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Spe 126161 MS
Spe 126161 MS
Spe 126161 MS
Abstract
This paper addresses a critical step on the road to having in-situ reservoir agents. It targets the limiting size of these
devices and endeavors to model their transport mechanisms in the rock matrix. It also details an experimental study
on nanofluid coreflood experiments in the ARAB-D formation of the giant Ghawar field in Saudi Arabia. The study
aims to test the feasibility and future reality for displacing molecular nanoagents in the reservoir. The testing
objectives, process, and results are further detailed herein.
Introduction
The initiative for deploying nanoagents in the reservoir is part of an umbrella initiative for in-situ sensing and intervention
(ISSI) at Saudi Aramco. The ISSI focus area works at identifying and developing enabling micro-nano-technologies
(MNT) in support of the company’s upstream E&P (i.e. exploration, drilling, production, and reservoir) operations.
Logically, having in-reservoir nanodevices will require first and foremost determining the maximum usable size of these
devices before attempting to develop interrogatable (passive) nanosensors or steerable (active) nanomachines. And this
critical step has its own roadmap that involves [1]:
(1) making an assessment of the rock’s pore throat size distribution to establish a first rough estimate on a usable
size or size range for these agents, (2) acquire or formulate stable, uniform, and inert nanoparticle suspensions with
narrow distributions of different particle sizes, and (3) conduct coreflood experiments to validate the particles
stability and their transport continuity under realistic conditions.
The paper is concerned with the coreflood testing that intends to identify and understand the needs to implement the
idea in the field. Conceptually, nanofluid coreflooding is rather simple. It involves injecting a slug (about one tenth
of a pore volume or 1 cc) of a well characterized nanofluid solution at one end of a core sample and follow this with
continuous injection of ultra-filtered particle-free water. The effluent fluid at the other end of the core is then
monitored and characterized for its content in nanoparticles. As such, it is hoped to formulate an idea on the
transport potential of these particles within the rock matrix. In the particle concentration versus injected volume plot,
the influent response is a Heaviside type function and the effluent response is generally a skewed bell-shaped
function. Though the concept is simple, the process is
2 NANOFLUID COREFLOOD EXPERIMENTS IN THE ARAB-D SPE 00000
rather involving. In addition to the obvious coreflood apparatus, the process involved using a host of very
sophisticated instruments for it to be successful. The rest of the paper elaborates further on the elements of
the roadmap that are ultimately geared towards an upcoming field test of the concept.
Figure 1: A bimodal response of the pore size distribution in the ARAB-D. The
nanoparticles size upper limit for direct plugging is set at about 500 nm and for
bridging at about 100 nm.
NMR techniques provide a corresponding method to address the pore size characteristics of carbonate
reservoirs and, accordingly, it constituted an invaluable tool for sample selection with the desired rock
1 ARAB-D is the most prolific oil bearing formation of the Ghawar field in the Kingdom of Saudi Arabia. Ghawar is the
largest oil field discovered in the world today. From its northern extremity the field extends southward some 150 miles (240 km)
as essentially one long continuous anticline, about 25 miles (40 km) across at its widest point.
SPE 00000 KANJ et al., SPE, SAUDI ARAMCO 3
quality for use in the nanofluid coreflood testing. As with other advanced imaging techniques, NMR is a
non-destructive process that can be used under both static and dynamic conditions rendering the samples
usable for further tests. NMR measurements are based on the surface and bulk interactions of the rock with
hydrogen containing fluids. Measured values are classified by the time-dependent relaxation behavior of the
NMR signal. With a suitable assignment of surface relaxivity, the exponential time decay curve of an NMR
signal can be associated with pore sizes. The relaxation time T2 can be related to the surface relaxivity (ρS ),
and the surface to volume ratio, S/V , by the following equation:
1 S
= ρS · (1)
T2 V
NMR curves for three of the samples illustrating this correspondence with the response from mercury injection
are shown in Figure 2. In the case of NMR measurements, the breakdown of macro and micro pores occurs
at a T2 time of approximately 350 ms based on a surface relaxivity of 0.0157 μm/ms.
ed12000
uit
lp
m
Al 8000
an
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S 4000
R
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1E+02 1E+03 1E+04 1E+05 1E+06 1E+07
Spin-Spin Relaxation Time (T2), µs
Nanoparticle Suspensions
Now that we have established a rough basis on usable sizes, the obvious remaining question is: “What
type of nanoparticles to use?” Acquired or functionalized nanoparticles, nanodevices, or nanoagents, should
be safe to handle and dispose of. They should be environmentally friendly so that we can inject them with
no concern into reservoir formations. The particles should be stable in suspension, should remain dispersed
4 NANOFLUID COREFLOOD EXPERIMENTS IN THE ARAB-D SPE 00000
Figure 3: Thin section and SEM pore cast images of the ARAB-D. (After Cantrell
and Hagerty, 1999 [2].
in solution, and should have little or no affinity (tendency to get adsorbed) to the carbonate rocks of the
ARAB-D under reservoir conditions. The stability should be measured in years instead of days or weeks. A
number of potential nanoparticle solutions were examined. These included among others magnetite (Fe3 O4 )
micro-precipitates form of ferric/ferrous chloride and perchloric acid, barium iron oxide (BaFe12 O19 ), barium
sulfate (BaSO4 ), and co-polymer suspensions. We also looked at Silica, Manganese, and Zinc oxides. The
requirement on surface chemistry sophistication to properly suspend particles is also a key controlling factor
in the selection of one particle type.
Co-polymer suspensions satisfied the majority of the set conditions for preliminary testing under room
temperature conditions. These are polystyrene beads cross-linked with di-vinyl benzene (DVB) solubilized
in ultra pure water. The nanoparticle suspensions come in different concentrations and particle sizes and
a narrow band of size variation in the solution. The mean sizes used in testing varied from 20 nm to
200 nm. One polymeric nanoparticle type was provided in solution as water turbidity standards. These were
supplied in a variety of turbidity values ranging from 0 NTU 2 to 10,000 NTU. Samples with 50, 500, and
800 NTU turbidity values are demonstrated in Figure 5-B. An environmental scanning electron micrograph
(ESEM) of an evaporated solution with a reported turbidity of 500 NTU is shown in Figure 5-D and 5-E.
Though we confirmed the particles mean size and size distribution in solution, particle concentration in
relation to turbidity was not possible. Accordingly, the test results obtained with this fluid using an in-
house turbidity meter were more qualitative than they were quantitative. Next, we opted for research grade
solutions. These included white latex spheres (Figure 5-C) and fluorescent latex spheres (Figure 5-A). The
particles have a density of 1.05 g/cm3 and a refractive index of 1.59 measured at a wave length of light of
589 nm. These have a shelf life exceeding 2 years. The fluorescent microspheres are hard-dyed with the dye
incorporated throughout the polymer matrix and accordingly photobleaching and dye leaching in aqueous
media is minimal. The latter particles emit bright and distinctive colors when illuminated by light of shorter
wavelengths than the emission wavelength. The particle count per milliliter from particle concentration (%
solids) is determined analytically according to:
Dp−3
Np = 1.9 × 1021 (2)
(1 + ρ◦ /C − ρ◦ )
where Np is the particle count per milliliter of solution; Dp is the mean diameter of the particles in solution in
nm; ρ◦ is the unitless ratio of the density of the solvent to the density of the polymeric particles; and C is the
particle concentration by mass (% solids/100). Initial checks of the morphology, size, size distribution, and
concentration of nanoparticles were made using appropriate analytical techniques. Table 1 lists the various
techniques, the measured quantities and the general remarks associated with each method. Measurements
confirmed the manufacturers’ reported specifications.
Figure 5: General purpose latex particles (polymer microspheres) were used in the
coreflood experiments at room temperature but emulated reservoir pressure and
flow rate conditions. Both white and fluorescent particles were included in these
tests.
Figure 6: The nanofluid coreflood testing system. The arrow in the photo on
the left points to the coreflood cell that holds the core plug. A schematic of the
nanoparticle injection system is demonstrated to the right. Injection and pore
pressures up to 5,000 psi can be set while confining pressures up to 10,000 psi and
reservoir temperatures up to 110 ◦ C can be maintained by auxiliary systems.
SPE 00000 KANJ et al., SPE, SAUDI ARAMCO 7
test). (The slug volume varied from 5% to 100% the total pore volume of the core sample at hand.) If
nanoparticles are not detectable in the effluent during a WAN test, a continuous injection of nanofluid is
attempted (CIN test). Now, if nanoparticles were detected in the effluent during the CIN phase, continuous
ultra-pure water injection is applied (CIF test). This multi-phase process is needed to establish the suitability
of a particle size and concentration selection and identify any interaction affinity to the carbonate matrix.
At any given water injection rate, one of four outcomes maybe reached. These are demonstrated in Figure 7.
The first outcome is indicative of a successful test with the right combination of particle size (D), particle
concentration (C), and minimal particle-rock interaction level (I). The remaining outcomes are indicative of
plugging, bridging, or interaction problems. Interaction between the nanoparticles and the rock matrix is
probably the most critical as the particles would need to be properly refunctionalized.
The Sample demonstrated in Figure 8 was tested using a commercially acquired 100 nm copolymer
beads solution. WAN testing at varying injection rates demonstrated no nanoparticle flow on the effluent
side. Similar tests on plugs from the same core added that particles are detectable in CIN but not in CIF
testing. This fact lead us to conclude that there is high interaction between the particles and the carbonate
matrix. The resulting particle retention was viewed using the ESEM images taken from the inside of the rock
at different distances from the inlet. These images and their location in the sample are shown in the figure. In
Figure 8, “A” indicates the inlet end (injection side) of the core. The photomicrographs show reduced particle
deposition with increased distance from inlet. The particles coat the carbonate crystals in a fashion similar
to Chickenpox. Stability tests conducted in our labs demonstrated the flocculations and agglomerations that
took place in the original solution in the presence of salt and carbonate fines (limestone) as demonstrated in
Figure 9. Instabilities were also confirmed by examining the absorbance spectra generated following mixing
the nanofluid with sodium chloride and potassium chloride in amounts ranging from 0 to 100,000 ppm. By
placing polymer chains (ligands) on the surface of the nanoparticles, an unfavorable entropic penalty will
need to be overcome in order for any agglomeration and precipitation to occur. And the modified solution
is rendered stable (Figure 9-C).
Using this modified nanofluid solution, we run a chain of parametric study tests to ascertain an optimal
combination of the various influential parameters. In particular, a test that was conducted at field comparable
conditions. The experiment used a nanofluid at low concentration of nanoparticles (1000 ppm). A slug of
SPE 00000 KANJ et al., SPE, SAUDI ARAMCO 9
Figure 8: ESEM results from a coreflood test using a commercially acquired poly-
meric nanofluid. Magnifications range from 15,000 to 30,000 times. Each of these
particles is in the order of about 100 nm. The scale bar on the ESEM images
measures 2 μm.
B
+
1 (10,0) (50,0) (100,0) (10,5) (50,5) (100,5) (0,0)
g
o
f
C
a
C
O
3
A C
Figure 9: Stability tests. The original solution was deemed unstable in the presence
of carbonate fines (A) and salts (B). The pair of numbers indicate the concentration
of NaCl or CaCl2 in Kppm units. The modified solution is stable (C).
10 NANOFLUID COREFLOOD EXPERIMENTS IN THE ARAB-D SPE 00000
1 cc of this solution was injected into a one end of the core in a WAN mode. Water was injected at a low
rate of 0.1 cc/min which is comparable to 1-2 ft/day of flood front movement in the field. The core sample
has a pore volume in the order of 11.9 cc, a porosity of 24.6%, and a brine permeability of 142 mD. Collected
fluid samples at the effluent end were characterized for its content in nanoparticles. The nanoparticle
concentration response curve is demonstrated in Figure 10 as a function of the Injected water flood volume
in pore volume (PV) units. At specific data points on this curve, images of samples of the effluent solution are
being demonstrated to reflect on its turbidity and accordingly on the change of its content in nanoparticles.
The area under the curve is an indication of the amount of the nanoparticles mobilized in this process. This
compared favorably with the amount injected at the influent end; generally with more than 90% recovery.
Figure 11 further demonstrates the high level of success that was achieved in mobilizing the nanoparticles
inside the rock. All ESEM slides demonstrate that the sample is practically particle-free.
%
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C
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ic
t
r
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P
0
0 0.5 1 1.5 2
Figure 10: Nanoparticle concentration response curve from a WAN test that uses
the modified nanofluid solution.
Summary
This project worked to identify the usable size of nanoparticles in reservoir rocks and validate their transport
potential. We demonstrated the feasibility of mobilizing nanoparticles in the ARAB-D through nanofluid
coreflood experiments. Conceptually, the experiments are simple. However, the process is very involving. It
involves picking a representative rock sample, having a stable/compatible nanofluid, and using the right set
of characterization tools for the rock, the fluid, and the particles.
We targeted the prolific ARAB-D reservoir for its importance. We analyzed a large number of ARAB-
D samples with high-pressure mercury injection tests. This yielded some starting points for particles size
selection for plugging and bridging limits consideration.
The experiments are based on an optimized testing program that we developed following a number of
preliminary but structured tests. The program is a function of the size of particles, the concentration of
particles in the solution, the interaction level between the nanoparticles and the rock matrix, and the influent
rate. As such, we ascertained an optimal combination of influential parameters. Proper functionalization
or surface chemistry is crucial. It enhances the nanoparticles’ stability, reduces flocculation/aggregation,
enhances homogeneity, and most importantly reduces the interaction with the rock matrix.
In the near term plan, the nanoagent concept could simply be materializing as smart tracers and in-
situ reservoir chemical markers. In the medium term, however, this could enable traceable nanofluids and
chemical delivery agents. And on the long run, the concept could mature to realize remotely interrogatable
nanosensors and maybe even steerable nanomachines to undertake real intervention tasks in the reservoir.
SPE 00000 KANJ et al., SPE, SAUDI ARAMCO 11
Figure 11: Typical images from a successful nanofluid coreflood test. The ESEM
micrographs demonstrate that the sample is practically particle-free.
Reservoir nanoagents are the ultimate dream machines of the upstream E&P for illuminating the reservoir.
It is hoped that through these simple concept experiments, this huge dream is soon to become a reality.
Acknowledgment
The authors of this paper would like to acknowledge the experimental support that they received during
the different phases of this research from Mr. Salah H. Al-Saleh.
References
[1]. Kanj, M.Y., Funk, J.J., and Afaleg, N.I. (2008) “Towards In-Situ Reservoir Nano-Agents,” Proceedings
of the NSTI Nanotechnology Conference and Trade Show, Boston, MA, June 1–5.
[2]. Cantrell, D.L. and Hagerty, R.M. (1999) “Microporosity in Arab Formation Carbonates, Saudi Arabia,”
GeoArabia, 4, No. 2, 129–154.
[3]. Clerke, E.A. (2007) “Permeability and Microscopic Displacement Efficiency of M1 Bimodal Pore Sys-
tems in Arab-D Limestone,” SPE#105259 presented at the 15th SPE Middle East Oil&Gas Show and
Conference, Manama, Kingdom of Bahrain, March 11-14.
[4]. Jones, P.J., Shafei, E.N., Halpern, H.I., Dubaisi, J.M., Ballay, R.E., Funk, J.J. (2004) “Py-
rolytic Oil-Productivity Index Method for Predicting Reservoir Rock and Oil Characteristics,” U.S.
Patent# 6823298, Saudi Arabian Oil Co.