AADE-03-NTCE-36

Progression of Water-Based Fluids Based on Amine Chemistry

– Can the Road Lead to True Oil Mud Replacements?
R. Schlemmer, A. Patel, J. Friedheim, S. Young M-I L.L.C and B. Bloys, ChevronTexaco
Copyright 2003 AADE Technical Conference

This paper was prepared for presentation at the AADE 2003 National Technology Conference “Practical Solutions for Drilling Challenges”, held at the Radisson Astrodome Houston, Texas, April 1 - 3,
2003 in Houston, Texas. This conference was hosted by the Houston Chapter of the American Association of Drilling Engineers. The information presented in this paper does not reflect any position,
claim or endorsement made or implied by the American Association of Drilling Engineers, their officers or members. Questions concerning the content of this paper should be directed to the individuals
listed as author/s of this work.

Abstract rock. The isolated aqueous phase and induced

Ammonia-derived chemicals including amines, amides, wettability changes prevent or delay hydration of clays
polyamides, imines, nitriles and amino acids are used in within sensitive shales. The non-aqueous carrier fluids
many water-based drilling fluid components. Addressed of NAF readily wet the surface of drilled shale but do not
in this paper are those derivatives, which contribute to freely enter the permeable porous matrices of the rock
clay and shale stability. itself. The non-aqueous carrier cannot enter pores of
Ammonium chloride was tested more than 30 years the rock because the water-wetted character of the shale
ago as a shale inhibitor. Diammonium phosphate has pores is maintained by a capillary effect.2 A significant
been used for more than 20 years. Organo-amines were differential pressure of hundreds to thousands of pounds
more recently introduced. Relatively simple organic per square inch is required to displace water wetting the
amines were first added to drilling fluids 15 years ago to inside of shale pores. The pressure required depends
enhance cuttings and wellbore stability. Offering upon the pore size and the wettability characteristics of
performance approaching that of potassium cation, the NAF.3
simple amines effectively carry on in many regions for The emulsified internal phase of NAF, is a
specific applications. Complex amine chemistry is now discontinuous aqueous dispersion, usually a brine,
better understood and the application of such typically a solution of calcium chloride of 100,000 to
compounds in the field is increasing. Several classes of 300,000 mg/L. The emulsified aqueous brine phase is
diamines and polyamines provide a basis for effective isolated from the shale pores by a non-aqueous film of
water-based fluids that have been used to replace emulsifier-surfactant and carrier fluid. This film serves
synthetic-based drilling fluids on several offshore wells. as a semi-permeable membrane and allows an osmotic
An extension of the latest amine technology has pressure differential to develop across the surface of the
enabled design of a membrane-forming water-based shale rock. The osmotic pressure is measurable and
fluid with near 100% membrane efficiency. Recently controllable by adjustment of salt concentration and
introduced amine-based fluid designs are engineer surfactant chemistry and concentration.
friendly, reduce dispersion and hydration of clays, Consequently, these NAF have two easily
reduce drilling costs, and promise to provide shale established characteristics which prevent contact of
stability at surprisingly high temperatures shale with water and contribute significantly to shale
stabilizing characteristics of the fluids. These NAF
Introduction characteristics serve as design targets to many
Shale instability is a continuing and costly drilling researchers of aqueous-based system seeking to
problem despite increasing use of non-aqueous fluids achieve NAF system performance when using a WBM.
(NAF) which include mineral oils, esters, olefins, or other The shale-stabilizing advantages of NAF have
non-aqueous carriers. Shales make up more than 75% associated costs. Additional costs of NAF include, but
of formation drilled and cause in excess of 90% of are not limited to, the actual purchase price of the fluid,
wellbore-instability problems. Use of non-aqueous and environmental considerations, disposal concerns, health
highly inhibitive water-based drilling fluids (WBM) have and safety issues, and detrimental effects on the drilling
not eliminated shale-related wellbore instability operation or reservoir performance. The increased risk
problems. The majority of drilling problems are of circulating losses when drilling with a NAF can
attributed to water sensitivity of shale.1 negatively affect the economics of a drilling operation.
The characteristic benefits of invert emulsion drilling The same capillary effect described above, while
fluids are usually cited as the technical goals of an preventing ready penetration of the formation by drilling
“ultimate” water-based mud. Improved shale stability is mud base fluid, may contribute to serious whole NAF
attributed to use of NAF because of their non-aqueous losses to induced fractures. The full hydrostatic
character. Properly formulated NAF contain emulsifiers pressure of the fluid column is available at the drilling
and surfactants which embed water or brine in an fluid-shale interface. Increased stresses can cause
internal phase and cause “oil” wetting of the contacted increased fracture roughness, increase in fracture
2 R. Schlemmer, A. Patel, J. Friedheim, S. Young and B. Bloys AADE-03-NTCE-36

conductivity, and loss of fracture compliance.4 Rock Osmosis, membranes, and hydrated ion diameter were
fracture results in loss of tens of thousands of barrels of serious topics of conversation, sometimes even at the
invert emulsion and synthetic drilling fluids every year. wellsite.
Induced rock fracturing is not as evident when drilling Another cation which promised to be as effective as
with water-based drilling fluids presumably because the potassium was the ammonium ion < NH4+ >. This
hydrostatic pressure differential extends deeper into the understanding, it can be argued, lead to development of
surface of the formation. Distribution of wellbore simple mud additives, complex long-chain polymers,
stresses more deeply into the formation helps avoid surfactants, and substituted glycols, to mention a few,
stress concentrations, fracturing, or fracture roughness. which contained ammonium, quaternary amines, amides
Observations in the field suggest that developed among other nitrogen-centered derivatives. This paper
fractures heal more readily when induced with water- will briefly revisit 11 nitrogen-centered additives, discuss
based drilling fluids. Fractures induced with WBM are a new amine technology, and present the next steps in
more readily sealed with conventional "lost circulation the evolution of amine chemistry in drilling fluids.
material". Fracture healing may be facilitated by
otherwise detrimental hydrational effects and clay History of Ammonium and Amine-Based & Treated
swelling. Mud Systems
It is easy to imagine, that by analogous mechanism,
aqueous-based fluids might provide similar benefits. Ammonium Salt Mud Systems
When exposed to conventional water-based drilling Ammonium chloride salt substitutes an ammonium ion
fluids, shales will have an immediate tendency to take up for potassium as an effective inhibitive cation. Both
water from the drilling fluid. Depending on the chemical ammonium and potassium have been reported with
characteristics of the shale, this can result in a rapid similar hydrated ion diameters7 at typical drilling fluid pH.
swelling or dispersion of the shale matrix due to an Intuitively, many would presume that the two salts
increase in pore pressure within the shale. Altering the should perform equally well. However, operationally,
chemistry of the aqueous phase (e.g. by inclusion of ammonium chloride, NH4Cl, was found to be a real
high concentrations of anions) can slow down the water troublemaker with its free liberation of ammonia gas as
uptake, or by including some active cations (e.g. mud pH climbed. Apparently in the 1960s it was, and
potassium or calcium) the potential for shale matrix remains, impossible to prevent mud engineers or
separation can be reduced. In addition high-molecular- derrickmen from adding an extra sack of caustic soda to
weight “plugging’ materials (e.g. PHPA, cloud-point the mud system. Waves of ammonia gas cleared the
glycols) can be added to physically try to block the drill floor, probably on the first and last well that
capillary network on the shale surface. All of these ammonium chloride salt was evaluated. The same pH
mechanisms can be used to slow down the process of sensitivity problem can manifest itself when drilling green
water uptake, however in an aqueous environment, the cement.
overall mechanism of water uptake into the shale matrix
will prevail and the shales will fail over time.
For 50 or more years, hundreds of chemical H Cl
concoctions have been prepared from water and brines
which through a variety of mechanisms might be claimed H N H
to somehow retard swelling of clays within shales. H
Some of the earliest of these aqueous fluids were based
on sodium chloride and starch; silicate muds have been Another ammonia-based inhibitive salt added
tested; lime muds and dispersed calcium sulfate-based routinely to field muds was fertilizer-grade diammonium
fluids were of interest for many years. phosphate or DAP. DAP buffers the drilling fluid to a pH
Enthusiasm for KCl/polymer drilling fluids began at of about 8 and use of additional caustic soda is not so
the close of the 1960s.5 KCl is defined as the starting tempting. Combination of DAP and polyanionic
point for this revisit of the evolution of ammonium and cellulose, PAC, was recommended as a system in the
amine-based drilling fluids. early 1970s as a cheap and environmentally friendly
In the early 1970s potassium, usually as a chloride replacement for saturated salt muds. DAP-PAC muds
salt, was added to drilling fluids and found to be an received attention again in the late 80s in the Rockies
effective inhibitor for clay swelling. With ongoing because of their lack of chlorides and improved
application of the then almost exotic salt, some environmental acceptability.8 Temperature and
understanding of “clay chemistry” and the correct performance limitations confined the material to a narrow
chemical jargon became essential for the ambitious mud market.
engineer. An “osmotic effect” was attributed to the Maximum temperature practicable for such
potassium chloride/PHPA muds which may be more phosphate-treated drilling fluids is about 150°F.9 DAP-
correctly called suppression of osmotic swelling.6
AADE-03-NTCE-36 Progression of Water-Based Fluids Based on Amine Chemistry – Can the Road Lead to True Oil Mud Replacements? 3

based muds have long had a market in California poly(dimethylamine-co-epichlorohydrin on a series of

because of their ability to tolerate a high content of 60-70 wells drilled in the North Sea.13
lb/bbl low-gravity solids typical of the low temperature CH3
OH
and shallow wells drilled using rigs with minimum or no Cl
N
solids-control equipment. The pH buffering of DAP
muds makes them somewhat more resistant to CH3
increases in pH. Drilling green cement can cause
breakout of ammonia gas and release at the bell nipple The cationic quaternized amine group is strongly
and flowline. adsorbed on the clay, reducing its charge and repulsive
forces, inhibiting swelling and dispersion. Typically
these polymers may contain anywhere from 400 to 7500
H cationic sites. This means that association of the
H N H polymer with clay is essentially an irreversible process.14
Cationic polymer systems may be the most inhibitive of
O H water-based fluids. The cationic polymers appear to
O P O adsorb on the negatively charged clay-mineral surfaces.
H The adsorption mechanism is consistent with an ion-
O
H N H exchange reaction. Exchangeable cations in the surface
clay lattices are replaced by a pendant cationic group
H from the polymer. This was shown in a simple lab
experiment where a suspension of API bentonite in de-
PHPA - Partially Hydrolyzed Polyacrylamide ionised water was mixed with a solution of cationic
“Partially hydrolyzed polyacrylamide” or PHPA can be polymer in de-ionised water. Measurements on the
viewed as an anionic cousin of ammonium cation-based filtered water 2 hours after mixing demonstrated a
systems. The first field test of a PHPA potassium reduction in the cationic polymer concentration and a
chloride drilling fluid was run in 1969 in the foothills area marked increase in both soluble sodium and calcium
of Canada.5 PHPA and variants continue to be used in content indicating cation exchange had taken place.
many inhibitive mud formulations. In PHPA muds used The polymer is very large compared to simpler cationic
in the North Sea, potassium chloride is preferred as the materials. The size of the molecule prevents penetration
exchangeable cation to replace or exclude sodium and into pores of shale or low-permeability producing zones.
prevent clay swelling. For US "deep water" drilling in the The permanency of its association with clays is likely to
Gulf of Mexico PHPA is used with an industry standard cause formation damage in higher permeability, shaley
18-22% sodium chloride.10 producing zones. Cationic polymers are typically applied
H2 H2 H2
in a range of 3 to 8 lb/bbl concentration. Due to high
H H H consumption (leading to high related cost and
O O O engineering difficulties) and high marine toxicity, the
cationic polymers originally developed are not widely
O NH2 O used today.
Na Na
Organic Cationic Materials – Quaternary Alkyl-
Occasionally DAP has also been used to provide the amines
inhibitive cation in PHPA treated drilling fluids and is Patented in 1988 was an application for tetra methyl
effective in low temperature applications. ammonium chloride or TMAC. TMAC, marketed as a
The degree of "hydrolysis" of PHPA is significant. “potassium substitute”, is an elegantly simple and
The standard 30% hydrolyzed PHPA variety preserves intriguing but toxic molecule. The application patent
shale stability via attraction of the anionic sites along the holder and distributors of TMAC claim that only 1/10 the
polymer chain to the cationic sites on the edges of the concentration compared to potassium chloride is
clay platelets. It is likely that the hydrolyzed anionic sites required to provide clay inhibition and shale
on the 30% hydrolyzed polymer more closely match the stabilization.15
spacing of substitutable sites on clay platelets.11 Cl
CH3 CH3
Organic Cationic Materials – Quaternary Cationic
N
Polymers
In 1989 polyamines with cationically charged groups
were introduced.12 Cationic polymers come in several CH3 CH3
flavors, but early Amoco work applied quaternized
4 R. Schlemmer, A. Patel, J. Friedheim, S. Young and B. Bloys AADE-03-NTCE-36

The low treatment concentration reduces chloride medically. Laboratory tests have shown that 5 to 6 lb/bbl
anion introduced to frac fluids or muds and enables a of HETMAC provides inhibition equivalent to 6% KCl.
degree of shale stability on land jobs with anion or Unlike KCl, HETMAC maintains its effectiveness in muds
conductivity restrictions. With a molecular weight of only containing moderate amounts of sodium chloride. This
74, the tetra methyl ammonium cation is small and effective, efficient amine continues to be widely used.
mobile. An MSDS lists an LD50 (rat) for TMAC of 50
mg/Kg. Toxicity is mitigated somewhat as TMAC readily Amphoteric Poly-amino Acids
combines with clays which allow it to pass most oilfield In 1993 an innovation introduced both cationic and
toxicity studies. TMAC is readily absorbed through skin anionic character to a single molecule.18
and personal protection is necessary. TMAC does not H
have widespread application in drilling fluids but is
N
applied in frac fluids.
Several variations on TMAC have been described CH3
including tetra-alkyl ammonium chloride and dimer and C=O
trimer versions of the molecule. Used with the cationic
polymers discussed above, Amoco selected two of what O
the company called "quaternary ammonium surfactants" Amine and a carboxylic acid groups were combined
in 1989. The quaternary alkyl amines used were in a polymeric configuration. The correctly sized
dimethyl dialkyl ammonium chloride and trimethyl alkyl amphoteric hydration suppressant when used at a pH
ammonium chloride. The dialkyl version presented here between 5 and 9 can satisfy all charges on a clay
was configured with x equal to 10 or 16. particle. The amphoteric chemical, a synthetic complex
amino acid,19 displays shifting anionic-cationic behaviour
Cl
with pH change over the applicable range. The chemical
CH3 CH2 ( CH2 ) CH3
x
is compatible with both anionic and cationic mud
additives. This amphoteric material has been widely
N
used in Canada, South America, and in Eastern Europe.
CH3 CH2 ( CH2 ) CH3 The small molecular size and amphoteric character
x
make these poly-amino acids especially useful as clay
hydration suppressants in “drilling-in fluids”. Clays in
Organic Cationic Materials – Quaternary Hydroxy
shales and in permeable sands can be stabilized and a
Amines
damaging decrease in permeability prevented.
High-molecular-weight cationic polymers have a large
molecular size and cannot penetrate the clay layers as
Alkyl-diamines
effectively as a low-molecular-weight monomers or
A less toxic, yet effective, replacement for TMAC was
oligomers. As a result, adsorption of high-molecular-
introduced by D. Horton and A. Jones in 1996.14
weight polymers occurs primarily on the exterior
Hexamethylene diamine (HMDA) is primarily marketed
surfaces of shale or cuttings as an encapsulating
by frac and stimulation companies. Based on CST test,
coating. Consequently, desorption of exchangeable
performance, 0.75% HMDA is equivalent to 0.15%
cations and reduction of cationic exchange capacity are
TMAC. The application patent covers several members
less significant when compared to low-molecular-weight
of the alky amine family.
materials.16 Low-molecular-weight cationic materials
may be regarded as "hydration suppressants" rather
NH2
than cationic encapsulators. A very effective and non- NH2
toxic low-molecular-weight quaternary monoamine
material is the patented18 chemical, β-hydroxyethyl-
trimethylammonium chloride (HETMAC).
Polyamine-glycols
There were two very effective amine glycols introduced
CH3
Cl
CH2 CH2 OH in the mid-1990s.20 Unlike other available glycols these
proprietary products did not require potassium chloride
N
for optimum performance. The interesting non-cloudpoint
CH3
glycols provided a degree of shale stability in fresh water
CH3
and were very effective in sodium chloride brines. The
glycols were able to effectively bind within the shale
With a molecular weight of 104, the cation can easily
layers by cationic substitution and fix clay spacing.
penetrate shale pores and serve as a potassium
Apparently "the amine group bound the molecule to the
substitute at relatively low concentration. HETMAC is a
clay minerals and the glycol groups stabilized the clay".20
non-toxic chemical that has primarily been used
Addition of these types of materials to previously used
AADE-03-NTCE-36 Progression of Water-Based Fluids Based on Amine Chemistry – Can the Road Lead to True Oil Mud Replacements? 5

muds with more than 15 lb/bbl of previously dispersed surpassed PHPA drilling fluid performance and more
low-gravity solids could cause unmanageable closely resembled the reference invert emulsion drilling
flocculation. fluid.

RO Shale Stability – "Slaked Durability" Test

RO N In the Slaked Durability test cuttings were rolled and
N RO physically stressed in a rotating "squirrel cage" type
screening device. Cuttings remaining at the end of the
RO
test were weighed and the percentage recovery
These glycols and newer variants demand to be reported. The test demonstrates a 31% increase in
treated as fundamental components of a freshly shale stability at pH 9 when a proprietary polymer
prepared base mud and not as simple additives. A additive is added to HPWBM formulation. At pH 10
member of this unique chemical family provided the best recovery values were equal or slightly better than
shale stabilizing characteristics of all the glycol-treated recovery from standard HPWBM but differences were
muds tested in a one joint industry study performed in not dramatic. Data is presented graphically in Fig. 1.
2000-2001. In 1996 on a well in the Gulf of Mexico, Test details are presented in Table 2.
without an effective anti-accretion additive yet available,
the efficiency of the material led to sometimes frustrating Shale Stability – Conventional Hot Roll Evaluation
bit and collar balling. Due to cost considerations and Conventional hot roll stability test data for the HPWBM
misunderstanding of proper application these variant series is presented graphically in Fig. 1. HPWBM at pH
glycols never achieved widespread use in the US. 9 with or without the polymeric additive displayed
excellent recovery values. Cuttings appeared to be
slightly more intact than cuttings rolled in HPWBM with
New Amine Technology and the HPWBM
the polymeric additive at pH 10 (HPWBM-4). The
recovery trends in this test were not unlike those
Ether/Glycol Polyamines
A key inhibitive ingredient of a new high performance recorded in the Slaked Durability study. In both cases
water-based mud (HPWBM) is a material similar to the fluid formulation HPWBM-5 outperformed fluid
polyamine glycol. A novel ether amine was introduced formulation HPWBM-4. Test details are presented in
last year to the Gulf of Mexico. This ether amine21 is one Table 2.
component of a mud system which includes a relatively
short-chain, mildly cationic terpolymer, an effective anti- Shale Stability - Bulk Hardness Test
crete additive and efficient filtration control additives of Measurement of shale stability based on retained or
narrow molecular-weight distributions. A typical supplemented shale hardness is presented in Fig. 2,
formulation is presented in Table 1. Drilling fluids which compares cuttings hardness measured using a
formulated around these primary components have proprietary "Bulk Hardness Tester" that most closely
shown a high degree of flexibility; good inhibition resembles a compact pasta press. After cuttings or
performance has been seen using base fluids as varied broken shale has been hot rolled for a specific period in
as freshwater to saturated NaCl. Unlike the earlier the drilling fluid of interest, the cuttings are extruded
cationic polymers the ether amines do not show a through a perforated steel plate. The force required for
tendency for high polymer depletion on exposure to extrusion is recorded as "Bulk Hardness". Data includes
active shale, and are considered to be of low toxicity. turns of a feed screw and recorded torque at each unit of
rotation. Test parameters are presented in Table 2.
In the presented data, cuttings are tested to compare
R the stabilizing performance of four variants of an
HPWBM drilling fluid. Cuttings rolled in HPWBM
NH2 NH2 containing the membrane-forming additive retained the
( ) highest level of hardness. Data collected using a PHPA
O x
mud is presented for comparison. Performance of the
R HPWBM with or without the membrane-forming additive
exceeded performance of the PHPA system. The
improved performance was observed at low and high
HPWBM Performance Tests pH.
Several formulations are shown in Table 1 which
describes variants of a new amine-based HPWBM. The HPWBM and Accretion
variants include conventional and membrane-forming Accretion tests were run using the same fluids described
versions. Also included Is a comparative formulation for in Table 1. Fig. 3 presents graphical comparison of
a PHPA system. In all cases the new HPWBM greatly
6 R. Schlemmer, A. Patel, J. Friedheim, S. Young and B. Bloys AADE-03-NTCE-36

accretion performance of the HPWBM variants one shale. Low-molecular-weight polymers from several
through four. Included for comparison is accretion data suppliers were tested and while a variety of cellulose
for a PHPA and an invert emulsion mud. Photographs of derived and polyacrylate oligomers provided enhanced
the steel test bars with accreted material are presented osmotic pressure, one proprietary material remained
as Fig. 4. Accretion results of the HPWBM with consistently interesting throughout testing during 2001
membrane-forming additive were superior to the and 2002.
accretion results measured using standard HPWBM and The acid-soluble oligomer compared favorably to
comparable to accretion typical of an invert emulsion similarly performing proprietary acrylic acid derived
drilling fluid. oligomers. The experimental oligmer is totally soluble in
virtually all types of aqueous-based fluids including KCl-
HPWBM – Comments on Formation Damage polymer, calcium-based muds, bromide and formate-
As was found with HMDA, tests of the new ether amine- based fluids, and the currently used ether amine
based system on Berea sandstone core have inhibited HPWBM systems used in the Gulf of Mexico,
demonstrated minimum damage. However, use of an Canada and southern Europe.
inhibitor will not reduce formation damage caused by This very soluble oligomer provides both the sub-unit
solids invasion. Mud solids management must provide for a highly crosslinked polymer membrane and
suitable particle-size distribution to prevent introduction contributes to shale stability and improved HTHP filtrate
of damaging mud solids to productive sands control. The two personalities of the new HPWBM can
Most basic components of this HPWBM system are be seen with change in pH. At pH above 9.5, a
intrinsically non-damaging with the exception of barite crosslinked-polymer membrane readily forms to coat the
and drilled solids. However, one secondary component, formation. At lower pH, the material does not readily
a proprietary, mildly cationic terpolymer similar to PHPA, polymerise but supports clay inhibition and stabilization.
can precipitate under certain circumstances. This Available amine and oligomeric additive can easily enter
proprietary acrylamide derivative is not a conventional the lamellae of the clay and serve as a complementary
PHPA and it is more compatible with acid than PHPA. A hydration suppressants.
photographic comparison of a 2 lb/bbl of PHPA and a The original fluid evaluation was performed using
cationic terpolymer solution, each in 15% HCl, is donated preserved West African shale. The majority of
presented as Fig. 5. The cloudiness of the jar containing shale/clay membrane development work was run in 20%
PHPA indicates polymer precipitation. The clear fluid in salt-based muds. Gulf of Mexico deepwater wells
the second jar indicates acid solubility of the cationic typically specify 20% sodium chloride for suppression of
terpolymer. gas hydrate crystallization in the drilling fluid.10 The 20%
The compatibility of this product with acid over a sodium chloride concentration also serves as an osmotic
range of temperature and salinity conditions has not yet driver. The calculated potential osmotic pressure
been tested. Calcium ion, for example, can be expected development available from a 20% salt solution
to reduce the solubility of the polymer in acid. separated from de-ionized water by a semi-permeable
membrane is approximately 3500 psi.3
Membrane Development and Osmosis The potential of one such 20% NaCl brine-based
A research project begun in 1999 led to design and mud is seen in Fig. 7. The chart displays the applied
construction of five standard test cells that have now mud pressure labeled as "wellbore and confining
been used to screen in excess of 300 mud formulations pressure". The chart displays the developing pore
since the inception of the project.3 Several familiar fluid pressure labeled as "reservoir pore pressure. If no
types were found to be membrane formers, based on osmotic potential exists due to lack of membrane
osmotic pressure development tests. The traditional efficiency, reservoir pressure stabilizes to within a few
fluids tested which readily effect a membrane within or psi or equalizes to wellbore pressure in a relatively short
on shale include silicate, high concentration sugar-based time.
systems, and invert emulsion-based fluids. The test presented as Fig. 7 demonstrates
This new HPWBM provides both an efficient substantial osmotic pressure development in excess of
membrane and shale stability. The ether amine inhibitor 1500 psi. The near horizontal curve implies that
reacts with other additives to form a networked polymer membrane efficiency is near 100% up to the developed
membrane which supports osmotic pressure develop- osmotic pressure differential of 1500 psi; there is limited
mint in excess of 1500 psi on preserved West African exchange or movement of water or ions across the
and outcrop Pierre 1E shales. The detached polymer membrane.
membrane which formed on a 1-inch diameter shale This membrane-forming technology can be
core is clearly visible in Figure 6. established in many types of water-based muds but it is
Work with polyacrylates, sugars, and glucosides led a natural extension of the amine-based HPWBM system.
to an understanding of the role played by low-molecular- A proprietary oligomer additive is used with the HPWBM
weight polymers in membrane development in and on to generate a membrane in a polymerization reaction. It
AADE-03-NTCE-36 Progression of Water-Based Fluids Based on Amine Chemistry – Can the Road Lead to True Oil Mud Replacements? 7

was determined that membrane formation is dependent The new glycol and ether amines combined with the
upon pH. Fig. 8 presents osmotic pressure development proprietary oligomer now provide for very easy to run
curves at pH of 9 and pH of 10. Development of osmotic and predictable shale inhibitive water-based muds which
pressure is indicative of membrane formation. As can readily and optionally support creation of an efficient
displayed in Fig. 8, osmotic pressure development at pH shale membrane and high osmotic pressure.
10 is profound. Membrane development is inhibited The standard HPWBM reduces bit balling and
when pH is reduced. accretion tendencies as measured in laboratory tests
and in field experience. To date >25 well sections have
Future Amine Development for Water-Based Muds been drilled with the HPWBM with the overwhelming
Drilling fluids applying cationic and anionic nitrogen conclusion that correct application of this new amine-
centered groups have developed steadily for more than based technology can give a water-based fluid
35 years. The earliest applied ammonium salts did not performance similar to that of a non-aqueous fluid.
provide acceptable pH or temperature stability for a When the proprietary oligomeric additive is applied in
majority of drilling fluid applications. High-molecular- a similar HPWBM formulation, cuttings inhibition and
weight anionic and cationic polymers served as resistance to bit balling and accretion can be further
encapsulators of cuttings but not particularly well as clay improved. The complete membrane-forming drilling fluid
inhibitors. It was only in the last decade that low- system has been demonstrated to provide excellent
molecular-weight polyamine chemistry and direct shale stability and effective accretion control and it is
measurement of osmotic pressure in water-based muds anticipated that the goal of a true non-aqueous fluid
have come together to permit development of inhibitive replacement will be met with the field use of the system.
fluids which also provide a predictable and measurable The HPWBM and oligomer enhanced HPWBM can
osmotic contribution to overall shale stability. effectively replace NAF in selected applications:
Development is continuing which addresses issues • When temperature < 300°F
pertinent to amine-based mud chemistry. Develop- • When density requirement is < 16 lb/gal
mental goals for the coming years include: • If the drilled shales are compatible with the
• Extension of amine and oligomer performance to HPWBM chemistry for the period of time required
higher temperatures to drill and case and interval.
• Economically tailor oligomers to optimum and
consistent molecular weight and configuration for Acknowledgments
improved filtration control and membrane The authors express their appreciation to M-I for
development granting permission to prepare and publish this paper.
• Source less expensive amines which meet Special thanks go to Robert O'Connor (S&S.), Emanuel
performance expectations. Stamatakis (M-I), Jerry Hinkel, (Special Products), Ken
• Investigate of a broad range of organic and Slater (M-I).
inorganic osmotic drivers which complement
membrane development. References
1. Steiger, R.P. and Leung, P.K.: "Quantitative Deter-
Conclusions mination of the Mechanical Properties of Shales,"
Application, in water-based muds, of an efficient shale SPE Drilling Engineering (Sept 1992) 181.
membrane and subsequent osmotic pressure 2. van Oort E., Hale, A.H., Mody, F.K., and Roy, S.:
development may seem to be a good idea based upon “Critical Parameters in Modelling the Chemical
experience with NAF. However, reviews of drilling and Aspects of Borehole Stability in Shales and in
laboratory data suggest that osmotic pressure Designing Improved Water-Based Shale Drilling
development in traditional water-based muds may create Fluids,” SPE 28309, SPE Annual Technical
accretion and bit balling problems. Conference, New Orleans, Sept 25-28, 1994.
A recently introduced amine-based shale inhibitor 3. Schlemmer, R., Friedheim, J., Growcock, F., Bloys,
has been found to contribute to creation of membrane on J.B., Headley, J.A., and Polnaszek, S.C.:
or in shale when used with a proprietary oligomer. The "Membrane Efficiency in Shale - An Empirical
membrane effect is controlled by adjustment of pH. Use Evaluation of Drilling Fluid Chemistries and
of the membrane-forming additive at the pH at which Implications for Fluid Design," SPE 7466, SPE/IADC
tendency to form membrane is greatest yields Drilling Conference, Dallas, Feb 26 – 28, 2002.
acceptable cuttings stability as measured by hardness 4. VanDam, D.B. and de Pater, C.J.: "Roughness of
and stability testing. Use of the membrane-forming Hydraulic Fractures: Importance of In-Situ Stress
additive at a pH less likely to support a requisite and Tip Processes," SPE 56596, SPE Annual
reversible reaction and membrane formation also yields Technical Conference, Houston, Oct 3 – 6, 2000 and
improved cuttings stability. revised as SPE 68775, SPE Journal (March 2001)
8 R. Schlemmer, A. Patel, J. Friedheim, S. Young and B. Bloys AADE-03-NTCE-36

4-13. 14. Horton, C. and Jones, A.: "Clay Stabilizing Agent

5. Clark, R.K., Scheuerman, R.F., Rath, H., and Van and a Method of Use in Subterranean Formations to
Laar, H.G.: “Polyacrylamide/Potassium-Chloride Inhibit Clay Swelling," US Patent 5,771,971 (June
Mud for Drilling Water-Sensitive Shales,” SPE 5514, 30, 1998).
Journal of Petroleum Technology (June 1976) 719- 15. Himes, R.E. and Vinson, E.F.: "Fluid Additive and
727. Method for Treatment of Subterranean Formations,"
6. Van Olphen. H.: An Introduction to Clay Colloid US Patent 4,842,073 (June 27, 1989).
Chemistry, Second Edition; John Wiley & Sons 16. Retz, R., Friedheim, J., Lee, J., and Welch, O.: "An
(1977) 107. Environmentally Acceptable and Field-Practical,
7. Grim, R.E.: Clay Minerology, First Edition; McGraw- Cationic Polymer Mud System," SPE 23064, SPE
Hill (1953) 148. Offshore Europe Conference, Aberdeen, Sept 3 – 6,
8. Vesely, D.P.: "New DAP Mud System Shows 1991.
Promise for Rocky Mountain Environmentally 17. Patel, A., Thaemlitz, C.J., McLaurine, H.C. and
Sensitive Areas," SPE 17511, Rocky Mountain Stamatakis, E.: "Drilling Fluid Additive and Method
Regional Meeting, Casper, Wyoming, May 11 – 13 for Inhibiting Hydration," US patent 5,908,814 (June
1988. 1, 1999).
9. Lummus, J.L. and Azar, J.J.: Drilling Fluids 18. Bruton, J.R. and McLaurine, H.C.: "Modified Poly-
Optimization – A Practical Field Approach; PennWell Amino Acid Hydration Suppressant Proves
Publishing Co. (1986) 25. Successful in Controlling Reactive Shales," SPE
10. Strickland, S.D.: "Polymer Drilling Fluids in the 26327, SPE Annual Technical Conference, Houston,
1990's – Will They Replace Oil-Based Muds?" SPE Oct 3 – 6, 1993.
29211, Journal of Petroleum Technology (Aug 1994) 19. Patel, A.D. and McLaurine, H.C.: "Drilling Fluid
692. Additive and Method for Inhibiting Hydration," US
11. Gray, G.R. and Darley, H.C.H.: Composition and patent 5,149,690 (Sept 22, 1992).
Properties of Oil Well Drilling Fluids," Fourth Edition; 20. Brady, M.E., Craster, B., Getliff, J.M. and Reid, P.I.:
Gulf Publishing Co. (1980) 175. "Highly Inhibitive, Low-Salinity Glycol Water-Base
12. Beihoffer, T.W., Dorrough, D.S. and Schmidt, D.D.: Drilling Fluid for Shale Drilling in Environmentally
"The Development of an Inhibitive Cationic Drilling Sensitive Locations," SPE 46618, SPE International
Fluid for Slim-Hole Coring Applications," SPE 19953, Conference on Health, Safety, and Environment in
SPE/IADC Drilling Conference, Houston, Feb 27 – Oil and Gas Exploration and Production, Caracas,
Mar 2, 1990. June 7 – 10, 1998.
13. Beihoffer, T.W., Growcock, F.B., Deem, C.K., 21. Patel, A.D., Stamatakis, E. and Davis, E.: "Shale
Dorrough, D.S., Bray, R.P., Munro, R., Guild, G.J., Hydration Inhibition Agent and Method of Use," US
Hanni, G.L., and Prewet, H.H.: Field Testing of a patent 6,247,543 (June 19, 2001).
Cationic Polymer/Brine Drilling Fluid in The North
Sea," SPE 24588, SPE Annual Technical
Conference, Washington DC, Oct 4 – 7, 1992.
AADE-03-NTCE-36 Progression of Water-Based Fluids Based on Amine Chemistry – Can the Road Lead to True Oil Mud Replacements? 9

Table 1 – Mud Formulations

Units PHPA-1 HPWBM-2 HPWBM-3 HPWBM-4 HPWBM-5
no no
Type membrane membrane membrane
membrane membrane
freshwater (l) ml 249 222 222 222
seawater (l) ml 300
PAC (s) g 1
prop cellulosic (s) g 3.25 3.25 3.25 3.25
biopolymer (s) g 0.5 1 1 1 1
cationic terpolymer (s) g 1.5 1.5 1.5 1.5
PHPA A (s) g 1
PHPA B (s) g 1
bentonite (s) g 6
sodium chloride (s) g 54.4 62.3 56.5 55 55
potassium chloride (s) g 13.6
ether amine (l) g 10.5 10.5 17.5 17.5
anticrete (l) ml 10.5 10.5 10.5 10.5 10.5
barite (s) g 161 184 187 187 187
rev dust (s) g 25 25 25 25 25
initial pH adjustment pH 8 8.5 - 9 8.5 - 9 8.5 - 9 8.5 - 9
Oligomer - membrane (s) g 25 25 25
Adjust pH to pH 8 8.5 - 9 8.5 - 9 to 10.5 AHR to 10.5 BHR

Figure 1
Slaked Durability (abrasion) Test - Arne Shale
Hot Roll Test - G of M Cuttings
Increased Recovery Value is Better
110%

100%
90%

80%
Recovery by weight

70%
60%

50%
40%

30% Slaked Durability

20% Hot Roll Data
10%

0%
PHPA - 1 HPWBM - 2 HPWBM - 3 HPWBM - 4 HPWBM - 5 SBM 80/20
no Membrane A Membrane B Membrane C Reference
membrane
additive
10 R. Schlemmer, A. Patel, J. Friedheim, S. Young and B. Bloys AADE-03-NTCE-36

Figure 2
Bulk Hardness Comparison
Arne Shale
450
PHPA
400 HPWBM standard
Feed Screw Torque, in-lb

HPWBM Membrane pH 9
350
HPWBM Membrane, pH 10
300 Reference Invert

250

200

150

100

50

0
4 5 6 7 8 9 10 11 12 13 14 15

Extrusion Test Device - Rotations of Feed Screw

Figure 3
Accretion Test
Steel bars rolled with 50 g Arne Shale for 20 minutes
Reduced Accretion Value is Better
45

40

35

30
Accreted Shale, g

25

20

15

10

0
PHPA - 1 HPWBM - 2 HPWBM - 3 HPWBM - 4 HPWBM - 5 SBM 80/20
no membrane Membrane A Membrane B Membrane C Reference
additive
AADE-03-NTCE-36 Progression of Water-Based Fluids Based on Amine Chemistry – Can the Road Lead to True Oil Mud Replacements? 11

Table 2 – Test Details

Hot Roll Stability Test
oven type OFI 5 Roller Laboratory Oven
temperature 150°F (65.6°C)
time 16 hours
description of material Field Cuttings - Gulf of Mexico
shale size through 4 on 7 mesh
grams material 30 g
sieve screen used 20 Mesh (0.85 mm)

Slaked Durability (Cage Test)

Rotation Speed 45 RPM
Temperature ambient
Shale Type Arne Shale
Shale Size through 4 on 7 mesh
Test Screen Size 14 mesh
Rolling AbrasionTime 4 hours
grams material 30 g

Bulk Hardness Test

pretreatment Shale Rolled in Fluid of Interest
oven type OFI 5 Roller Laboratory Oven
temperature 150°F (65.6°C)
time 16 hours
description of material Arne Shale
shale size through 4 on 7 mesh
grams material 35 g
sieve screen used 20 mesh
extruder plate 37 x 0.109 in (2.77 mm)
material extruded 30 g

Accretion Test
oven type OFI 5 Roller Laboratory Oven
temperature 80°F (26.6°C)
test duration 20 minutes
description of material Arne outcrop shale
shale size through 4 on 7 mesh
grams material 50 g
23mm D x 150mm L
roller dimensions
(approx. 0.9 in D x 5.9 in L)
roller weight 475 g
material P-110
12 R. Schlemmer, A. Patel, J. Friedheim, S. Young and B. Bloys AADE-03-NTCE-36

Figure 4 – Accretion Photos

PHPA Mud HPWBM 2 HPWBM 3 HPWBM 4 HPWBM 5

Figure 5 - Polymer Solubility in 15% HCl

AADE-03-NTCE-36 Progression of Water-Based Fluids Based on Amine Chemistry – Can the Road Lead to True Oil Mud Replacements? 13

Figure 6 – Membrane and Shale Core

Figure 7
Shale Membrane Test - 072302rps
Cell 5 - HPWBM Membrane in NaCl 20%
on Preserved West African Shale
1800 163

1600 161

1400 Wellbore Pressure 159

Pore Pressure 5

Temperature, °F
1200 157
Pressure, psi

Temperature
1000 155

800 153

600 151

400 149

200 147

0 145
0 24 48 72 96 120 144 168 192 216
Time, hr
14 R. Schlemmer, A. Patel, J. Friedheim, S. Young and B. Bloys AADE-03-NTCE-36

Figure 8
Shale Membrane Test - 092502rps
Cell 2 - HPWBM Membrane pH 9
Cell 3 - HPWBM Membrane pH 10
in NaCl 20% on Pierre 1e Outcrop 162
600
161

500 160

Wellbore Pressure 159

Temperature, °F
400
Pressure, psi

Pore Pressure 2 158

Pore Pressure 3
300 Temperature 157

156
200 155

154
100
153

0 152
0 6 12 18 24 30 36 42
Time, hr