SPE 106476
Advances in Inhibitive Water-Based Drilling Fluids—Can They Replace
Oil-Based Muds?
Arvind Patel, Emanuel Stamatakis, Steve Young, and Jim Friedheim, M-I Swaco
Copyright 2007, Society of Petroleum Engineers
This paper was prepared for presentation at the 2007 SPE International Symposium on Oilfield
Chemistry held in Houston, Texas, U.S.A., 28 February–2 March 2007.
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Abstract
This paper discusses the systematic design and development
of high performance water-based muds and provides insight
into the unique chemistry and inhibition characteristics of
various amine inhibitors. Equally important, performance
correlations of inhibitive systems in laboratory testing as
compared to state-of–the-art inhibitive systems are included.
Invert emulsion drilling fluids have long been effective in
drilling reactive shale. Developing high performance (highly
inhibitive) water-based drilling fluid that would perform like
invert emulsion drilling fluid has long been cited as the
ultimate technical goal of the drilling industry. Progressive
development of inhibitive water-based drilling fluids based on
amine chemistry has made some impact on reaching this goal.
Amine-based inhibitive drilling fluids have steadily gained
popularity with service and oil companies.
However, these fluids have not always been completely
successful in inhibiting the hydration of highly water-sensitive
clays. The short-comings are particularly evident when
drilling highly complicated and reactive shale formations.
Keeping this in mind, an innovative highly inhibitive water-
based drilling fluid has been systematically designed with the
performance characteristics of oil-based muds.
The newly developed high performance water-based mud
(HPWBM) comprises a unique polymeric amine shale
intercalator for shale inhibition, an amphoteric polymeric
shale encapsulator, a high performance lubricant/anti-
accretion agent and a specialized fluid-loss additive. The
newly developed HPWBM performed like an oil-based mud in
laboratory testing as well as in offset wells using invert
emulsion drilling fluids (OBM) due to highly complicated and
reactive shale formations.
Introduction
To address the drilling problems associated with shale
instability various non-aqueous drilling fluids (NADF) such as
mineral oils, saturated and unsaturated poly alpha olefins and
esters have been developed and utilized in the field.1-4 Along
with the shale stability benefits of these NADF, various other
benefits like lubricity, temperature stability, and anti-accretion
are attributed to NADF. These distinguished benefits of
NADF usually are cited as the technical goal of an ultimate
HPWBM.
Along with those advantages, NADF have disadvantages,
such as high cost, environmental limitations, disposal
problems, health and safety issues and detrimental effects on
the drilling and completion of the pay zone. Consequently, a
water-based drilling fluid which performs like an oil-based
mud has been an ambitious goal of the drilling industry. Two
characteristics of the HPWBM have been identified that
contribute significantly to performance of the drilling fluid –
shale stabilization and lubricity properties. These OBM
characteristics serve as design targets to many researchers of
aqueous-based systems striving to achieve the performance of
OBM system when using a WBM.5-8
When water-sensitive shale is exposed to conventional
water-based drilling fluids, shale has an immediate tendency
to take up water from the drilling fluid. Depending upon the
chemical characteristics of the shale, this can result in a rapid
swelling or dispersion of the shale. Consequently typical
problems such as bit-balling, disintegration of cuttings,
borehole wash-out, high torque and drag, and stuck pipe are
often encountered as a result of water adsorption by water
sensitive shale.9-10
For more than the past five decades, various chemicals
have been used for inhibition of water-sensitive shales.
Among the earliest and most widely used method relies on the
use of high concentration of salts such as potassium chloride,
sodium chloride and divalent brines. These salts through a
variety of mechanisms might be claimed to somehow retard
swelling. The early development of the shale inhibition fluids
included sodium chloride/starch muds,11 silicate muds,12 lime-
muds and calcium sulfate-based gyp muds.
However, these salts in large quantities adversely affect the
chemical and biological ecosystems. These salts also pose
limitations such as drilling fluid additive compatibility and
flexibility in mud formulations. In the late 1960’s and early
1970’s, polymer/KCl muds became popular.13 A variety of
2 SPE 106476
polymers in combination with KCl were evaluated to achieve
a higher level of shale inhibition as compared to potassium
chloride alone. High-molecular-weight partially hydrolyzed
polyacrylamide/KCl was found to be effective at low
concentrations of polymer. However, surface swelling due to
insufficient shale inhibition and high viscosity of polymers
offered little to partial success in providing the satisfactory
results. The PHPA polymer also can be harmful to human
health due to evolution of ammonia from hydrolysis of
acrylamide as well as the residual acrylamide monomers.
PHPA/KCl muds contain anywhere from 2% to 8% KCl by
weight. The disposal of these high salinity fluids can be a
problem affecting marine ecology and land farming. In any
case, the potassium chloride salt became the work horse in
shale inhibition and has been used in combination with various
other salts and fluids.
The disadvantage of these polymer/KCl-based drilling
fluids in drilling operations is their dependency on electrolytes
for optimum shale inhibition. Such materials can have a major
impact on some receiving environments, which can limit their
use, restrict their discharge or sometimes require costly
treatment prior to discharge.
The glycol and polyglycol in combination with KCl and a
KCl/polymer system14 were applied in the field in 1990’s with
limited success. Again the level of inhibition even with this
combination was not enough and only limited application was
found.
As mentioned earlier, interest in silicate-based drilling
fluids, which had waned from the 1940s until the mid 1990s15,
was renewed with use of the silicate in combination with
potassium and led to use in a number of drilling fluid
applications in various regions of the world. This fully
formulated silicate-based drilling fluid contained high
concentrations of potassium/silicate. The level of inhibition
using these high concentrations was found to be very good,
however there are several limitations such as high torque and
drag due to precipitation of silica, high pH becomes a health
hazard and limitation in mud formulation has limited its
application.
Potassium normally in chloride salt form was added to
drilling fluids and was found to be an effective shale inhibition
for swelling clays. This has become the starting point for the
evolution of some exotic salts as well as ammonium and
amine-based chemistry for shale inhibition in high
performance water based muds.
Evolution of Nitrogen-Based Shale Inhibitors
Ammonium Cation Shale Inhibitors
The simplest form of the ammonium-based cation is ammonia
neutralized with acid (Fig. 1).
NH3 + HA ------------Æ N+H4.A–
Fig. 1 – Ammonium chloride cation.
Advantages: As the ammonium cation has a very similar
hydrated volume as potassium cations16 it can enter into the
clay platelets like potassium ion and function as a shale
inhibitor. Also, ammonia and ammonia neutralized salts are
relatively inexpensive. Due to its economic advantages it was
also used in combination with other acids and anionic
materials such as phosphoric acid and polyanionic cellulose,17
These salts were preferred due to their application in chloride-
free environments.
Disadvantages: The application of ammonia-based salts as
shale inhibitors was short lived and found only very limited
application due to maximum temperature stability of 150°F.18
At higher pH, which were normally used in water-based mud,
the ammonia salts will dissociate into ammonia and the odor
of the ammonia becomes obnoxious as well as a hazard to
personal working around the drilling site.
Quaternary Alkyl Ammonium Salts
To mitigate and deal with the obnoxious odor of ammonia,
higher molecular weight ammonium salts made their way into
shale inhibition applications. Various derivatives of ammonia
were developed by substituting alkyl groups for hydrogen.
R
+
N
R
R R
Fig. 2 – Tetra alkyl ammonium salt.
The smallest and lowest molecular weight derivative of
ammonia which found application in shale inhibition is tetra
methyl ammonium chloride also known as TMAC (Fig. 2).19
Somewhat higher molecular weight quaternary amine salts
which are in the surfactant category made their way into shale
inhibition in the late 1980’s.20 These compounds were
quaternized tertiary amines such as dimethyl dialkyl
ammonium chloride and various derivatives.
Advantages: Compared to simple ammonium salts, these
amines had less of an amine odor and were somewhat user
friendly. Also these inhibitors required a lot less concentration
than the counterpart potassium chloride or other inorganic
salts to achieve similar results. The low concentration
treatment also reduces the amount of chloride introduced and
enables a degree of shale stability on land jobs with chloride
or conductivity restrictions.
Disadvantages: The effectiveness of quaternary amines is
pH dependant. They function better at lower pH. TMAC and
other high-molecular-weight quaternary amines are found to
be toxic especially to the marine environment. In addition,
high-solid fluids are severally flocculated by quaternary
amines products and compatibility with anionic drilling fluid
additives has been a major draw back in drilling fluid
formulations.
Introduction of Polyamine Acid
To overcome some of the problems associated with pH
limitations and toxicity issues associated with aforementioned
cationic shale inhibitors, modified poly-amino acid hydration
suppressant was brought to market in 1993.21 The product was
SPE 106476 3

prepared by reacting chloroacetic acid with polyalkylene Disadvantages: The only draw back to this chemistry is
amine (Fig. 3). the low level of inhibition and solid tolerance.
COOH
Enhancing Shale Inhibtion Properties of Quaternery
NH2
Amines
NH
In mid 1990’s23 a new class of amines was introduced to
enhance the shale inhibition properties of quaternary amines.
Cl + Unlike the quaternary and tertiary amines, these were primary
COOH HOOC
HN mono and di-amines. The hexamethylendiamine (HMDA) (fig
N
5) became popular in the Canadian market due to its
availability and shale inhibition properties. The primary
application of this shale inhibitor was in facturing and
NH2 stimulation fluid.
NH

H2N
NH2
COOH
Fig. 3 – Polyamino acid.
Fig. 5 – HMDA

Functionally, polyaminoacid can be described as a

Advantage: HMDA is readily available and performs well
hydration suppressant limiting the ability of smectite clay to
as a shale inhibitor. It also is less toxic than some of the
hydrate and swell when exposed to water. The amphoteric
cationic shale inhibitors used in the past.
polyaminoacid has a low molecular weight and a low charge
Disadvantage: Optimization of shale inhibition is limited
density and posses an amphoteric character.
to the insolubility of the higher chain length diamines in water.
Advantages: This shale inhibitor is completely water
The lower molecular weight diamines have toxicity and odor
soluble, and thermally stable. As it has no hydrolysable
issues, while higher chain length mono-amines are not
functionality, it is environmentally acceptable for use in
effective shale inhibitors.
offshore applications. Unlike cationic products, the polyamino
acid is compatible with drilling fluid additives including salts.
Polyethoxylated Diamines as Shale Inhibitors
Also, it has very little to no limitation on fluid formulations or
During this time several polyethoxylated diamines24 were tried
limitations on use of drilling fluid additives.
as shale inhibitors (Fig 6).
Disadvantages: While the polyamino acid is effective as a OH
hydration suppressant, it does not dehydrate the hydrated
HO
clays. In addition, it does not perform well in highly active
solids-contaminated systems. Overall, the product worked
well but shale inhibition was not to the optimum levels. N
N
Introduction of Polyhydroxylated Alkyl Ammonium Salt
In mid 1990s,22 a new class of amines was introducd to deal
with toxicity, performance and compatibility issue for their
potential application as shale inhibitors. These compounds OH
OH
were hydroxyl alkyl and polymeric hydroxylated alkyl
ammonium chlorides. Fig. 6 – Ethoxylated diamine.
HO HO
Advantages: Polyethoxyalted amines have low toxicity and
low ammonia odor.
Disadvantages: Shale inhibition below average.
+ +
N N
OH
A New Class of Primary Diamines
HO O
To mitigate the limitations of HMDA chain length and
CH3 CH3
molecular design, a new class of primary diamines was
introduced in the market during the early 2000’s.25 These
Fig. 4 – Polyhydroxylated alkyl ammonium salt
amines are polyether diamines (Fig. 7). These amines are
prepared by reductive amination of polyglycols.
Advantages: These compounds are compatible with
anionic drilling fluid additives and are found to be HO O NH2
environmentally acceptable for application in the Gulf of OH
O H2N
Mexico (GOM). Choline chloride has advantages over other
H3C CH3 CH3
hydroxyl alkyl quaternary amines due to ready availability, H3C

low cost, biodegradability and low toxicity. Fig. 7 – Polyetherdiamines.

4 SPE 106476
Advantage: Polyether diamines eliminated the limitations
of chain length due to the higher polarity introduced by ether
linkages in the molecule. These ether linkages allowed the
variation in chain length and structure to optimize the shale
inhibition performance.
The polyether diamines have very low ammonical odor
specifically when used in water-based muds. They exhibit low
marine toxicity for offshore applications. These polyether
diamines are compatible with other common water-based
drilling fluid additives. Since it has no hydrolysable
functionality, it is stable to high temperature in aqueous
system.
The unique optimized molecular structure of diamine
perfectly fits between clay platelets tending to collapse the
clay’s hydrated structure and greatly reduce the clay’s
tendency to imbibe water from an aqueous environment (Fig.
8).
Unlike other quaternary amines and shale inhibitors,
polyetherdiamines require very little salinity for optimum
performance and performance well in absence of potassium
cation.
Fig. 8 – Molecular model of hydration suppressant binding
mechanism to shale layers.
Recent Development in Lipophilic Polymeric Amine
Inhibitors
Recently, highly lipophilic amines were introduced26 as very
potent ant shale inhibitors in HPWBM. These amines are
excellent shale inhibitors in water-based muds at or below 9.5
pH. At these pH’s amines are protonated or at least partially
protonated and become water dispersible and are very
effective shale inhibitors. These economically tailored, less
expensive polyamines (Fig. 9) meet the performance criteria.
However, sometimes at certain pHs these lipophilic amines in
their protonated form behave like a surfactant and impart some
foaming, which can be dealt with by use of deformer.
R R'
NH
NH
Fig. 9 – Lipophilic amine.
Development of HPWBM
The advent in research and development of novel amine
chemistry represented the significant improvement in shale
inhibition and development of HPWBM. Key new
components of this HPWBM are the unique primary di- and
poly-amines. As aforementioned, carefully tailored poly
etherdiamines fit perfectly between clay platelets and binding
the plates together. This prevents water absorption from the
surrounding aqueous liquid and prevents the shale from
swelling. Moreover, the unique molecular structure and blend
of polyamines adsorbs on the shale surface, thus entering
inside the clay platelets and providing excellent shale
inhibition. Along with these novel shale inhibitors, four other
specifically designed components are incorporated in newly
developed HPWBM formulations. The brief description of
these four components follows:
Dispersant Suppressant. This is a low-molecular-weight
partially quaternized water-soluble copolymer. The optimized
cationic charges and molecular weight of the copolymer allow
it to be adsorbed on negatively charged clay surface keeping
the clay plates togather without imparting excessive viscosity
to HPWBM. Unlike other dispersion suppressants this
copolymer provides superior shale inhibition without
restricting the mud formulations.
Antiaccretion Agent. This is a unique blend of surfactants
and lubricants which is incorporated in the HPWBM to reduce
the accretion of hydrated shale cuttings on the drill bit and
prevent the agglomeration of drilled cuttings. The components
of this antiacreation agent are compatible with other drilling
fluid additives of HPWBM.
Fluid Loss Control Agent. This is a low-viscosity
modified cellulose polymer. The low viscosity of the polymer
allow its functional characteristic and utility in high solids
(active and inert) containg drilling fluids, such as highly solids
contaminated or high density water-based muds. The polymer
provides fluid loss control without affecting the other
functional properties of drilling fluid.
Rheology Modifier. This is a blend of natural polymers to
impart high low-shear viscosity for efficient carrying capacity
in HPWBM. The synergistic performance of this polymer
blend with shale inhibitor extends the utility of rheology
modifier in excess of 300°F.
HPWBM Design Criteria
As mentioned, the main objective of HPWBM is to obtain
drilling performance comparable to OBM. To achieve this, a
high level of shale inhibition, excellent lubricity and good
fluid loss control are needed. The development of HPWBM
fluid formulations began with the choice of shale inhibitor
followed by the addition of other drilling fluid additives to
achieve the drilling performance of OBM. Each component of
the HPWBM was tested individually for its utility in the
drilling fluid. To measure the ability of HPWBM to inhibit
the shale, the bentonite inhibition and bulk hardness tests were
SPE 106476 5

conducted. The bentonite inhibition tests were conducted on Base KCL Choline Chloride Polyether diamine Polyamine
unviscosified water-based fluid and bulk hardness tests were
conducted on fully formulated fluids. The lubricity and 350
antiaccretion tests were conducted using fixed weight and 300

10 min gel
250
fixed size steel rods. Hot roll dispersion tests were conducted
200
on fully formulated HPWBM using fixed size shale cuttings 150
and hot rolling at 150°F. The following is the detailed 100
description of each shale inhibition test procedure. 50
0
Shale Inhibition 50 70 90 110 130 150 170 190 200 210 220 230 240
The shales used were outcrop shales ranged from highly Bentonite (lb/bl)
swelling type like Wyoming Bentonite to highly depressive Fig. 11 – 10-minute gel comparison of Bentonite Inhibition Test.
like Arney Clay from Norway. Two other shales included in
this study, Foss Eikeland and Oxford clays, were mixed clay.
Along with these shales, various other field shales were
utilized for evaluation. The inhibition test methods are
described below.
Bentonite Inhibition Test. The bentonite inhibition test
method is used routinely as a screening method to determine
the ability of a product to prevent bentonite from swelling and
maintain a low rheological profile. This test method is
designed to simulate the incorporation of highly active drilled
solids into a drilling fluid similar to what occurs while drilling
water-sensitive shale in the real-time field application. The test
method determines the maximum amount of API bentonite
Fig. 12 – Bulk Hardness Tester
that can be inhibited by a single treatment of shale inhibitor.
Normally, 8.0 lb/bbl of shale inhibitor is used for this test.
Bulk Hardness Test. This test is used to determine the
Figure 3 series compares the performance of several amine-
hardness of the shale sample after exposure to a test fluid. The
based shale inhibitors and potassium chloride. In this test 350
hardness of the shale sample indicates the inhibitive properties
mL of water containing 8.0 lb/bbl of shale inhibitor was
of the drilling fluid being evaluated, i.e., the shale inhibitor
treated daily with 10 lb/bbl of API Bentonite after heat aging
greatly reduces the clay’s tendency to imbibe water from the
at 150°F for 16 hours. After heat aging each day, the
aqueous environment of the drilling fluid. This can translate
rheological properties were measured (Figs. 10 and 11).
into good shale inhibition and stronger wellbore strength
160
during the drilling operation resulting in trouble-free drilling
of water-sensitive shale formation.
140 The bulk hardness tester is shown in Fig. 12. In this test a
Base
KCl fixed size and amount (30.0 g) of shale cuttings are hot rolled
120 Com m ercial Shale Inhibitor
Shale Inhibitor in the test fluid at 150°F for 16 hours. After hot rolling, the
Yield Point (lb/100 sq ft)

100 shale cuttings are sieved (1mm), washed with brine and placed
into a bulk hardness tester. The shale cuttings are extruded
80
through perforated plates using a torque wrench. The torque
60
required to extrude is measured after each turn in
compression. Depending upon the efficiency of the shale
40 inhibitor and hardness of the shale, the torque may reach
maximum torque (250 psi) and form a disc or continue to
20
extrude and form ribbons. Highly efficient shale inhibitors will
0
yield harder shale cuttings and higher torque readings. The
0 20 40 60 80 100 120
test results and comparison of various state–of-art HPWBM
Bentonite (lb\bbl)
and the HPWBM using some innovative amine chemistry
Fig. 10 – Yield point comparision of Bentonite Inhibition Test.
areshown in Fig. 13 and Fig. 14.
6 SPE 106476
Fig. 13 – Comparison of shale inhibitors with Bulk Hardness Test.
Fig. 14 – Extrusion of shale from Bulk Hardness Tester. From left
to right, the fluids in which the shale was immersed were Silicate,
Polyether diamine, Polyamine and PHPA/Glycol.
Hot Roll/Dispersion Test. This test provides the long term
exposure of the shale to the fluid under the normal condition
of drilling when cuttings are brought out and removed from
the borehole.
In this test a weighed quantity of sized shale cuttings are
added to a base fluid or fully formulated drilling fluid using a
conventional fluid cell. Afterwards, the fluid with the cuttings
is rolled in a conventional roller oven at 150°F for 16 hours.
After hot rolling, the cuttings are screened through a 1 mm
size sieve and washed with water. After drying the cuttings,
the amount and percent recovery is determined.
Low dispersion and high recovery is an indication of
functional characteristic of better dispersant suppressant and
better shale inhibition in dispersive shale formation. The test
results obtained from new HPWBM formulations and their
comparison with other state of art mud formulations are given
in Fig. 15.
Fig. 15 – Hot roll dispersion test results.
Accretion Test. In the past, one of the primary reasons for
the failure of HPWBM to perform up to OBM standards was
due to accretion known as “bit balling” where partially
hydrated shale cuttings are compressed onto the drilling
assembly, resulting in poor rate of penetration (ROP) and
other drilling performance limitations. Accretion and
accretion-related problems are very complex and troublesome.
Factors impacting accretion include the type of shale
formation being drilled, drilling fluid, lubricity and other
drilling parameters such as rate of drilling.
The simple laboratory test for accretion consists of placing
a fixed size and weight steel bar in a cell containing the test
fluid and a certain weight of shale cuttings. The cell is then
placed in a rolling oven and rolled for an appropriate period.
After the time laps, the cells are removed from the oven. The
steel bars are removed from the cell and photographed. The
amount and the percent of accretion is determined by
removing, drying and weighing the accreted shale cuttings on
a steel bar.
Again, various high performance WBM formulations were
evaluated and compared against each other for their
performance as anti accreting properties. The results of these
tests are given in Figs. 16 and 17.
Fig. 16 – Results of the AccretionTest using Oxford shale. From
left to right, the test fluids were PHPA NaCl, Polyether diamine,
KCl polyglycol, Polyamine, Silicate, and PHPA Glycol.
Fig. 17 – Accretion Test using Arnie shale.
Results and Disscussion
Bulk Hardness
Figure 13 illustrates the bulk hardness of shales evaluated in
different mud formulations. From the evaluations it can be
seen that the mud formulations containing etheramine and
polyamine shale inhibitors performed the best when compared
with other state-of-the-art inhibitive mud formulations. The
performance compared well against OBM formulation.
Figure 14 illustrates the visual data on bulk hardness after
extruding the shale through a Bulk Hardness Tester. The
SPE 106476
formation of disc is the indication of inhibited hard shale. In
these tests new HPWBM containing etheramine and
polyamine outperformed the other inhibitive mud systems.
Hot Roll Dispersion
Figure 15 graphs the percent recovery of various shales from
several mud formulations using the Hot Roll Dispersion tests.
Again, the percent recovery of shales was highest in the
etheramine and polyamine shale inhibitor mud formulations
than that of other inhibitive drilling fluid systems.
Bentonite Inhibition
Figures 10 and 11 compare the performance of several amine-
based shale inhibitors and potassium chloride. In bentonite
inhibition tests, polyetheramine and polyamine shale inhibitors
inhibited the highest amount of bentonite in these tests. Again,
these inhibitors outperformed other shale inhibitors in these
tests.
Accretion
Figures 16 and 17 show the visual accretion on steel bars.
These tests show that the minimal accretion of shale samples
occurred in the mud formulations containing etheramine and
polyamine shale inhibitors and anticreate agent of new
HPWBM. In these tests new HPWBM outperformed other
inhibitive muds.
Are We There? Does WBM Perform Like OBM?
Significant progress has been made through the advent of
amine chemistry which represents a huge step-change
improvement over earlier attempts to develop a WBM which
would perform like an OBM. The laboratory results reveals
that the newly developed high performance water-based
drilling fluid system significantly reduces clay dispersion,
hydration, and accretion outperforming previously developed
inhibitive WBM systems and reaching into the performance
territory of OBM. The comparative bulk hardness study in Fig.
14 shows that the inhibitive performance of newly developed
HPWBM performed very close to OBM. The new HPWBM
has been designed with a total system approach. Products have
been chosen to satisfy the requirements of performance of
OBM such as high inhibition, nondispersive, antiaccretion and
superior lubricity. The new HPWBM is extremely flexible in
mud formulations, uses a variety of aqueous base fluids and
has temperature stability to 275°F. The system has been
applied with a high rate of success in a variety of field
applications. The system can easily be prepared and exhibits
outstanding drilling performance. The overall performance
and easy of handling are two significant attributes that
significantly brings this system close to performance of OBM.
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