SPE 94523

A New Inhibitive Water-Based Fluid: A Completely Cationic System

R.C.R.S. Rosa, A.L.A. Rosa, S.B. Farias, M.H. Garcia, and A.S. Coelho, Poland Química Ltda.

Copyright 2005, Society of Petroleum Engineers Inc.

purpose to minimize damaging reactions between the mud and
This paper was prepared for presentation at the SPE Latin American and Caribbean reservoir.
Petroleum Engineering Conference held in Rio de Janeiro, Brazil, 20 – 23 June 2005.
Many problems are caused by incompatibility between
This paper was selected for presentation by an SPE Program Committee following review of
information contained in a proposal submitted by the author(s). Contents of the paper, as
water and shales. This may be solved by using oil/water
presented, have not been reviewed by the Society of Petroleum Engineers and are subject to emulsion mud or 100% oil mud. This isolates water from
correction by the author(s). The material, as presented, does not necessarily reflect any
position of the Society of Petroleum Engineers, its officers, or members. Papers presented at shales and prevents hydration1,3. However, oil muds are
SPE meetings are subject to publication review by Editorial Committees of the Society of
Petroleum Engineers. Electronic reproduction, distribution, or storage of any part of this paper
becoming increasingly difficult to use in some areas due to
for commercial purposes without the written consent of the Society of Petroleum Engineers is environmental concerns and government regulations changes.
prohibited. Permission to reproduce in print is restricted to a proposal of not more than 300
words; illustrations may not be copied. The proposal must contain conspicuous Water-based drilling fluids (WBDF) may use various chemical
acknowledgment of where and by whom the paper was presented. Write Librarian, SPE, P.O.
Box 833836, Richardson, TX 75083-3836, U.S.A., fax 01-972-952-9435.
inhibitors to control reactive shales. These special drilling
fluids are formulated to provide lubricity, inhibition, solids
Abstract suspension and borehole stability. They also have to protect
The development process of new technologies in drilling pay zones by forming an effective filter cake to control fluid
fluids has established that the fluid should have viscosity loss, stay intact during completion operations and clean up
control and clays inhibition. Some other aspects as fluid loss easily4-5.
control and grout thickness had become almost that decurrent Several researches have been developed to minimize the
of the action of the main products. The search of a highly shale hydration by WBDF. The KCl addition on these kinds
inhibitive water-based drilling fluid (WBDF) system has been of fluids works by changing places with sodium atoms in the
a continuous purpose in the drilling fluid industry. clay structure and, as potassium ion is smaller than sodium
We have designed and developed new materials that will ion, this causes the clay structure to shrink rather than
improve the inhibition capacity of water-based fluid, besides expand1. A recent development is the use of soluble silicates
favoring a complete rheology and fluid loss control of the in clay stabilization. These are soluble at high pH, but
system. Parameter viscosity reached great evolution in the last precipitate out of solution if the pH drops. Tiny amounts enter
decades with the implantation of high performance polymer, the pore space between crystals, the pH drops, silicate
capable of substituting the bentonite. Through this, the fluid precipitates and form a barrier to further water penetration.
with low solid became the key of the success in perforation Use of silicates seems to cause the clay to harden over time1.
fluids. Systems using a blend between KCl and glycols as inhibitors
The developed system consists of an environment-friendly in WBDF have been Applied7-8. In these systems, xanthan
cationic polymer as shale inhibitor, a fluid-loss control, and a gum and dextrin were used as viscosifying and loss filtrate
polymer that provides viscosity and gel structure. control respectively. Other useful chemicals include
Components were designed for high performance water-based polymers. Clay crystals have electrostatic charges on their
drilling fluids, and present the versatility to be used as much faces and edges. If a polymer molecule also has opposing
with industrial water, as seawater or saltwater, maintaining the charges along its length, polymer sticks to the clay crystal and
fluid performance. This work will discuss some properties of prevent water from reaching it1. This is the principle of water-
this system, comparing with the traditional system used by based cationic drilling fluids.
Petrobras - Brazil. The development of a WBDF, which could exhibit similar
drilling characteristic to an invert emulsion drilling fluid, has
Introduction been an ongoing endeavor of the drilling fluid industry9-10.
The Drilling fluids play several functions in drilling well. Different WBDF systems have been developed over the past
If the mud properties are incorrect, safety and economics may ten years aiming to approach the drilling performance of an oil
be severely compromised. To each drilling fluid, its behaviors based mud. However, the developed fluids have not been
are major guarantee of drilling operation success1-2. In completely successful in inhibiting the hydration of highly
selecting the most suitable type of drilling fluid, many water sensitive clays. The cationic polymer systems used
different factors must be considered. What is required is a actually give a more oil based fluid-like inhibition. But, the
mud system that provides lowest overall cost of drilling each cationic polymer toxicity (generally an organ chloride
hole section. When drilling through the reservoir, the main material) and their incompatibility with other anionic additives
for water drilling fluids, have limited the system success.
2 SPE 94523

The main purpose of this paper is the development of Experimental

individual products, designed to further enhance the Fluid Preparation. Laboratory testing fluids were prepared
performance characteristic of these systems. on a Hamilton Beach mixer, at medium velocity. Table 1 and
2 show the traditional fluid composition and the NI-WBDF
Development composition. Polymeric and solid materials were stirred for
The incompatibility between a cationic polymer, which is 10 min while liquid material were stirred for 5 min. The
responsible to the inhibition of reactive shales, and an anionic addition order follows the tables. The pH of both kind of fluid
polymer, has limited the use of this system in WBDF. The was adjusted to 9,2 by addition NaOH (0,1N). The pre-
mixture between aqueous solutions of a cationic polymer with hydration of polymers was not necessary. The prepared fluids
an anionic polymer results in the formation of an insoluble were analyzed by its rheological properties, fluid loss control
complex in water (Figure 1). However, when the mixture of and by its clay inhibition ability using MBT (methyl blue test)
the aqueous solutions of both the types of polymers occurs in methodology. The same fluids were prepared in presence of
presence of salts as NaCl and KCl, occurs the shield effect that bentonite (20, 30 and 40 ppb), to evaluate its inhibition
prevents the precipitation of the formed complex, but does not capacity. The fluid properties were also evalutd after heating
prevent the reaction between cationic and anionic polymers. aging at 200 °F for 16 hours.
To avoid the relative problems of incompatibility, to
increase the inhibition of reactive shales, and to minimize the Rheological Measurements. The fluids of Tables 1 and 2,
toxicity effect of cationic polymers, were developed three new were analyzed by its rheological behavior using a FANN 35
materials: Rheometer (B1-R1 Couette), which can measure the shear
a. A cationic fluid loss control (CFLC-1); viscosity between 3 and 600 rpm. The measurements were
b. A cationic viscosifying system (CVS-1);
done at 25 °C and 1 atm.
c. A cationic polymer with low chloride content
(CPLCl). Fluid Loss test. The fluid loss test was determined using the
A modified starch is unique that can serve as viscosifier
API filter press multi-units. The filtered one was analyzed in
and fluid loss additive. The cationic modified starch is accordance with the American Petroleum Institute (API), that
specially processed to obtain a high-molecular weight recommends a standard 100 ± 1.0 psi (690 ± 6.9 kPa) cell
branched-chain. A new environmentally safe cationic polymer
pressure be applied within 30 seconds for a 30 minute test.
with low chloride content exhibits excellent shale inhibitive
characteristics in the WBDF. This newly developed material Bentonite Inhibition. The shale inhibitor ability to prevent
is a quaternary ammonium based molecule, which is water-
the swelling of bentonite is the simplest useful test for the
soluble and has low toxicity (96 hour LC50 = 530,000 for evaluation of shale inhibitors. Carrying out a series of
Mysidopsis juniae species). In addition to its excellent shale- inhibition tests in fresh water performed an experiment based
inhibition properties and low toxicity, the CPLCl is
on such a concept. The test determines the degree of clay
compatible with others common additives for WBDF. Stuies swelling in presence of different clay inhibitor concentrations
show evidence that the newly developed shale inhibitor may (0 the 8 ppb) in 100 ml of distilled and immineralized water.
inhibite shale involving specific binding of protonated
The water treatment has as objective to prevent the effect of
ammonium quaternary groups of the shale inhibitor with the the presence of soluble salts in the water, which could mask
clay in place of the metal cations in an ion exchange the result. This solution was stirred in Hamilton Beach in
mechanism11.
average speed for 5 min. After this time, was added in each
A time where all the polymeric components of the new solution 2 ppb of bentonite, and the system was kept under
inhibitive water-based drilling fluid (NI-WBDF) present stirring by 10 min. The final solution was immediately shed
cationic character, then tend to function in synergism,
for a test tube, and the system was kept under rest for 24 hours
improving the main characteristics of the fluid. The CPLC1 and analyzed the swell of the clay and the appearance of the
provides reduction in clay dispersion and some shale
up water. The performance of the new shale inhibitor in the
inhibition by encapsulation of shale particles. NI-WBDF was compared with a commercial quaternary amine
The most appropriate chemistry groups selection was made shale inhibition.
from previous research works, and these new materials and its
This ability was also evaluated in fluids contaminated with
formulated fluids were subjected to fluids performance testing clay, applying itself the methyl blue test (MBT). To this
(filtration, rheology, contamination performance, inhibition analysis, 1 ml of prepared and contaminated fluid was
capacity) to evaluate their overall performance. The test
collected and placed in becher of 100 ml. To this system was
results achieved were compared to the traditional cationic added 10 ml of distilled water, 1 ml of sulfuric acid 5,0 N, 10
water-based drilling fluid (used in Brazil), that use xanthan ml of H2O2 20 vol. The system was then warm until boil for
gum and carboxymethyl cellulose of high viscosity in salty
about 10 min. After cooling, the system was diluted up to 50
water (CMC-HVSW) as viscosifier, and carboxymethyl ml. The methyl blue was added to this system in small ratios.
cellulose type II (CMC-type II) as fluid loss controller. The To each addition of the methylene blue, a drop of the system
final results of this work were a new inhibitive water-based
was dripped on a filter paper, until the comment of the
drilling fluid, which exhibited laboratory performance coloration change (a green-blue aureole). Each ml of
characteristic. methylene blue expense corresponds the 5 ppb of incorporated
clay to the fluid, or either, not inhibited.
SPE 94523 3

Results and Discussion The shale inhibitor ability evaluated in fluids contaminated
Rheological properties. The Rheological behavior of the with clay, applying itself the methyl blue test, is showed in the
fluids presented in Tables 1 and 2, are shown in the Figure 1 Figure 7. The results, one more time, show the high capacity
(before ageing-BA) and in the Figure 2 (after ageing-AA). The of clay inhibition of the NI-WBDF, presenting efficiency
results presented in the Figure 1a show that the New Inhibitive higher than 90% and confirming the presented data
Water-Based Drilling Fluid present almost the same rheology, previously. In any clay concentrations, the new inhibitive
being contaminated it with clay or not. It shows a perfect water-based drilling fluid presented higher inhibition ability
ability of clay inhibition of the system, what it tends not to that the standard traditional fluid.
intervene with Rheological properties. The same is not Conclusions
observed for Standard Traditional Fluid (STF), which tends to A new, highly inhibitive, water-based drilling fluid system has
have its rheology increased in function of increase clay been developed. Laboratory studies have shown that the
contamination (Figure 2b). Such effect in the STF should have system significantly reduces clay hydration and swelling. The
been caused by the reaction between anionic and cationic inhibitive components of the NI-WBDF have been specially
polymers in the system, and the efficiency of clay inhibitor designed to impart maximum stabilization of dispersível clay
was reduced. The results evidence that the completely cationic formations. The developed products were chosen to satisfy the
character of the NI-WBDF favors a perfect clays inhibition in requirements of highly inhibitive fluids. The designed fluid is
the system, being able to be compared with oil based fluid. flexible and could be formulated with a variety of base brines
The Figure 3 shows the rheological behavior of the same from freshwater to saturated KCl. By the found laboratories
fluids after aging at 200 °F for 16 hours. It can be observed results, this fluid can be indicated to perforate zones that
that the rheology of the NI-WBDF was almost remained contain highly reactive clays, keeping the integrity and
constant, with very similar values found before the aging. stability of the well. Done assays after aging, shown that the
This suggests a complete system stability, besides showing properties of the fluid are practically kept constant after
that the developed polymeric materials present resistance to exposition to 200 °F for 16 hours.
the temperature and to the shear generated during the test of
aging of the fluid. However, the STF continued presenting Acknowledgements
rheological values varied although to possess components that We thank the Poland Química Ltda for granting the
are sufficiently resistant to the temperature and to the shear. permission to publish this work, and the technicians Larissa de
Moraes, Rafael Marques, Gláucia Mello, Andréa Ferreira,
Fluid Loss test. Fluid loss control for a mud is achieved by Alexandre Souza, Gizelle de Fátima, Sandra da Silva, Flávio
several means, one of which is by addition of fluid-loss- Borba, Marcos Leal, Edson Brito and Diego de Castro.
control materials to the mud system. The cationic fluid loss
control (CFLC-1) is a chemically modified starch, which was References
designed to have complete synergism with the cationic system. 1. Devereux, S.: Drilling Technology, in non-Technical
The low viscosity contribution of the modified polymer allows Language”, First Edition, PennWell, Oklahoma, 1999.
for optimal filtration control. The Figures 4a and 4b show the 145.
results of fluid loss for the NI-WBDF and the STF, before and 2. Rui, Z., Ruihe, W. ad Zhengsong, Q.: “A Novel
after the aging. In both the cases (BA and AA) the NI- Modeling Method for density of Drilling Fluid”
WBDF presented filtered volumes well below of the results www.paper.edu.cn
found for the STF, proveding a complete control of the 3. Patel, A., Stamatakis, E.; Young, S. and Cliffe S.:
filtered one. It can be observed that the filtered values gotten “Desing for the Future – A Review of the Design,
before and after aging for the NI-WBDF had been presented Development and Test of a Novel, Inhibitive Water-
almost constant. For the STF, however, a control not perfect Based Drilling Fluid” AADE 2002 Technical Conference,
of the filtered one before the aging can be observed. Besides, Texas, 2002.
after aging can be seem a certain uncontrol, presenting filtered 4. Ali, S.A. and Dearing, H.L.: “Evaluating water-based
values above of the waited one. The results evidence that the drill-in fluids for horizontal completions”, Wolr Oil,
CFLC-1 presents a perfect performance as controller of fluid Drilling´96, 71.
loss, being compatible with all the components of the NI- 5. Horton, R.L.; Tresco, K.O.; Dobson Jr, J.W.; Bye, G.K.;
WDBF. Knox, D.A.; Svodoba, C.F.; Foxemberg, W.E. and Green
T.C.: “A New Biopolymer-Free, Low-Solids, High-
Bentonite Inhibition. The cationic polymer with low Density Reservoir Drilling Fluid: Laboratory
chloride content (CPLCl) performance, in aqueous solutions, development and Field Implementeation”, SPE Drilling
was compared with a commercial quaternary amine shale and Completion, (March 2004) vol.10, n° 1.
inhibitor, and the results are shown in the Figures 5 and 6. It 6. Solanet, F.; Rico, C. And Rodríguez R.: “Glicoles para
can be observed that the fluids prepared in presence of an perforar Arcillas de alta reactividad”, V Jornadas de
inhibitor had resulted in one fluid contends a completely Perforación – Fluidos de Perforación y su Control
dispersed clay. The results show clearly that the presence of a Ambiental, Instituto argentino del petroleo y del Gas,
clay inhibitor favors the decantation of the same one. The buenos Aires, 1997, 169-177.
newly developed shale inhibitor showed excellent inhibitive 7. Dolan, B. and Cliffe, S.: “Mechanism of Shale Inhibition
properties compared with the inhibitor commercial quaternary by Polyols in Water-Based Drilling Fluids”, SPE 28960,
amine shale, in any tested concentration. 1995.
4 SPE 94523

8. Aston, M.S. and Elliot, G.P.: “Water-Based Glycol Chemical Stabilization of Reactive Shale Formation”, ” AADE
Drilling Muds: Shale Inhibition Mechanisms” – SPE 2001 National Drilling Conference, “Drilling
28818, 1994. Technology-The next 100 Years”, Texas, 2001
9. Dowens, J.D. et al.: “Tame: A New Concept in Watrer-
Based Drilling Fluids for Shales,” SPE 26699, Offshore.
Europe Conference, Aberdeen, Sept 7-10, 1993.
10. Retz, R.; Friedheim, J., Lee, J. and Welch, O.: "An
Environmentally Acceptable and Field-Practical, Cationic
Polymer Mud System," SPE 23064, Offshore Europe 91,
Aberdeen, Sept 3-6, 1991.
11. Patel, A.; Stamatakis, Friedheim, J.E. and Davis, E.: “High
InhibitiveWater-Based Fluid Systema Provides Superior

Figure 1: Complexes precipitate formed by mixture

SPE 94523 5

Figure 2: Before aging rheological behavior of: a) NI-WBDF, b) Standard traditional Fluid. The both systems were contaminated with 0, 20, 30
and 40 ppb of bentonite

Figure 3: After aging rheological behavior of: a) NI-WBDF, b) Standard traditional Fluid. The both systems were contaminated with 0, 20, 30
and 40 ppb of bentonite
6 SPE 94523

Figure 4: Fluid Loss content for NI-WBDF and for STF: a) before aging, b) after aging

Figure 5: Bentonite inhibition in presence of a commercial quaternary amine shale inhibitor:

a) without inhibitor, b) with 2 ppb, c) with 4 ppb, d) with 6 ppb, e) with 8 ppb
SPE 94523 7

Figure 6: Bentonite inhibition in presence of CPLCl:

a) without inhibitor, b) with 2 ppb, c) with 4 ppb, d) with 6 ppb, e) with 8 ppb

Figure 7: MBT inhibition for NI-WBDF and for STF: a) before aging, b) after aging.
8 SPE 94523

Table 1: Standard Traditional Fluid (STF) composition

Materials Content (ppb)

Industrial water QSP
KCl 21,7
CMC-HVSW 1,5
CMC type II 1,0
Traditional
Cationic 6,0
Polymeric
Xhanthan Gum 1,5
Baritine 34

Table 2: New inhibitive water-based drilling fluid (NI-WBDF) composition

Materials Content (ppb)

Industrial water QSP
KCl 21,7
CVS-1 2,4
CFLC-1 3,5
CPLCl 4,0
Baritine 34