Fuel 184 (2016) 222–232

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Fuel
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Full Length Article

Effect of nanoparticles/nanofluids on the rheology of heavy crude oil

and its mobility on porous media at reservoir conditions
Esteban A. Taborda a, Camilo A. Franco a,b,⇑, Sergio H. Lopera b, Vladimir Alvarado c, Farid B. Cortés a,b,⇑
a
Grupo de Investigación en Fenómenos de Superficie – Michael Polanyi, Facultad de Minas, Universidad Nacional de Colombia-Sede Medellín, Colombia
b
Grupo de Investigación en Yacimientos de Hidrocarburos, Facultad de Minas, Universidad Nacional de Colombia-Sede Medellín, Colombia
c
Department of Chemical Engineering, University of Wyoming, Dept. 3295, 1000 E. University Avenue, Laramie, WY 82071, United States

a r t i c l e i n f o a b s t r a c t

Article history: In this work, we evaluate the effect of nanoparticles and nanofluids as viscosity reducers for heavy crude
Received 20 May 2016 oil (HO). The effect of alumina, silica and acidic silica nanoparticles was evaluated through n-C7 asphal-
Received in revised form 4 July 2016 tene adsorption and aggregation tests using UV–vis spectrophotometry and dynamic light scattering. The
Accepted 4 July 2016
nanoparticles of acidic silica were used to prepare a water-based nanofluid at different concentrations in
distilled water, and also with the addition of 2.0 wt% of a non-ionic surfactant. The shear rheological
response was obtained as function of nanoparticle concentration, temperature (from 298 to 323 K) and
Keywords:
shear rate (ranging from 0 to 100 s
1). Experimental results indicate that increasing the concentration
Rheology
Heavy crude oil
of nanoparticles in the mixture, up to 10,000 ppm, leads to a viscosity reduction of approximately 90%
Asphaltene in comparison with the nanoparticle-free crude oil. At higher concentration of nanoparticles, the effec-
Nanoparticles tiveness of the heavy-oil viscosity reduction diminishes. Rheological tests showed a non-Newtonian
Nanofluids behavior for the mixtures tested at 298 K. However, as the temperature reaches 323 K the specimens
Adsorption behave in a Newtonian fashion. Coreflooding tests were conducted under typical reservoir conditions
of pore and overburden pressures, i.e. 2600 and 3600 psi, respectively, and at 360 K. Results indicate that
the addition of nanoparticles increases the heavy oil mobility and leads to an improvement in oil recovery
of roughly 16%.
Ó 2016 Elsevier Ltd. All rights reserved.

1. Introduction lower than 20° and the corresponding value for EHO is lower than
10° [5,7,9]. HO and EHO are also characterized by containing large
The world’s reserves of crude oil amount to 30% in conventional concentrations of heavy metals and heteroatoms, and heavy com-
and 70% in non-conventional reservoirs, respectively. Among the pounds such as asphaltenes, as well as low H/C ratio [10], which
latter reservoir type, heavy oil (HO) and extra-heavy oil (EHO) rep- directly influence the observed crude oil viscosity, typically higher
resent approximately 25% and 45% of these resources, respectively than 100 cP at reservoir conditions [10].
[1,2]. Latin America possesses the largest reserves of HO and EHO Asphaltenes are refractory molecules with high molecular
worldwide, with Venezuela and Colombia having the first and fifth weight that can impact the different stages of the production sys-
of largest reserves in the region [3,4]. However, the production, tem and refining streams [11]. Asphaltenes contain heteroatoms
transport and refining of HO and EHO represent a considerable such as O, N and S and metals such as Ni, Fe and V. The presence
set of technological challenges [5–7]. The main challenging charac- of heteroatoms and their location in the structure make asphalte-
teristics of these crude oils, namely their high specific gravity and nes the most polar molecules present in crude oil, leading to their
high viscosity, complicate their production, transport and refining self-association and further formation of large asphaltic flocs.
[5,6,8]. In the context of this research, a HO has an API gravity These flocs also cause an increase in the HO viscosity, which in
some cases leads to formation damage [11–14] and precipitation/
⇑ Corresponding authors at: Grupo de Investigación en Fenómenos de Superficie
adsorption problems in production facilities [12,15,16]. At high
– Michael Polanyi, Facultad de Minas, Universidad Nacional de Colombia-Sede
concentration of asphaltene, namely >40,000 mg/L, the increase
Medellín, Kra. 80 # 65-223. Bq. M3-100A, Colombia. in viscosity is mostly due to the formation of a viscoelastic network
E-mail addresses: caafrancoar@unal.edu.co (C.A. Franco), fbcortes@unal.edu.co of nanoaggregates [17,18]. In addition, sulfur can form strong CAS
(F.B. Cortés).

http://dx.doi.org/10.1016/j.fuel.2016.07.013
0016-2361/Ó 2016 Elsevier Ltd. All rights reserved.
 E.A. Taborda et al. / Fuel 184 (2016) 222–232 223

and C@S bonds, which can also contribute to an increase in the 2. Experimentation
crude oil viscosity [14,19].
To improve production, transport and refining of HO and EHO, 2.1. Materials and reagents
several techniques under reservoir and surface conditions have
been used, namely: (i) emulsification of oil-in-water (O/W) emul- n-Heptane (99%, Sigma-Aldrich, St. Louis, MO), and Toluene
sions [20–22] that can drastically reduce the fluid viscosity and (99.5%, Merck KGaA, Germany) were used as received. A Colombian
hence improve the crude oil mobility; (ii) use of annular flow as heavy crude oil of 13°API and a viscosity of 1.2  105 cP at 298 K
a method for reducing the drag forces [23–26]; (iii) deasphalting was used as source of asphaltenes. n-C7 asphaltenes were extracted
oil using CO2 [27–29], n-alkanes of low [30–32] and high molecular following a standard procedure as described in previous works
weight [33,34]; (iv) application of thermal processes based on heat [65,66,68]. The elemental analysis of asphaltenes shows a C:
injection through steam and other gases [35–39] to reduce oil vis- 81.4 wt%, H: 7.5 wt%, O: 8.8 wt%, N: 2.3 wt%. A non-ionic surfac-
cosity; and (v) in-situ upgrading such as the various modes of air tant, Tween 80 (Sigma-Aldrich, St. Louis, MO), was used for dis-
injection, e.g. in-situ combustion (ISC) [40,41], thermal cracking persing the nanoparticles in the water-based nanofluid. The
[14,42–44] and its catalytic variations [45–47]. nanofluid was prepared using distilled water with a conductivity
One of the most frequently used techniques for reducing HO of 3 lS/cm. Three kinds of nanoparticles were evaluated: (1)
and EHO viscosities has been the dilution with solvents and light unmodified synthesized silica (SiO2), (2) silica NP with a modified
hydrocarbons such as naphtha [48–50], toluene [51], xylene [49], acid surface (SiO2A) and (3) NPs of commercial alumina (Al2O3).
gasoline [52], diesel [53,54], light oil [51], or mixtures thereof Al2O3 nanoparticles were purchased from Sigma-Aldrich (St. Louis,
[55] as well as some chemical compounds based on R = O (buta- MO). SiO2 nanoparticles were synthesized with tetraethyl orthosil-
none type, among others) [55]. Several authors have reported on icate, TEOS (>99%, Sigma Aldrich, United States), ethanol (99.9%,
the dilution of HO and EHO [55–58] with different solvents and Panreac, Spain), NH4OH (30%, J.T. Baker, United States) and deion-
the changes to the rheological behavior of mixed fluids ized water [73]. For SiO2 nanoparticles surface modification, H2SO4
[56,59,60]. Recently, Mortazavi-Manesh and Shaw [61] studied (95–97%, Merck KGaA, Germany) was used.
the effect of toluene, n-heptane and a mixture 50/50 vol% of
toluene and butanone on the rheological properties of Maya crude
oil as a function of temperature. Their results showed that the mix- 2.2. Synthesis and characterizations of nanoparticles/nanofluids
ture of toluene + butanone caused the largest viscosity reduction.
Naphtha has been so far the most used diluent [57,62,63]. In some SiO2 nanoparticles were synthesized according to the sol-gel
instances, mainly in Venezuela and Colombia, the quantity of method as described in previous works [73,74]. In summary, a
naphtha used in the upgrading of these crude oil types can reach solution with tetraethylorthosilicate (TEOS) as the precursor of sil-
20–40 vol% [58]. Adding naphtha can effectively reduce the viscos- icon, ethanol and NH4OH, is prepared and the mixture is manually
ity and increase the API gravity of HO and EHO [56,59,61]. The stirred, in a process that continues for 1 h and finally dried at 80 °C
excessive use of naphtha for diluting crude oil implies an increase for 24 h to remove any remaining water fraction. The molar ratio of
in the operational costs [51], becoming an impractical technology TEOS:H2O:NH4OH was 1:1.1:0.2. The procedure for acidification of
[51]. Dilution with naphtha is an unfriendly technology for humans the surface of SiO2 nanoparticles consisted of mixing nanoparticles
due to its lower boiling point, 100% volatiles content, and low and sulfuric acid at 0.3 wt% to obtain a solution at pH = 4. A Horiba
explosive limits [51]. Navih pH meter was used for pH measurements. The solution was
Nanoparticles have been used by the oil industry for formation sonicated for 2 h at room temperature, then further stirred mag-
damage inhibition [64–67], HO and EHO upgrading [68], enhanced netically at 100 rpm for 12 h and subsequently centrifuged at
(EOR) and improve oil recovery (IOR) processes [66,69], and 4500 rpm for 15 min. The nanoparticles were dried at 393 K for
wastewater remediation [70]. Due to their particle sizes, between 4 h. In this work, nanoparticles without modification and acidified
1 and 100 nm, large available surface area, high dispersibility and nanoparticles are referred to as SiO2 and SiO2A, respectively. The
tunable physicochemical characteristics, nanoparticles are prone carrier fluid used was composed of a mixture of distilled water
to selectively adsorb asphaltenes and inhibit their self- and 2 wt% surfactant. The procedure followed for the preparation
association [71]. In a previous study [66,69,72], our research group of the nanofluid is described elsewhere [75,76]. In brief, the
focused on using silica, c-alumina and magnetite nanoparticles to nanoparticles and the carrier fluid are stirred at 500 rpm for
inhibit the aggregation of asphaltenes under varying temperature, 20 min at room temperature, then subject to ultrasound for 12 h
solvent ratios and asphaltene concentration [69]. Silica nanoparti- at 298 K. The nanofluid has a viscosity of 8.2 cP, a density of
cles can induce significant reduction in the asphaltene mean aggre- 0.96 g/cm3 and a pH = 7.3.
gate size, which could prevent the formation of large viscoelastic The mean particle size of the nanoparticles (dp) was measured
networks and reduce the oil viscosity as a result. However, to the using dynamic light scattering (DLS) with the help of a nanoplus-
best of our knowledge, there are no studies reporting the rheolog- 3 from Micromeritics (Norcross,GA) at 298 K and equipped with
ical behavior of crude oil in the presence of nanoparticles and their a 0.9 mL glass cell [69]. The BET surface area (SBET) of the nanopar-
impact on relative permeability curves and crude oil recovery (%) ticles was measured through nitrogen physisorption at 77 K using
under flow conditions in porous media at typical reservoir temper- an Autosorb-1 from Quantacrome BET, after outgassing samples
ature and pressure, based on ‘‘huff-n-puff” type stimulations. In this overnight at 413 K under high vacuum (10
6 mbar).
order, the aim of this paper is to evaluate the effect of nanoparti- Total acidity of the nanoparticles surface was determined via a
cles on the rheological properties of a Colombian HO at varying NH3-Temperature programmed desorption. The NH3 desorption,
conditions of temperature, shear rate and dosage of nanoparticles. previously adsorbed on the surface of the nanoparticles, is a direct
The selection of the nanoparticles, optimized towards the adsorp- measure of the degree of acidity of the materials evaluated. We
tion and size reduction of asphaltenes, was achieved using adsorp- used a ChemBet TPR/TPD (Quantachrome Instruments, USA) to this
tion isotherms and the growth kinetics of asphaltenes. In addition end. The procedure involves drying the sample at 470 K in an inert
to rheological responses, coreflooding tests at reservoir conditions atmosphere. Then, the sample is cooled down to 370 K in the pres-
were also performed. The results in this paper are expected to open ence of NH3 to promote the adsorptive process. Subsequently, the
a wider landscape on the use of nanoparticles in IOR processes physisorbed amount is removed by flowing He for 1 h. Finally, the
based mainly on ‘‘huff & puff” configurations. specimen is heated at a constant heating rate of up to 1170 K for
224 E.A. Taborda et al. / Fuel 184 (2016) 222–232

Table 1 the mobility of oil at reservoir pressure and temperature condi-

Estimated mean particle size, BET surface areas and NH3 uptake for selected tions can be evaluated.
nanoparticles.
We anticipate that the penetration of nanoparticles suspended
Material dp50 (nm) SBET (m2/g) NH3 uptake (mmol/g) in an aqueous medium will modify the flow behavior of the oil
SiO2 11 210 1.19 phase once they enter in direct contact with it, increasing its
SiO2A 11 187 1.42 mobility in addition to altering the wettability of the porous med-
Al2O3 35 123 0.34 ium. The selected core has a length of 25 cm, with a diameter of
3.81 cm and a porosity of 11%. The injection fluid consisted of a
synthetic brine of 2 wt% of KCl. The core absolute permeability
complete desorption of NH3. The desorbed amount is calculated was estimated as 1.1 Darcy, through the injection of 20 pore vol-
using a calibration curve [71,77]. Table 1 shows the dp50, SBET umes (PV) of the prepared brine until reaching steady state. The
and values of NH3 uptake obtained for the nanoparticles used in nanofluid used for performing the test is prepared according to
this study. the results of the rheological measurements according to the one
that generates greater viscosity reduction. Fig. 1 presents a sche-
2.3. n-C7 asphaltenes adsorption matic representation of the experimental test. During the core-
flooding tests, pore and overburden pressures were maintained
Adsorption isotherms for n-C7 asphaltenes on the nanoparticles at 2600 and 3600 psi, respectively. The operating temperature
were collected at 303 K, in a concentration (Ci) range of 100– was set at 360 K.
1500 mg/L and at a ratio of nanoparticle-to-solution of 100 mg The ‘‘base system test” aimed at determining the oil and water
per 10 mL [78,79]. An UV–vis spectrophotometer Genesys 10S relative permeabilities in the absence of nanoparticles. Regardless
(Thermo Scientific, Waltham, MA) was used to determine the of the origin and mineralogical composition of the porous media,
asphaltene concentration in solution before and after the adsorp- during the producing life of a reservoir, the reservoir’s wettability
tion process. Hence, the amount of n-C7 asphaltenes adsorbed can vary [48]. For this reason, the ‘‘base system test” consisted of
(Nads) onto the selected nanoparticles could be estimated by a mass subjecting the porous media to a period of aging time needed for
balance analysis once adsorption equilibrium is reached [80]. Addi- wettability restoration. This is achieved by continuous injection
tional information on the procedure can be found in previous pub- of heavy oil for 15 days. Once the system is assumed to have
lications [65,68,79]. become more oil-wet, oil (ko) and water (kw), corresponding to
the end-point effective permeabilities of the oil and water phases,
2.4. n-C7 asphaltenes aggregation experiments respectively, are measured. This is performed first by injecting 20
PV of water at conditions of oil residual saturation (Sor) followed
DLS measurements of heavy oil model solutions in the presence by 20 PV of oil at conditions of water residual saturation (Swr).
and absence of nanoparticles were performed to evaluate the aver- Then, oil (kro) and water relative permeability (krw) and oil recov-
age aggregate size of n-C7 asphaltenes as a function of nanoparticle ery curves are obtained. Posteriorly, the sample is saturated with
addition. n-C7 asphaltenes were dissolved in a mixture n-heptane/ oil again, in a secondary drainage process, in order to prepare the
toluene (Heptol) 40% v/v at a concentration of 1000 mg/L. The mix- core for nanofluid injection. The ‘‘post nanoparticles injection” sys-
ture was magnetically stirred at 300 rpm and aliquots were taken tem is obtained by injecting 1 PV in production direction and then
to obtain the mean asphaltene aggregate size as a function of time. letting it soaking for a period of 12 h. Then values of ko, kw, krw,
The dosage of nanoparticles was fixed at 10 g/L to guarantee total
decantation of the nanoparticles and thus obtain an accurate esti-
mate of the n-C7 asphaltenes aggregate size [69].
9
2.5. Evaluation of nanoparticles/nanofluids as viscosity reducers
9
Rheological measurements were performed using a Bohlin rota-
tional rheometer C-VOR 200 (Malvern Instruments, Worcestershire
- UK), equipped with a Peltier plate for temperature control, with a
plate-plate geometry with diameter of 20 mm and a gap of
150 lm. To analyze the change in viscosity induced by the addition
11 3 1
of nanoparticles, several concentrations were evaluated, namely 0,
1, 3 and 4 wt% at room temperature at shear rate values 0–100 s
1.
2
Each measurement was repeated three times.
A nanofluid was prepared with water + 2% v/v of nonionic sur- 10
factant and the best-performing nanoparticles in adsorption tests
8 6
as well as tests of aggregates n-C7 asphaltenes fragmentation.
9
The nanoparticle concentration in the nanofluid was variable
ensuring nanoparticles concentrations in heavy oil of 0, 10, 1000, 5 6
10,000 and 40,000 mg/L. A fixed dosage of nanofluid of 4% v/v
7
was added to HO and viscosity measurements were conducted at
a constant shear rate of 10 s
1. After this, the optimal concentra-
tion was selected to run the complete rheological study between
0 and 100 s
1 at a temperature of 298 K. 4

2.6. Coreflooding tests

Fig. 1. Schematic representation of the coreflooding system: (1) core holder, (2)
core (Ottawa Sand packing), (3) pore pressure transducer (diaphragm), (4) pump
From the analysis of relative permeability curves and oil recov- one – positive displacement pump, (5) pump two, (6) displacement cylinder, (7)
ery, before and after the treatment, the effect of nanoparticles on filter, (8) pressure multiplier, (9) manometer, (10) valve and (11) test tube.
 E.A. Taborda et al. / Fuel 184 (2016) 222–232 225

kro and recovery curves are constructed following the aforemen- fragmentation tests, (ii) rheology measurements of crude oil in
tioned procedure. absence and presence of nanoparticles/nanofluid and (iii) effect
of nanofluid on heavy-oil mobility under reservoir conditions. Rhe-
3. Modeling ology tests were performed for various nanoparticles/nanofluid
dosages, temperatures and shear rates.
3.1. Solid liquid equilibrium model
4.1. Adsorption isotherms
The SLE model developed is based on the theory of the adsorp-
tion of self-associative molecules onto solid surfaces and expressed Once the nanoparticles come into contact with crude oil, they
as [81,82]: have the ability to adsorb asphaltenes and other heavy compo-

 nents in crude oil such as resins [87]. However, nanoparticles exhi-
wH w bit selectivity for n-C7 asphaltenes adsorption compared to resins,
CE ¼ exp ð1Þ
1 þ Kw N ads;m as demonstrated in our previous publication [87] in which the
competitive adsorption between asphaltenes and resins on
where
pffiffiffiffiffiffiffiffiffiffi   nanoparticles of different chemical natures was demonstrated,

1þ 1þ4Kn N ads;m Nads
w¼ 2K
;n ¼ Nads;m
Nads
, and Nads (mg/g) and Nads,m (mg/g) independently of the concentration of these compounds in the
are the amount of n-C7 asphaltenes adsorbed onto the nanoparticle crude, always showing preferential affinity by asphaltene [87].
surface and the maximum adsorption capacity of the nanoparti- Fig. 2 shows the experimental adsorption isotherms of n-C7
cles, respectively. CE (mg/g) is the equilibrium concentration of n- asphaltenes onto nanoparticles evaluated at 298 K along with the
C7 asphaltenes. The SLE parameters K (g/g) and H (mg/g) are the solid-liquid-equilibrium (SLE) model. Fig. 2 shows that the n-C7
adsorption constants related to the degree of n-C7 asphaltenes asphaltene adsorption isotherms follow a Type I behavior accord-
self-association over the nanoparticles surface and the Henry’s ing to the International Union of Pure and Applied Chemistry
law constant related to the preference of the n-C7 asphaltenes in (IUPAC) classification. Indeed, it can be clearly seen that the
the liquid or adsorbed phases, respectively [82]. The correlation adsorptive capacity of the SiO2A nanoparticles is greater than that
coefficient (R2) and root mean-square error (RMSE %) were used of the other nanoparticles evaluated. The results indicate that the
to estimate the goodness of fit using the Solver feature in Excel adsorption ability to capture n-C7 asphaltenes by nanoparticles fol-
package 2015 [69,83]. lows the order SiO2A > SiO2 > Al2O3, which is supported by the
parameters values obtained from the SLE model, mainly the max-
3.2. Rheological model imum adsorbed uptake (Table 3). It is noted that the adsorptive
capacity of nanoparticles of acidic silica is greater than the rest,
Two rheological models extensively evaluated in the literature, especially at low concentrations (Henry’s Region) wherein the
i.e. Cross and Carreau, also known as Power Law rheological mod- affinity of the nanoparticles is greater than for others. This is con-
els, were used [84–86]. The temperature effect on the flow behav- firmed by the values of the H parameter of the SLE model in
ior index (N or m) was investigated. The flow behavior index increasing order SiO2A < SiO2 < Al2O3, showing the lower affinity
relates to the behavior of the fluid, whether it is more or less New- for the Al2O3 sample in comparison to the other ones. These results
tonian, which for values less than 1 is considered pseudo-plastic are in agreement with Nassar et al. [80], and Montoya et al. [88].
[84]. The asymptotic viscosity parameters (l0,c and l1,c) indicate This could be explained by the increased surface acidity of the
the behavior of the fluid when subjected to conditions correspond- nanoparticles (see Table 1) and is in agreement with those
ing to zero and infinite stresses. The characteristic relaxation time reported by Nassar et al. [89] and Guzmán et al. [79], who found
(ac and kc ) refers to the time required for the fluid to exhibit a that the n-C7 asphaltenes adsorption increased concomitantly with
response to a perturbation generated by agitation, which for a
Newtonian fluid is 0. In Table 2, each model equations with their
600 SiO2A
respective variables are presented.
500 SiO2
4. Results and discussions Al2O3
400
Nads (mg/g)

SLE Model
Results are divided in three sections: (i) selection of nanoparti- 300
cles from n-C7 asphaltene adsorption and aggregation-
200

100
Table 2
Equations and parameters of the Cross and Carreau models. 0
0 500 1000 1500
Model Parameter Equation
CE (mg/L)
l (cP): Viscosity l
l
Cross l ¼ l1;c þ 1þð
0;c 1;c
ac cÞm
(2)
ac (s): Characteristic relaxation time Fig. 2. Adsorption isotherms of n-C7 asphaltenes onto nanoparticles of SiO2, SiO2A
c (s
1): Shear rate and Al2O3 at 298 K.
m: Constant
l1,c (cP): Viscosity at infinite shear
rate
l0,c (cP): Viscosity at zero shear rate Table 3
l0;c
l1;c Parameters estimated from the SLE model for n-C7 asphaltene adsorption on
Carreau l (cP): Viscosity l ¼ l1;c þ (3)
ð1þðkc cÞ2 Þ
N
nanoparticles at 298 K.
kc (s): Characteristic relaxation time
c (s
1): Shear rate Sample H (mg/g) K  10
4 (g/g) Nads,m (mg/g) R2 RSME
N: Constant
l1,c (cP): Viscosity at infinite shear SiO2A 0.44 2.2 1172.1 0.96 6.84
rate SiO2 0.47 3.1 563.2 0.97 5.79
l0,c (cP): Viscosity at zero shear rate Al2O3 3.39 9.0 188.6 0.99 4.99
226 E.A. Taborda et al. / Fuel 184 (2016) 222–232

the surface increased acidity [88]. It was found that the Al2O3 has It can be seen that the SiO2A nanoparticles have greatest impact
affinity for asphaltenes, possibly due to the molecular interactions in reducing dasp. This is according to what is shown in Fig. 2, where
between aluminol group and O-, N. or S-containing functional SiO2A nanoparticles showed the highest adsorption of asphaltenes.
groups of the n-C7 asphaltenes [12]. However, besides of present- Therefore, the SiO2A nanoparticles were selected to conduct an
ing lower surface area than those of SiO2 and SiO2A nanoparticles, evaluation of the HO rheological changes.
the interaction between the hydroxyl links of n-C7 asphaltenes and
the silanol groups of the silica surface are stronger than the affinity 4.3. Rheology measurements
for alumina, and favors adsorption [12]. As the nanoparticle is acid-
ified, the content of silanol groups on its surface is increased, pro- 4.3.1. Effect of temperature and shear rate
moting greater adsorption [73,90]. First, we evaluate the effect of temperature and shear rate on
the fluids viscosity [84,93–95]. A temperature increase should gen-
4.2. n-C7 asphaltene aggregation test erate a decrease in viscosity, a behavior typical of liquids. In the
case of crude oil, it is important to determine the behavior of the
The affinity between nanoparticles and n-C7 asphaltenes of fluid subjected to conditions of temperature, high agitation, either
heavy crude oil was demonstrated by the results of adsorption iso- by the constant injection of fluids into the formation or increased
therms. However, the nanoparticles evaluated also must have the turbulence generated by pumping equipment for transportation
ability to reduce the mean size of asphaltene aggregates (dasp) in at the surface or pumping downhole. Fig. 4 shows the rheological
the fluid with the objective of impacting the configuration and dis- behavior of the crude oil at 298 K along with the rheological mod-
tribution of them in the oil matrix. In heavy crude oils with asphal- els evaluated. In addition, Table 4 summarizes the estimated rheo-
tene content above 5 wt%, the configuration of asphaltenes is logical models parameters found from regression analysis. In Fig. 4,
generally formed by a series of clusters of nanoaggregates, forming it is observed that the viscosity of the crude oil decreases as shear
a viscoelastic network of large size [17,18]. For this reason, it is rate increases. Fluids that exhibit this behavior are called pseudo-
expected for the nanoparticles to have the ability to break the plastic materials or shear-thinning, which is a widely reported
attachment points within the viscoelastic network and greatly behavior for heavy crude oil [61]. A significant number of fluids
reduce the size of the aggregates of asphaltenes, resulting in the such as the evaluated HO, present deviations from Newton’s law
reduction of the crude oil viscosity. Fig. 3 shows the mean aggre- of viscosity as their response is a function of the applied shear rate
gate size of n-C7 asphaltenes in heptol 40 in the presence and as opposed to a Newtonian fluid.
absence of nanoparticles evaluated at 298 K. In Fig. 3, the curve This shear-thinning behavior is commonly known as pseudo-
of n-C7 asphaltenes in absence of nanoparticles, initially reflects a plastic behavior with n and nH < 1 (Table 5) and was explained
growth in dasp as a function of time, followed by a reduction on this by Al-Zahrani [96] as the shear applied in the fluid breaks down
value until stabilization after approximately 300 min. This likely the internal structure. The rheological model that best fits the
occurs due to aggregation-fragmentation forces that exist under experimental data is the Cross model.
certain shear conditions, which in turn have a direct influence on Panels a and b from Fig. 5 show (a) viscosity and (b) shear stress
the mean asphaltene aggregate size (growth/reduction) as functions of shear rate for temperatures of 298, 313 and 323 K
[69,91,92]. The behavior of n-C7 asphaltenes in the presence of a
nanoparticle system is similar, but with a smaller dasp and a faster
1000000
stabilization after 180 min. The evaluated nanoparticles were able
Log Viscosity (cP)

to successfully reduce the dasp in decreasing order of effectiveness,

SiO2A < SiO2 < Al2O3. For example, after 80 min, the reduction in 100000
dasp is 21, 47 and 61% when using Al2O3, SiO2 and SiO2A, respec-
tively. Hence, higher n-C7 asphaltene uptake will result in the Exp
10000
decrease of the number of asphaltenes available in the solution Cross Model
for the aggregation-fragmentation process [69,91,92]. These
Carreau
results are consistent with those presented by Nassar et al. [69], 1000
who evaluated the reduction of the n-C7 asphaltene mean aggre- 0 20 40 60 80 100
gate size and found out that silica nanoparticles were more prone Shear Rate (s-1)
to reduce it as they had greater adsorption capacity.
Fig. 4. Rheological behavior of crude oil at 298 K together with the evaluated
rheological models.
1200

1000 Table 4
Estimated parameters of rheological Cross and Carreau models for crude oil at 298,
800 313 and 323 K.
dasph(nm)

Model Parameters Temperature (K)

600
298 313 323

400 Cross m 1.58 0.93 0.29

l1,c  103 (cP) 65.45 22.34 10.82
l0,c  103 (cP) 874.1 113.6 64.8
200
ac(s) 0.16 0.005 0.003
Virgin Asphaltenes Al2O3 SiO2 SiO2A RSME 2.75 2.14 2.95
0
Carreau N 0.620 0.012 0.001
0 50 100 150 200 250 300 350
l1,c  103 (cP) 69.3 63.2 56.3
Time (min) l0,c  103 (cP) 851 427 353
kc ðsÞ 0.45 0.39 0.22
Fig. 3. Effect of nanoparticles on mean aggregate size of n-C7 asphaltene in heptol RSME 5.15 6.56 7.76
40 solutions at 298 K.
 E.A. Taborda et al. / Fuel 184 (2016) 222–232 227

Table 5
Estimated parameters of Cross and Carreau rheological models for crude oil in presence of SiO2A nanoparticles, carrier fluid and the selected nanofluid at 298 K.

Model Parameters Condition

Crude 10,000 mg/L of 30,000 mg/L of 40,000 mg/L of Carrier Nanofluid with 10,000 mg/L
oil nanoparticles nanoparticles nanoparticles fluid of nanoparticles
Cross m 1.58 1.25 1.56 1.59 1.63 2.29
l1,c  103 (cP) 65.45 27.51 10.31 5.21 9.18 0.60
l0,c  103 (cP) 874 698 640 492 342 159
ac(s) 0.16 0.20 0.41 0.61 0.77 0.78
RSME 2.75 2.41 3.93 3.11 4.06 8.88
Carreau N 0.62 0.46 0.74 0.74 0.66 0.97
l1,c  103 (cP) 69.3 33.0 17.4 7.7 4.8 4.0
l0,c  103 (cP) 851 642 619 489 340 158
kc ðsÞ 0.45 0.31 0.34 0.71 1.84 1.87
RSME 5.15 8.05 8.82 6.46 8.12 7.55

298 K infinity for Cross and Carreau models, respectively, are consistent
a 1000000 313 K with the experimental data and follow a well-defined and expected
trend as the temperature increases, so the fluid can be considered
Log Viscosity (cP)

323 K
100000
Cross Model Newtonian. These results are similar to those reported by Rao et al.
[99] and Lomba et al. [100].

10000
4.3.2. Effect of nanoparticles on oil viscosity
Fig. 6 shows the results of the rheological study for samples
1000 with different dosages of nanoparticles at 298 K. The nanoparticles
0 20 40 60 80 100
selected to evaluate the performance as viscosity reducing agents
Shear Rate (s-1)
were SiO2A, since they were shown to possess the highest adsorp-
tive capacity, the greatest selectivity for n-C7 asphaltenes and gen-
b 5000 298 K erated the largest reduction in the size of the asphaltene
313 K
Shear Stress (Pa)

4000 aggregates present in the liquid medium.

323 K
As shown in Fig. 6, as the concentration of nanoparticles in the
3000
fluid increases, the viscosity is reduced. For the highest concentra-
2000 tion evaluated (4 wt%), viscosity reductions of more than one order
of magnitude for all shear rates evaluated are observed. When an
1000
amount equivalent to 1 wt% of nanoparticles is added to the oil,
0 the decrease in viscosity is minimal with similar values to those
0 20 40 60 80 100 of heavy oil. The behavior described by the curves shows the
Shear Rate (s-1) non-Newtonian rheological behavior, with decreasing viscosity,
while the content of each of the evaluated nanoparticles mixtures
Fig. 5. (a) Viscosity and (b) shear stress as function of shear rate for temperatures of
increases. The classical Einstein’s theory considers that by adding
298, 313 and 323 K for virgin crude oil.
solid particles to a liquid medium, its viscosity should increase in

for the untreated crude oil. Besides the effect of shear rate and time 0 ppm
of application thereof, viscosity is strongly temperature-
a 10000 ppm
1000000
Log Viscosity (cP)

30000 ppm
dependent. The results reveal that for a fixed value of shear rate, 40000 ppm
the crude oil viscosity decreases as temperature increases. The 100000
change in viscosity with increasing temperature exhibits a decay-
ing exponentially trend, and considering that the content of 10000
asphaltenes does not change, and viscosity reduction should only
occur by effects of temperature and not due to a structural change 1000
0 20 40 60 80 100
in asphaltenes. It is worth mentioning that asphaltenes play a
Shear Rate (s-1)
dominant role on the high viscosity of the heavy crude oils
[14,97]. These results are consistent with those presented by
Ghanavati et al. [14], and Gu and Luo [97]. At 313 and 323 K, the b 5000 0 ppm
Shear Stress (Pa)

viscosity decreases as attractive binding energy is reduced, result- 4000 10000 ppm
ing from the reduction in the cohesive forces of the molecular com- 30000 ppm
3000 40000 ppm
ponents of crude oil [98]. At low temperatures some of the crude
oil components behave as solids and the system viscosity would 2000
depend on their breakage or alignment [61]. This is corroborated 1000
by Fig. 5b, where one can observed that as the temperature
0
increases, the yield point required to start the flow decreases [59]. 0 20 40 60 80 100
In Table 4, the fitting parameters of the two evaluated models
Shear Rate (s-1)
are presented. In general, all parameters follow a logical tendency
to decrease in value as temperature increases. Parameters l0,c and Fig. 6. (a) Viscosity and (b) shear stress as function of shear rate for crude oil in
l1,c related to viscosity values measured at shear rate zero and absence and presence of different dosages of SiO2A nanoparticles at 298 K.
228 E.A. Taborda et al. / Fuel 184 (2016) 222–232

direct proportion to the volume fraction of solids added [101]. In discern the individual effect of each component. A concentration
contrast, for this particular case, classical Einstein theory does of 10,000 mg/L of SiO2A nanoparticles and 4% v/v of the prepared
not explain the behavior of heavy oil once it has been contacted carrier fluid were selected. Panels a and b in Fig. 8 show (a) viscos-
with SiO2A nanoparticles due to the interactions between heavy ity and (b) shear stress as function of shear rate for the crude oil in
molecules such as n-C7 asphaltenes and nanoparticles, generating absence and presence of the prepared carrier fluid at 4% v/v, SiO2A
fragmentation of high molecular weight aggregates. Due to this nanoparticles at 10,000 mg/L the selected nanofluid. It is observed
fragmentation, a redistribution of n-C7 aggregates asphaltenes that the treated samples followed the same trend as the untreated
remaining in the liquid medium to be smaller, breaking the bonds sample, but has lower values due to the addition of the nanofluid.
forming the viscoelastic large network and hindering further for- As can be seen in Fig. 8a, there is a high impact in reducing oil vis-
mation. At the time that the asphaltenes aggregates viscoelastic cosity by adding only the carrier fluid medium (nanofluid without
network is created, the oil viscosity is very high, and for this rea- nanoparticles). The maximum viscosity change occurs at low shear
son, the nanoparticle has the ability to inhibit the formation of this rate values. The effect yielded on the sample by the nanofluid can
viscoelastic network, which greatly reduces the oil viscosity. From be seen even at low agitation conditions. It can be noticed that
Fig. 6b, it is also observed that the inclusion of nanoparticles under these conditions, the slope is greater, showing high DVR.
reduced significantly the shear stress and the yield point in com- When evaluating the DVR as a sum of the effect generated by the
parison with the fluid in absence of SiO2A nanoparticles. addition of nanoparticles plus the effect generated by the addition
of the carrier fluid separately, an approximate 94% reduction is
4.3.3. Effect of nanofluid on oil viscosity obtained. However to directly evaluate nanoparticles dispersed in
It is noticed that the addition of solid nanoparticles to heavy fluid, a DVR of 99% is obtained. Nevertheless, it is necessary to ana-
crude oil generates a viscosity reduction, which offers the neces- lyze these reductions in viscosity as changes in orders of magni-
sary conditions for optimizing oil mobility. However, for a possible tude, when added separately nanoparticles and carrier fluid, the
industrial IOR application, nanoparticles have to be suspended in a viscosity reduction is about one order of magnitude, whereas when
carrying fluid in order to supply injectivity requirements. Particles the nanofluid is added with the dispersed nanoparticles, the reduc-
in a liquid medium will have greater dispersion thus can come into tion is about two orders of magnitude, and here lies the importance
contact with as much fluid as compared to the case if solid of using nanofluid with nanoparticles dispersed in it. By using the
nanoparticles are added. The performance of a nanofluid formed nanofluid, a synergistic effect is observed. The synergy between the
by the mixture water-surfactant-nanoparticles was evaluated. Five nanofluid and the nanoparticles is observed through the viscosity
nanofluids with different contents of nanoparticles, i.e. 10, 100, reduction that is greater than the case when either the carrier fluid
1000, 10,000 and 40,000 mg/L, were mixed individually with HO or the nanoparticles are used separately. This could result from a
at percentages of 4 and 96% v/v, respectively. The viscosity of the greater dispersion of particles in a liquid medium that conse-
mixtures was measured at 298 K and a fixed shear rate of 10 s
1, quently will offer a greater available surface to contact oil compo-
along with the degree of viscosity reduction (DVR, Eq. (4)) [59]: nents as compared to the case when solid nanoparticles are added
separately. In effect, the addition of a liquid medium to transport
ðlref
lnanof Þ the nanoparticles is favorable for reducing viscosity, which could
DVR% ¼  100 ð4Þ
lref be due to two main reasons: (1) the liquid medium serves as a par-
tial extender of oil, and (2) the nanoparticles are scattered in the
where lref and lnanof are the reference and the after-nanofluid-
inclusion viscosity values, measured at 10 s
1, respectively.
Fig. 7 shows the viscosity reduction produced by the addition of Crude oil
the prepared nanofluids. Again, it is seen that as the concentration a SiO2A Nanoparticles 10000 ppm
Carrier Fluid 4%v/v
of nanoparticles increases in the nanofluid, the mixture viscosity 1000000
Nanofluid
Log Viscosity (cP)

decreases. The optimum point is at a concentration of 10,000 mg/ Cross Model

L, where a maximum DVR is obtained. However with increasing 100000
concentration of nanoparticles up to 40,000 mg/L, the DVR is much
lower (33%), which is possibly due to aggregation of the solid par- 10000
ticles in the nanofluid, hence reducing interaction with asphaltenes
1000
present in crude oil.
In order to analyze the effect of nanofluid designed to reduce
100
the oil viscosity, rheological tests as a function of shear rate were
0 20 40 60 80 100
conducted with silica nanoparticles and the carrier fluid alone to Shear Rate (s-1)

140000
123014 92% 92% 92% 94% 99% 100% b 5000 Crude Oil
SiO2A Nanoparticles 10000 ppm
Shear Stress (Pa)

120000 Carrier Fluid 4%v/v

80% 4000
Nanofluid
Viscosity (cP)

100000
82500
60% 3000
80000
DVR

60000 40% 2000

40000 33%
20% 1000
20000 0% 10300 10215 10005 6930 1324
0 0% 0
Virgin 0 10 100 1000 10000 40000 0 20 40 60 80 100
Crude Shear Rate (s-1)
Oil Concentration (mg/L)
Fig. 8. (a) Viscosity and (b) shear stress as function of shear rate for crude in
Fig. 7. Viscosity of crude oil in absence and presence of nanofluid with different absence and presence of the prepared carrier fluid at 4% v/v, SiO2 nanoparticles at
concentrations of nanoparticles at 298 K and a shear rate of 10 s
1. 10,000 mg/L the selected nanofluid.
 E.A. Taborda et al. / Fuel 184 (2016) 222–232 229

medium and when mixed with oil they can occupy more space and 1 Kro After Nanofluid 0.02
foster greater contact with the asphaltenes present in crude in Krw After Nanofluid
comparison to the case when they are mixed in solid form [72]. 0.8
Kro Base 0.015
However the viscosity change generated only by the addition of Krw Base
nanofluid compared with the addition of either solid nanoparticles 0.6

Kro

Krw
or only the carrier fluid, is larger than the untreated crude oil or 0.01
adding solid nanoparticles, concluding that the nanoparticle inter- 0.4
action with asphaltene has a greater impact on the viscosity reduc- 0.005
0.2
tion over the dilution phenomenon that can generate the amount
of surfactant added to nanofluid.
0 0
In Table 5, the parameters of all models evaluated for mixtures 0 0.2 0.4 0.6 0.8 1
between HO matrix and nanoparticles/nanofluids are presented. Sw
Similar to the results shown in Table 4, the model that best-fits
the experimental data of mixtures of oil with nanoparticles/ Fig. 9. The relative permeability curves for the base, the core with crude oil-wet
and the treated system after nanofluid injection in their respective formation plug.
nanofluid, is the Cross model. The data follow a sensible trend
The relative permeability curves oil (Kro) and the relative permeability curves
for curves that have a viscosity reduction at all shear rates water (Krw).
evaluated.
Parameters related to viscosity at zero and infinity shear rates,
are consistent with the experimental data following a well- viscosity and the relative permeability, which in turn depends on
defined trend as the content of nanoparticles/nanofluid in the HO the system’s wettability [66,105]. Hence, it could be inferred from
matrix is increased. The constant m, related to the flow index, sug- the results of the static tests, that the nanofluid inclusion reduce
gests that fluids exhibit non-Newtonian behavior, but tending to the oil viscosity and therefore increases mobility of oil in the por-
increase up to 1, and this can occur because the fluid in the pres- ous medium. In addition, wettability changes are apparent as
ence of nanoparticles/nanofluids reaches a more Newtonian residual saturations of water and oil reflect a change in the wetting
behavior at lower rate shear compared to the untreated crude oil. state of the system after injecting the nanofluid. Table 6 shows the
Several authors have modeled the rheological behavior of heavy effective permeabilities at residual fluid saturations obtained in the
crudes based on the content of asphaltene [14,97,102] and the con- core-flooding tests and the state of saturations for each system.
sistency of the sample. Ghanavati et al. [14] define the constant of Comparing the results before and after the injection of nanofluid,
solvation as the ratio of volume of the solvated asphaltene particles it is possible to determine changes from 5.6 to 12.8% in the case
after dispersion to the volume of the dry asphaltene particles of Swr and from 23.1 to 10.4% for Sor from the systems before
before dispersion, and this value is directly proportional to viscos- and after nanofluid inclusion, respectively. In addition, the point
ity, i.e. if the viscosity decreases, also the constant of solvation where the relative permeabilities of water and oil are equal (cross-
decreases. If we consider that the viscosity of the fluid decreases over point), switches to the right from 45 to 86% for the system
in the presence of nanofluid, possibly due to a change in the struc- before and after nanofluid, respectively, which according Craig’s
ture of asphaltene, more specifically the relationship between the rules of thumb [106], indicates a change in the wetting condition
size before and after the addition of nanofluid. The parameter of the system as the crossover point can be found at a Sw value
related to the relaxation time increases as the concentration of higher than 50% [107]. This is due to increasing Swr and reduced
nanoparticles/nanofluids in the medium is increased, therefore, Sor due to the alteration of the wettability of the medium as
the system presents a greater delay in reaching equilibrium when nanoparticles get retained by the rock and act as a coating agent
subjected to a disturbance, which is possibly due to the change in at nanoscale [72,105,106]. While these results are suggestive of
the internal structure of the fluid associated to the presence of wettability changes and should not be taken at face value, addi-
nanoparticles. tional wettability analysis (not shown) turned out consistent with
these observations.
4.4. Coreflooding test Oil recovery curves are obtained by making a record in time of
the volume of oil recovered as the crude oil is displaced with water.
The nanofluid yielding the best results as modifying agent of oil These curves are constructed using the maximum volume of
flow properties is used. According to rheological measurements, mobile crude oil recovered throughout the test, which in this case
SiO2A nanofluid was used in corefloods. Fig. 9 shows the relative is that after the injection of the nanofluid. Fig. 10 shows that for a
permeability curves for each scenario evaluated. For the construc- 81% oil recovery obtained for the base system and after injection of
tion of relative permeability curves in heavy oil a drawback occurs nanofluid, 97% of recovery is obtained, i.e., the system increases its
because the water/oil viscosity ratio is very low, making it difficult oil production capacity by 16%, reflecting the importance and
to observe the contrast of the two curves as the curve relative impact of the proposed technology as optimizer agent mobility
water permeability lies well below the oil. For the construction heavy oil. This is especially important in IOR processes with huff-
of relative permeability curves, the absolute permeability is used n-puff configurations where a soaking time is required.
as a reference permeability to reduce uncertainties. Relative per-
meability curves are constructed according to the analytical mode
developed development by Buckley and Leverett [103], and
Table 6
expanded by Johnson, Bossler and Naumann (JBN technique) Effective permeabilities at residual fluid saturations before and after SiO2A nanofluid
[104]. The JBN technique is frequently used to derive the relative injection.
permeability experiments in transient or unsteady-state condi-
Property Moment
tions. Ko values for the base and the after nanoparticles systems
were 453 and 1017 mD, respectively. Before nanofluid injection After nanofluid injection

It can be observed in Fig. 9 that the kro curve for the treated sys- Ko at Swr (mD) 453 1017
tem is higher than that for the base system, indicating that the Kw at Sor (mD) 248 81
Sor (%) 23.1 10.4
treatment is effective in increasing the relative permeability of
Swr (%) 5.6 12.8
oil. The mobility of crude oil depends on two main factors, the
230 E.A. Taborda et al. / Fuel 184 (2016) 222–232

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