a r t i c l e
i n f o
Article history:
Received 16 May 2007
Accepted 14 April 2009
Keywords:
biopolymer
drilling mud
additive
rheology
HerschelBulkley
a b s t r a c t
Drilling muds are complex uids, generally used to clean the well, maintain hole integrity, transport the rock
cuttings, lubricate the drill bit and control formation pressures. Two basic types of drilling uids are used,
water based muds (WBM) and oil based muds (OBM). OBM are very effective but polluting, and environmental regulations continue to restrict the use of oil based muds in many areas of the world. In order to
reduce the mud toxicity, we developed water based mud systems using two biopolymers, which are xanthan
gum and scleroglucan, generally proposed for high permeability reservoirs or for complex geometries such as
horizontal wells. In this study, we evaluated the rheological behaviour of different samples and we determined the effect of components such as clay, calcium carbonate and potassium chloride. This formulations
exhibit non-Newtonian rheological behaviour which can be described well by the tree parameter in
HerschelBulkley rheological model.
2009 Elsevier B.V. All rights reserved.
1. Introduction
During the last few years, petroleum industry has developed new
drilling techniques such as horizontal and directional well. In order to
increase well productivity, directional drilling must reach rock reservoir i.e. high permeability and unconsolidated formation. In these
formations, drilling mud requires specic properties. The literature
reports that the most effective drilling uids are based on oil, crude or
synthetic, but their impact on environment pollution is very important. If horizontal and inclined drillings are also productive, it is
thanks to their passage in the reservoir. In these formations, the
drilling uid responsible of cutting ascent and good cleaning of the
hole must have specic properties. Horizontal wells are normally
selected for their ability to deliver high production rates and large
reserve volumes (Butler et al., 2000). Simulation studies indicate that
horizontal wells in thermal projects can increase recovery efciency
due to better area sweep, accelerate production which improves the
oil-steam ratio (OSR), shorten project life, and increase project
protability (Carpenter and Dazet, 1992). The role of drilling uid is
to pass through formations with high porosity while keeping all its
rheological properties and without causing damage to the crossed
formations. To reduce the mud toxicity, the water based mud was
developed. The studies carried out used a drilling uid containing
water, a natural or synthetic polymer and additives. Only the type
of polymer is different considering its molecular conguration, its
behaviour in aqueous medium as well as the viscosiers properties,
which it confers on mud. The polymers currently used in the oil industry are cellulosics, guar gum, xanthan gum, polyacrylates, polyacrylamides and maleic anhydride derivatives. Control of drilling uid
properties is essential when encountering unconsolidated formations in complex geometries. These properties include uid density,
rheological parameters (viscosity and yield stress).
This paper describes a study of water based mud used in complex
geometries, including both polysaccharide xanthan gum and scleroglucan. Among hydrophilic polymers, polysaccharides are the choice
material due to their no toxicity and acceptance by regulating authorities
(Bonferoni et al., 1993). Comparisons were made between xanthan
formulations and scleroglucan formulation at different concentrations.
The systems used in this study comply to API standards. The similar
formulations were studied for high temperature zone and/or high
permeability reservoirs (Sanchez et al., 2003). Other studies show that
the reservoir must be drilled with specic drilling uid because these
formations created some difculty and additives give precise properties
to the mud which help to control uid loss. Horizontal sections are
drilled with specialised reservoir drilling uid (RDF) that contains
primary polymers for viscosity, bridging agents like sized calcium
carbonate (CaCO3) or sodium chloride (NaCl) salt and additives (usually
starch or another polymer) tailored to control uid loss (Houwen et al.,
1997).
The system is composed of a biopolymer viscosier, a starch loss
agent and a bactericide calcium carbonate is needed to develop density. The clay High Mod Prima (HMP) is the solid added to WBM
system. Alkalinity is controlled with potassium hydroxide. The goal of
this work is to determine a water based drilling uid containing
biopolymer and additives which is not polluting for the environment
or with acceptable toxicity, and also to carry out a comparative study
between biopolymers in order to decide which product is the best. To
S. Baba Hamed, M. Belhadri / Journal of Petroleum Science and Engineering 67 (2009) 8490
85
Table 1
Products used.
Products
Commercial name
Clay
Biopolymere 1 scleroglucan
Biopolymere 2 Xanthan gum
Weight material
Starch
Potassium chloride
Biocide/bactericide
H.M.P
Biovis
Idvis
Id40
Ido
Company
Chemical composition
Use
Paraformaldhyde
Potassium hydroxide
Schlumberger
Panreac
Gifrer Barbezat
Panreac
CaCo3
C6 H10 o
KCL
O-ch2
O-ch2
O-ch2
KOH
Control pH to 8.59.0
2.1. Biopolymers
Both biopolymers used are polysaccharides, the xanthan gum and
the scleroglucan which have high properties viscosiers with low
concentrations.
Scleroglucan also known as schizophyllan (Van der Valk et al., 1977)
or lentinan depending on biological source) is a fungal polysaccharide
with immunostimulatory properties (Jong and Donovic 1989; Pretus
et al., 1991). This polymer is an exopolysaccharide chosen because of its
usefulness in enhanced oil recovery, food and pharmaceutical application (Sandford, 1979).
The biopolymers tested in this study were provided by the Degussa
and Schlumberger companies, they have different conformations and
present specic properties in aqueous medium. Scleroglucan, industrial name BIOVIS is produced by the Degussa society. BIOVIS is a nonionic, readily water-soluble biopolymer produced through fermentation of a carbohydrate by a fungus. BIOVIS solutions exhibit exceptional
shear thinning rheology and suspending ability. The advantages of
BIOVIS in comparison to other biopolymers are higher thermal stability, pH stability and tolerance of divalent and trivalent cations such as
Ca2+, Mg2+ and Fe3+. In an aqueous solution, BIOVIS molecules adopt
a triple-helical conformation and can be described as rigid rods. Under
static conditions, these rods form a web-like 3D structure. The resulting gel provides an excellent carrying capacity (Biovis, 2003). Its
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S. Baba Hamed, M. Belhadri / Journal of Petroleum Science and Engineering 67 (2009) 8490
molar mass is 5.106 Da. The xanthan gum of industrial name Idvis
was provided by the Schlumberger Company. Xanthan is used frequently in drilling uids, either in combination with the traditional
thickener, bentonite clay, or alone in clear muds (Linton et al., 1991). It
is reported, with respect to suspending ability, that xanthan gum
surpasses that of any other polymer currently used in drilling uid (Shah
and Ashtaputre, 1999). But Xanthan gum has a limited temperature
stability (Caenn and Chillingar, 1996).
Xanthan gum is a high molecular weight polysaccharide that can give
interesting properties to the drilling uids. It is used as a rheology
control agent in aqueous systems and as a stabilizer for emulsions and
suspensions. Its numerous areas of applications cover a broad spectrum
and range from the food industry to oil recovery (M'bodj et al., 2004).
Xanthan gum is a nonionic biopolymer. The molecule conforms in the
form of simple, double or triples helix which interacts with other
molecules of polymer to form a complex network. In dilute solution,
aggregates formatted with weak connections which could be dissociated by mechanical action as a shearing. Its molar mass is 2.106 Da.
Fig. 3. Flow curve in plate-plate system for two different values gaps.
2.2. Additives
The additives used are: clay High Mod Prima (HMP), the calcium
carbonate and the potassium chloride. Drilling muds containing the
biopolymers usually are treated with biocides to inhibit microbial
degradation of the polysaccharides. The bactericide used in this study
is paraformaldehyde. Starch is used for control of uid loss to permeable formations High Mod Prima (HMP) was added in some of the
formulations to simulate drilled solids. The microscopic structure of
HMP clay is analyzed using X-ray diffraction (XRD). The diagram of
XRD of Fig. 1 shows four spectrums of various forms: the spectrum A
represents raw clay i.e. untreated. In the spectrum B, clay was heated to
550 C after a 4 h transit by the drying oven. The spectrum C indicates
the clay treated with ethylene glycol during 24 h. The last spectrum D
represents the clay treated under the normal conditions, that is to say
under free air drying for 24 h duration. After different treatment,
diffraction of X rays represented in Fig. 1 showed that the clay was
primarily composed of kaolinite, illite and quartz. Kaolinite, Al2Si2O5
(OH)4, is a layered aluminosilicate with a dioctahedral 1:1 layer structure consisting of tetrahedral silicate sheets and octahedral aluminium
hydroxide sheets (Bailey, 1980). Sized calcium carbonate particles
(D50 ~ 40 m) are added to increase the uid density up 1.01 g/cm3.
Calcium carbonate particles, associated to biopolymers, control uid
loss in drilling muds. Scleroglucan and xanthan gum were considered
as viscosiers and uid-loss additives, while calcium carbonate
particles were considered to be the best bridging (JPT, 2003).
S. Baba Hamed, M. Belhadri / Journal of Petroleum Science and Engineering 67 (2009) 8490
87
Table 2
Fluid based biopolymers with various clay HMP concentrations measured at 25 C.
Biopolymers
Xanthan gum
Scleroglucan
(%)
(Pa)
(Pa.s)n
2.83
6
10
15
20
2.83
6
10
15
20
2.65
2.80
3.78
3.96
8.30
2.38
1.93
3.36
2.57
2.92
1.94
3.07
3.32
4.98
4.30
0.05
0.22
0.19
1.99
2.56
n
0.35
0.30
0.31
0.30
0.38
0.84
0.69
072
0.38
0.36
Fig. 4. Inuence of high mod prima on xanthan gum. Flow curve in permanent regime.
shear stress
shear yield stress
shear rate
Fig. 5. Inuence of high mod prima on scleroglucan. Flow curve in permanent regime.
The ow curves in permanent regime of the tested uids, containing a different voluminal fraction in calcium carbonate are represented in Fig. 6.
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S. Baba Hamed, M. Belhadri / Journal of Petroleum Science and Engineering 67 (2009) 8490
Scleroglucan
(%)
(Pa)
(Pa.s)n
9
15
20
25
30
9
15
20
25
30
3.11
3.16
3.17
3.13
3.08
3.14
3.14
2.09
3.82
1.81
2.84
2.14
2.10
2.14
2.60
0.03
0.08
0.31
0.52
0.60
n
0.34
0.37
0.37
0.38
0.36
0.88
0.82
0.62
0.58
0.57
S. Baba Hamed, M. Belhadri / Journal of Petroleum Science and Engineering 67 (2009) 8490
89
Table 4
Fluid based biopolymers with various potassium chloride Kcl concentrations measured
at 25 C.
Biopolymers
Xanthan gum
Scleroglucan
(%)
(Pa)
(Pa.s)n
1.5
2.0
2.5
3.0
1.5
2.0
2.5
3.0
2.52
2.00
2.42
2.21
2.66
3.71
2.83
2.72
0.30
0.73
0.60
0.56
0.05
0.06
0.04
0.05
n
0.48
0.48
0.53
0.55
0.81
0.81
0.86
0.88
90
S. Baba Hamed, M. Belhadri / Journal of Petroleum Science and Engineering 67 (2009) 8490
References
Bailey, S.W., 1980. In: Brindley, G.W., Brown, G. (Eds.), Crystal Structures of Clay Minerals
and their XRay Identication: Structures of Layer Silicates. Mineralogical Society,
London, pp. 139.
Biovis, 2003. Oileld PolymersConstruction chemicalsDegussa Edition August.
Bonferoni, M.C., Rossi, S., Tamayo, M., Pedraz, J.L., Dominguez_Gil, A., Caramella, C., 1993. On
the employment of -Carrageenan in a matrix system, I. Sensitivity to dissolution
medium and comparision with Na carboxymethyl cellulose and Xanthan gum. J. Control.
Release 26, 119127.
Bryant, Rebecca S., 1987. Potential uses of microorganisms in petroleum recovery
technology IIT Research Institute, National Institute for Petroleum and Energy
Research P.O. Box 2128, Bartlesville, Oklahoma 74005. Proc. Okla. Acad. Sci. 67, 97100.
Butler, B.A., Sharp, K.W., McDaniel, D.R., Bump, D.M., 2000. New generation drill-in
uids and cleanup methodology lead to low-skin horizontal completions SPE
58741. International symposium on formation damage held in Lafeyette, Louisiana,
2324 February 200.
Caenn, R., Chillingar, George V., 1996. Drilling uids: state of the art. J. Pet. Sci. Eng. 14,
22l230.
Camesano, T.A., Wilkinson, K.J., 2001. Single molecule study of xanthan conformation
using atomic force microscopy. Biomacromolecules 2, 11841191.
Carpenter, D.E., Dazet, S.C., 1992. Horizontal wells in a steamdrive in the Midway Sunset
Field. 24th Annual OTC in Houston, Texas, May 47.
Chenu, C., Pons, C.H., Robert, M., 1987. Interaction of kaolinite and montmorillonite with
neutral polysaccharides. In: Shultz, L.G., Van Olphen, H., Mumpton, F.A. (Eds.), Proceedings of the Int. Clay Conf., Denver 1985. The Clay Minerals Soc Bloomington Indiana,
pp. 375381.
Chnard, P.G., 1984. Composition of oil-based drilling muds. In: Greene, G.D.,
Engelhardt, F.R. (Eds.), Report of the Workshop on Environmental Considerations
in the Offshore Use of Oil-Based Drilling Muds. 234 May, 1984. Ottawa, Canada.
Technical Report 2. Canada Oil and Gas Lands Administration, Environmental
Protection Branch, Ottawa, Canada, pp. 1220.
Cobianco, S., Bartsek, M., Lezzi, A., Previde Massara, E., Guarneri, A., 2001. New solidsfree drill-in uid for low permeability reservoirs. Paper SPE 64979 presented at the
2001 Int. Symp. on Oileld Chemistry, Houston, Tx, Feb. 1316.
D'Angelo, M.V., Chertcoff, R., Rosen, M., 2001. Miscible ooding of polymeric solution in
porous media of double porosity. SPE 1624733, Grupo de Medios Porosos, Facultad
de Ingeniera, Universidadde Buenos Aires. Society of Petroleum Engineers Inc.
Hemphill, T., Campos, W., Pilehvari, A., 1993. Yield-power law model more accurately
predicts mud rheology. Oil Gas J. 91 (34), 4550 (Aug 23).
Houwen, O., Ladva, H., Meeten, G., Reid, P., Williamson, D., 1997. A new slogan for drilling
uids engineers. Oileld Rev. 9 (1), 216 (Spring).
Gallino, G., Guarneni, A., Poli, G., Xiao, L., 1996. Scleroglucan biopolymer enhances WBM
performances. Paper SPE 3642 presented at the 1996 ATCE Denver, Colorado, Oct. 69.
GEO Drilling Fluids, Inc. Technical services news letter, December 15, 2001 Volume V,
Number 6 http://www.geodf.com/pdfs/new121501.pdf.
Jong, S.C., Donovic, R., 1989. Adv. Appl. Microbiol. 34, 183262.
JPT (Nov), 2003. Optimized drill-in uid for an openhole gravel-pack completion. www.
SPE.Org.
Lauzon, R.V., Reid, K.I.G., 1979. New rheological model offers eld alternative. Oil Gas J.
51 (May).
Linton, J., Ash, S., Huybrechts, L., 1991. Microbial polysaccharides. In: Byrom, D. (Ed.),
Biomaterials. Stockton Press, New York, pp. 217261.
M'bodj, O., Kbir Ariguib, N., Trabelsi Ayadi, M., Magnin, A., 2004. Plastic and elastic
properties of the systems interstratied claywaterelectrolytexanthan. J. Colloid
Interface Sci. 273, 675680.
McWilliams, D., Rogers, J., West, T., 1973. Water soluble polymers in petroleum recovery.
Polym. Sci. Technol. 2, 105126.
National Research Council, 1983. Drilling Discharges in the Marine Environment. National
Academy Press, Washington. 180 pp.
Neff, J.M., McKelvie, S., Ayers, R.C., 2000. Environmental impacts of synthetic based
drilling uids. OCS Study MMS 2000-64. U.S. Dept. of the Interior, Minerals
Management Service, Gulf of Mexico OCS Program, New Orleans, LA. 118 pp.
Nehal, Ibrahim Abu-Lail 2003. The effect of biopolymer properties on bacterial adhesion:
An atomic force microscopy (AFM) study A Thesis in Chemical Engineering
Worcester Polytechnic InstituteDepartment of Chemical Engineering12 Septembre.
O'Brien, D.E., Chenevert, M.E., 1973. Stabilizing sensitive shales with inhibited,
potassium-based drilling uids. J. Pet. Technol. 25 (9), 10891100.
Parker, R., 1983. The market for chemicals in oil industry. In: Ogden, P. (Ed.), Chemicals
in the Oil Industry. Royal Society of Chemistry, London, pp. 179215.
Pretus, H.A., Ensley, H.E., McNamee, R.B., Jones, E.L., Browder, I.W., Williams, D.L., 1991.
J. Pharmacol. Exp. Ther. 257, 500510.
Power, D., Zamora, M., 2003. Drilling Fluid Yield Stress: Measurement Techniques for
Improved Understanding of Critical Drilling Fluid Parameters, paper AADE-03NTCE-35 presented at the 2003 AADE Technical Conference, Houston, 13 April.
Saldungaray, Pedro M., Troncoso, Juan C., Santoso Bambang, T., 2001. Simultaneous
gravel packing and lter cake removal in horizontal wells applying shunt tubes and
novel carrier and breaker uid. SPE 68205 the 2001 SPE Middle East Oil Show held
in Bahrain, 1720 March 2001.
Sanchez, E., Audibert-Hayet, A., Rousseau, L., 2003. Inuence of drill-in uids composition
on formation damage. Paper SPE 82 274 presented at 2003 at the SPE European
Formation Damage, The Netherlands 1314 may 2003.
Sandford, P.A., 1979. Exocellular microbial polysaccharides. Adv. Carbohydr. Chem.
Biochem. 36, 265312.
Shah, A.K., Ashtaputre, A.A., 1999. Evaluation of rheological properties of the exopolysaccharide of Sphingomonas paucimobilis GS-1 for application in oil exploration.
J. Ind. Microbiol. Biotech. 23, 442445.
Stokke, B.T., Brant, D.A., 1990. The reliability of wormlike polysaccharide chain dimensions
estimated from electron micrographs. Biopolymers 30, 11611181.
Van der Valk, P., Marchant, R., Wessels, J.G.H., 1977. Exp. Mycol. I, 6982.
Vuppu, A.K., Garcia, A.A., Vernia, C., 1997. Tapping mode AFM of scleroglucan networks.
Biopolymers 42, 89100.
Wanko, A., Bekkour, K., 2003. Caractrisation rhologique de mlanges argiles-polymres.
16me Congrs Franais de Mcanique. Nice 15 Septembre.