are relatively inexpensive and are extensively available throughout world. Also, they can be applied in
variety of drilling environments, such as high temperature and high pressure, and in wide range of pH conditions as they are
chemically very stable. However, in large quantities these salts may adversely affect the chemical biological ecosystems. For
example, above certain limits, these salts have an adverse effect on water quality and soil quality for agriculture use. This
impact by fluids with high salt concentrations has led to their undesirability in environmentally sensitive land-based drilling
locations and surface disposal restrictions imposed by environmental authorities. In exploratory drilling, high conductivity
from these salts interferes with the sensitivity of induction logs. These salts also bring other restrictions, such as
incompatibility with other drilling fluid additives and limited flexibility in drilling fluid formulations. Nevertheless,
potassium salt has been the workhorse in shale inhibition for many generations either used alone or in combination with other
type of inhibitors.
Silicate additives also have been used in drilling fluids for many years. The soluble silicates are metal salts of silicic acid
and exist in multiple polymeric forms in solution. Solid silicate products are also available. The three main components in the
silicates are: silica (SiO2), Alkali (Na2O or K2O) and water. The molecular structures of the silicates can vary from simple
chains of monomers to complex structures. The inhibition mechanism of the silicate consists of a combination of two
chemical reactions: gelation and precipitation. The gelation consists of the self-polymerization of the silicate structures to
form a gel structure. This chemical reaction is controlled by pH. The polymerization begins at pH below 10.5. Precipitation
of silicate is the cross-linking of silicate by multivalent cations. During the drilling process of shale formations, the pH of the
drilling fluid systems will drop below 10.5 when it is in contact with the formation fluids (pH~7). The precipitation also will
take place when multivalent cations present in the formation fluids react with the silicates to form insoluble precipitates (van
Oort 1996). The gelation and precipitation take place on the surface of the shale blocking the influx of fluids and pressure
into the formation. Sealing of microfractures also is attributed to the silicate reactions in the wellbore which prevent further
opening and weakening of the rock along fractures or bedding planes.
Organic Shale Inhibitors
To combat the environmental impact and performance-related issues associated with salts, particularly with potassium
chloride, a number of alternative cationic sources have been evaluated. This was the starting point for the development of
some exotic cationic amine compounds as shale inhibitors. These shale inhibitors are classified as a more permanent type of
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shale inhibitors and are also known as clay-stabilizers. These shale inhibitors chemically interact with shale by multiple or
single cation exchange mechanism, either by entering in to the shale matrix or reacting on the surface of the shale. These
amine-based shale inhibitors are very effective on shale with high cationic exchange capacity. Various types of cationic
organic amine salts have been used in the field; however, these salts were unstable at high-pH and high-temperature
conditions typically encountered in the field. Upon decomposing, these amine salts produce an obnoxious ammonia odor and
are rendered ineffective as shale inhibitors. To alleviate the problems associated with toxicity, odor, stability and performance
of some of these simple amine salts, a vast number of exotic amines and quaternary amine compounds have been developed
and applied in the field. Depending on the structure and chemistry, these compounds are classified in three major categories:
monomeric, oligomeric and polymeric amine shale inhibitors.
Monomeric Amine Shale Inhibitors.
In monocationic amine-based shale inhibitors, the sodium ions in the clay are substituted with cationic amine species by a
cationic exchange process. The low-molecular-weight monocationic amines (Fig.1) enter into the clay platelets and reduce
the amount of water adsorbed by the clay, thus reducing the clay swelling due to hydration. Another advantage of
monocationic amines is the reduced level of treatment required to attain a high level of inhibition as compared to inorganic
salts. However, most of these monocationic amine shale inhibitors have a lower level of shale inhibition and higher
ammoniac odors when compared with oligomeric or polymeric amine shale inhibitors and, therefore, their application as
shale inhibitors is limited. Various monomeric shale inhibitors, such as ammonium chloride, tetra-methyl ammonium
chloride, choline chloride and other ammonium derivatives have been developed and applied in the field with varied success.
R
NH 2
(
)
O
NH 2
x
R
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28
15
15
1
3
2
1
35
23
Arne
Clay
16
25
25
1
1
1
1
30
13
Norway
Shale
20
35
10
1
3
1
30
19
Wyoming
Bentonite
41
5
10
9
35
33
The clay content of these rocks is relatively high 45-65%. Reactive clay minerals are present in these rocks: Smectite,
Illite, and Kaolinite. The CEC data indicates that these samples have moderate to high reactivity (Stephens et al. 2009).
Another important feature of these rocks is the homogeneous structure. The thin-section photograph (Fig. 5) shows the
massive structure of the rocks (lack of bedding or poor laminated structures) which makes these samples excellent for
rock/fluid interaction studies. Consistency of the rock properties is important to be able to identify the effect of concentration
or chemical composition of the inhibitor additives.
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Oxford Clay
Arne Clay
Norway Shale
Wyoming Bentonite
In general, the structural characteristics of these rocks are simple. Minor variations in the mineral composition and size of
the grains are observed not only in the micron scale but also in larger scales (centimeter, meters, or more).
Figure 6 presents the results of bulk hardness tests conducted with the Oxford clay and different inhibitors. This test is
used to determine the hardness of the rock sample after exposing to a test fluid.
In this test, fragments of rock are exposed to the fluid under hot-rolling conditions. Then the fragments are recovered and
extruded through a perforated steel plate utilizing the bulk hardness tester. The data represents the number of turns of a feed
screw and the torque required for each turn. Depending upon the efficiency of shale inhibitor and hardness of the shale, the
torque may reach maximum torque of 225 inchlb and the sample form a disc-shaped extrusion. Highly efficient inhibitor
additives will yield harder rock indicated by higher torque readings. In this case the results show that the fluid formulations
containing oligomeric shale inhibitors performed better than other chemical combinations.
Bulk Hardness-Oxford Clay
250
Torque (inch-lb)
200
150
100
50
0
1
9 10 11 12 13 14 15 16 17
Number of Turns
KCl/Glycol
PHPA/NaCl
PHPA/Glycol
Oligo Cationic-1
Oligo Cationic-2
Poly Cationic
Figure 6. Bulk hardness test results for different clay inhibitors using Oxford clay
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Examples of pieces of rock with laminated and massive structures exposed to an oligomeric amine inhibitor are presented
in the Figures 9 and 10.. Note that the direction of the cracks and fractures is related to the structural characteristics of the
rock.
0.5 inch
0.5 inch
Figure 11. Cracking of shale samples during the exposure to fluids. Multiple breaks occur along the bedding
direction. Each rock also broke along a cross
cross-bedding
bedding natural fracture.
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Complex rock structures are also present in formations with significant clay content and potential for instability. The shale
formations are generally found close to oil traps creating the seal for the reservoirs. It is common to find irregular
stratification and cross-laminations in the transition zones near to the reservoir zone. Interbedding structures of shale,
siltstone, and sandstone are also important to evaluate because the clay content can vary significantly from high to low
content within a few centimeters. Figures 12 and 13 show an example of interbedding structures. The structure of the rock
exhibits lenses with predominance of silt-size quartz (light color material) and clay-rich beds (dark brown areas).
1 cm
Figure 12. Direct photograph of lenticular bedding
structure formed by shale and cross-laminated
siltstone.
It was found that the clay content of the two types of rock was very different. The dark gray rock had approximately 26%
clay while most of the light gray color rock had approximately 57% clay minerals. The highest clay content in a few layers
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was up to 88%. Predominance of smectite was identified in all the samples. Based on these analyses, it was necessary to
redirect the clay inhibition design of the drilling fluid to the most critical factor in this rock. The presence of highly reactive
layers of clay was evidently the initial target in this case. The testing method selected for the evaluation of the different fluids
was the linear swelling test (Stephens et al. 2009). This method specifically measures the swelling tendency of rock samples
with drilling fluids and is certainly the most appropriate technique when the rock samples have a significant amount of
swelling clays. Figure 16 shows the results of the swelling test. The data shows the final tests results after multiple tests
conducted for optimization of the salt concentrations. Based on the results, sodium chloride (NaCl) had a better inhibition
performance than the traditional KCl. Excessive swelling of the clays was observed with the use of a non-inhibited fluid.
Smectite-rich shale
Linear Swelling Test
100
90
Expasion (%)
80
70
60
50
40
30
20
10
0
0
200
400
7% NaCl
600
800
1000
Elapsed Time ( min)
7% KCl
1200
1400
Figure 17. Three illite-rich shales after fluid exposure. Development of fractures mainly along the bedding plane is observed in
these samples. The extent of fracturing varies from severe to minimum from left to right. Illite content also varies from high (~48%)
to low (~6%) from left to right.
Many illite-rich shales respond negatively to poor or non-inhibited fluids. Fracturing can be observed in the samples after
immersing the rock pieces in different fluids. Appropriate selection of the clay inhibition additives help to minimize
fracturing and weakening of the rock structure. Figure 18 shows pieces of shale with ~48% of illite. The samples were
exposed to the three fluids with different types of clay inhibitors. It was found that the fluid containing K-Silicate
significantly controlled the opening of the rock along the bedding plane.
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Figure 18. Illite-rich shale samples exposed to different fluids. From left to right 1) Freshwater/Gel/Polymer system
(non-inhibited fluid) 2) Polymer/amine system (inhibited fluid), and 3) K-Silicate system (inhibited fluid).
The use of sealing additives for a physical plugging of natural or induce fractures can be also prevent the invasion of
fluids into these hard and brittle shale formations. A combination of chemical inhibition and physical plugging is generally
recommended for gas shale applications.
Case 3. Reactive Silt Shale Formation with Sandstone Lenses
Interbedded shales present in the sandstone reservoir represent a challenge for reservoir drill-in fluid design and also for
completion fluid which needs to provide inhibition and control of clays in openhole completion operations. Unstable shale in
openhole sections may cause premature screenouts, reduction of the permeability of gravel packs, and inability to run
completion tools and assemblies (Shenoy 2008).
Samples from the interbedded silt and shale section of the reservoir zone in Equatorial Guinea were evaluated with the
completion fluids to understand the potential behavior of the rock material in contact with the fluids. The rock samples had
approximately 40 to 46% clay. Additionally, the rock had a significant amount of localized clay-rich areas close to permeable
sandstone lenses. Invasion of the brine through the permeable sandstone to reach zones with reactive clays was a concern for
the completion operation. Thin section images of the rock are presented in Figures 19 and 20.
The white grains in Figure 19 are mainly quartz and feldspar. The brown background is clay. The samples have some
fractures that may be caused by natural dryness of the unpreserved rock. The sandstone lenses in the samples were not well
consolidated. The blue areas in the Figure 19 are pores. Clay-rich areas are located close to the sandstone lenses.
The samples were exposed to freshwater, base brine, and base brine with a monomeric amine inhibitor additive. Test
results are shown in Figure 21. The results of the test with water showed that the sample had a strong reactivity and potential
for instability. The sample dispersed in water in few minutes. Unexpectedly, the samples remained intact in both brine
solutions. The calcium chloride (CaCl2) brine provided the right inhibition to this rock regardless of the multiple
characteristics of the rock which represented potential risks of instability.
10
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Figure 21. Silt shale with sandstone lenses (light color areas in the rock pieces) exposed to different fluids: from left to right 1)
Freshwater 2)10.2-lb/gal CaCl2 and 3) 10.2-lb/gal CaCl2 with 8-lb/bbl monomeric amine.
Other Observations
Other particular cases showed that some formations do not behave as expected according to the structural characteristics.
Although the preliminary analysis of the rock indicates that the strong laminated structures were potential factors for opening
fractures along the bedding plane, the response of the shale were different in the experimental phase. Highly laminated shale
dispersed totally in presence of freshwater instead of the anticipated breaking of the rock along the bedding. Development of
fractures in other directions different to the bedding plane was observed in the rock after the exposure to potassium formate
brine. Figure 22 shows an example of atypical behavior of a shale sample in fluids.
Figure 22. Strong laminated shale core pieces before and after fluid exposure. From left to right 1) Sample before fluid exposure. 2)
Sample exposed to freshwater. 3) Sample exposed to Potassium formate brine.
Conclusions
Understanding the individual properties of the rock and fluids is an important step to achievinf chemical control of clay
minerals using inhibitor additives. The mechanisms of interaction of the different type clay of inhibitor products are generally
well understood. However the properties and responses of shale formations to fluids are difficult to generalize and classify.
Each rock is a unique system with a unique combination of properties. The mineral composition, structure, grain distribution,
consolidation, and other geologic properties of clay-rich formations can vary significantly. Additionally, rock properties,
reactivity, and stability can not only change within a few feet along the shale sections but also can change within a few
millimeters especially in fine laminated shales. Complex interbedding structures, localized clay-rich zones, or the presence
of natural fractures represent potential factors for wellbore instability. Identification of these properties can help to select the
inhibitor additives, other clay control products, and the evaluation methods for the drilling and completion fluid design.
Although many of the rock/fluid interaction studies show that clay-rich formations behave according to what is expected,
some cases show that some formations can have atypical responses. In these cases, the data collected in the laboratory can be
the first piece of information to anticipate unexpected wellbore instability events, or it can be used to adjust the drilling plans
accordingly.
Acknowledgments
The authors thank the management of M-I SWACO, A Schlumberger Company for permission to publish this paper.
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