Behavior of Asphaltene Adsorption onto the Metal Oxide Nanoparticle

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Behavior of asphaltene adsorption onto the metal oxide nanoparticles surface and its effect on the heavy oil recovery Yousef Kazemzadeh, Seyed Ehsan Eshraghi, Keyvan Kazemi, saeed sourani, Mehran Mehrabi, and Yaser Ahmadi Ind. Eng. Chem. Res., Just Accepted Manuscript • DOI: 10.1021/ie503797g • Publication Date (Web): 18 Dec 2014 Downloaded from http://pubs.acs.org on December 22, 2014

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Behavior of asphaltene adsorption onto the metal oxide nanoparticles surface and its effect on the heavy oil recovery Yousef Kazemzadeh†, S. Ehsan Eshraghi‡*, Keyvan Kazemi‡, Saeed Sourani§, Mehran Mehrabi††, Yaser Ahmadi ⱡ † Department of Petroleum Engineering, Islamic Azad University of Lamerd, Fars, Iran ‡ Department of Chemical Engineering, Institute of Petroleum Engineering, Tehran University, Tehran, Iran § Department of Petroleum Engineering, School of Chemical and Petroleum Engineering, Shiraz University, Shiraz, Iran †† McDougall School of Petroleum Engineering, the University of Tulsa, Tulsa, Oklahoma, United States ⱡ Department of Petroleum Engineering, Science and Research Branch of Islamic Azad University, Tehran, Iran

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KEYWORDS Metal-Oxide

Nanoparticle,

Asphaltene

Precipitation,

Enhanced-Oil-Recovery

(EOR),

Micromodel, Heavy Oil

ABSTRACT

It is an important concern to prevent asphaltene related damages in hydrocarbon reservoirs. There are many investigations about asphaltene and its effects and how to reduce them during the oil production. In the present work, some experiments have been conducted to investigate the effect of the SiO2, NiO, and Fe3O4 nanoparticles on the oil recovery, and find out how they adsorb asphaltene and prevent its precipitation. Moreover, instead of crude oil, a synthetic solution with a given component concentration is used. Results of this study show that in solutions without nanoparticles, increase in the amount of normal heptane causes more asphaltene aggregation takes place; however, in the presence of nanoparticles, increasing the normal heptane would result in an increase in the asphaltene adsorption on the surface of nanoparticles. Furthermore, It is shown that the amount of oil recovery in the presence of different nanoparticles corresponds to the ordering: SiO2> NiO> Fe3O4.

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INTRODUCTION Components which contain the large amount of N, S, and O atoms are known as asphaltene [1, 2]. They have high molecular weight and complex combination with cyclic structures and paraffin chain which is connected to the NSO atoms [3, 4]. Asphaltene is dissolved in aromatic solvents such as toluene and benzene and are insoluble in n-heptane [5]. The presence of asphaltene in the crude oil might cause several severe production problems in oil reservoirs [6-9]; therefore, knowing the residual phase features, namely its saturation, cluster morphology, and cluster size distribution, which could be understood in the core scale (using image techniques such as X-Ray tomography) are significantly important to make an improved oil recovery scenario [10, 11]. Reduction in the amount of recoverable oil and snag in the wellbore and surface facilities are some of these problems which significantly increase the operational costs [12-16]. Accordingly, a solution to remove or reduce the dissolved asphaltene in the oil or prevent its precipitation is crucial [3]. Heavy organic material precipitation usually yields pore blockage and wettability alteration of the reservoir rock [17-18]. Asphaltene precipitation in the porous media can also lead to a decrease of 20 percent in effective permeability [19-20]. Due to the formation damage, reservoir oil and gas production rates would be decreased. When the reservoir pressure is close enough to the precipitation pressure, asphaltene precipitation in reservoir takes place; this, as a result, creates a failure condition at the wellbore wall [21]. Asphaltene precipitation process and its consequence, failure of the formation, have been shown to be very complex.

Many of presented methods are generally limited to specific scenarios with limited applications [22]. Therefore, employment of the modern technologies, including nanoparticles which have practical features, more efficiency and economic justification are suggested. Nanoparticles which have large surface to volume ratio, high capacity of adsorption and staying

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suspended, and good catalytic potency are considered to be one of the most promising solutions for preventing of asphaltene precipitation. Meanwhile, nanoparticles, metal particles or metal oxide, can remove the precipitated asphaltene from the surface by using their thermal catalytic feature [23]. Recently, researchers have made stable emulsion of water and oil with nanoparticles of metals and their oxides for EOR purposes. Nanoparticles, because of their adsorption capacity and catalytic properties, lead to the removal of the precipitated asphaltene in the porous media and well path [24]. Nassar et al. performed several experiments to investigate the effect of nanoparticles on heavy oil recovery [23]. They concluded that the “positive performance” of the metal oxides is in the order of NiO> Co3O4> Fe3O4. The “positive performance” refers to the oxidation ability, adsorption capacity, and catalytic potency [25]. Micro-sized particles exhibit better catalytic ability, and, however, the nanoparticles have higher adsorption capacity [26]. Asphaltene adsorption onto the nanoparticles surface is spontaneous and exothermic [27]. Some experiments have been done to examine the effect of various parameters such as contact time, Initial asphaltene content, temperature, and water content on the asphaltene adsorption onto the nanoparticles surface [28, 29]. The greater the contact time, the more the asphaltene adsorption onto the nanoparticles takes place. However, experiments have shown that, in a short period of time, large amount of asphaltene is adsorbed onto the nanoparticles; therefore, the amount of asphaltene left to be possibly adsorbed onto the rock pore surface is negligible. Initial asphaltene content is also proportional to the asphaltene adsorption. Oftentimes, asphaltene adsorption rate varies inversely with the amount of existing water, as respects, sometimes presence of water increases the asphaltene adsorption. Temperature has a reverse proportionality to asphaltene adsorption. In other words, asphaltene adsorption process is exothermic. Presence of n-heptane increases the

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asphaltene adsorption rate, as well [27]. Javeri et al. have shown that the magnetic field which is caused by casings vibrates the nanoparticles in the annular space. This vibration warms the media. The generated heat is transferred to the well stream by convection. Increase of the temperature of tubing causes the wax melts and flows [29]. Greff and Babadagli stated that, metal nanoparticles are effective in breaking the bonds between the carbon and sulfur atoms. The result of this phenomenon is asphaltene reduction and enhancement of saturated and aromatic substances, which would ultimately cause a significant decrease in oil viscosity [30]. Hamedi and Babadagli compared pure Nickel nanoparticles with Raney Nickel particles in the micron size range and achieved two important results: the catalytic performance of pure nanoparticles and injectivity of them is better, and the adsorption of these nanoparticles onto the rock surface is lower [31]. Greff et al. examined the effect of Nickel nanoparticles on oil recovery under the influence of electromagnetic waves. When the electromagnetic wave warmed the media, the efficiency increased. In other words, they observed positive performance of the nanoparticles [32]. Ogolo et al. showed that the performance of some nanoparticles might be improved in the presence of ethanol. They also demonstrated that the mechanisms by which nanoparticles improve their performance include rock wettability alteration, interfacial tension (IFT) reduction, oil viscosity reduction, mobility ratio reduction, and permeability changes [33]. Haroun et al. compared smart water injection and nanoparticles performances. They reported that the recovery factor for a reservoir during water flooding was between 46% and 63%; whereas, if a suitable nanoparticle had been selected the recovery factor could have increased to the range of 57% to 85% [34]. Nsar et al. studied the effect of asphaltene molecular weight on asphaltene adsorption rate in the presence of iron oxide nanoparticles. They realized that decrease in the asphaltene molecular weight accelerates the absorption rate. However, increase of asphaltene molecular weight

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improves the integrity of adsorption. They concluded that Iron oxide nanoparticles are an excellent adsorbent or catalyst for heavy oil recovery [35]. Some other researchers proved that in situ (in oil matrix) preparation of Nickel oxide, have had absorption capability as much as 2.8 grams per grams of nanoparticles. While, Commercial Nickel oxide has adsorption capability as much as 15% of this amount [36]. In the present work, the effect of different metal oxide nanoparticles on the recovery of heavy oil is investigated. Moreover, after running extensive number of flooding experiments, the optimal concentration of the iron oxide nanoparticles would be obtained. To understand the asphaltene adsorption behavior (i.e. the response of asphaltene adsorption as a function of the nheptane content of the oil) onto the iron oxide nanoparticles, several experiments have been conducted as explained below. METHODOLOGY AND MATERIALS ASPHALTENE ADSORPTION TESTS For more detailed study, synthetic solutions are used in our experiments. First, asphaltene adsorption onto the nanoparticles of iron oxide (Fe3O4) is studied. The synthetic solution is made of asphaltene which is extracted from a crude oil sample and then completely dissolved in toluene. The oil properties are given in table 1. Various standard methods exist to precipitate asphaltene. In this study, the ASTM D200780 method is used which leaded to acceptable results. In order to follow the ASTM procedure, nheptane should be added to the crude oil with a respect ratio of 40:1, i.e., the volume of n-heptane should be 40 times of the volume of crude oil. Commonly, 100 ml of the crude oil contains about

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1 to 10 grams of asphaltenes. Therefore, to ensure accurate determination of asphaltene content, proper amount of oil should be used. Crude oil volume is measured accurately and then n-heptane is added with the desired ratio. The lidded container of mixture is kept at room temperature for two days and is stirred 5 hours per day. Afterwards, the precipitated asphaltene is separated by using 0.22 micron filter. To obtain pure asphaltene sample, these steps should be repeated until the solution become almost transparent. The filtered asphaltene and the filter paper are dried in a lidded container for several days [12]. To avoid oxidization of asphaltene, it can be dried under nitrogen steam; even though, this step is not included in the ASTM method. In order to make the synthetic solution, provide two 50 ml beakers which contain the 5 wt% solution of the extracted asphaltene and solvent. Then, add 1wt% of pure iron oxide nanoparticles to one of the two beakers. Next, both beakers are located in a mixer with speed of 200 rpm for 24 hours and then the container which has asphaltene and nanoparticles are centrifuged with speed of 5000 rpm for about 100 minutes. Behind, the samples are ready for imaging to find out how much of the asphaltene are adsorbed onto the nanoparticles surface and also are prepared for injection into the glass micromodel to evaluate the oil recovery. Thereupon, a few globs of each beaker are dropped onto two distinct glass slides and are pictured with the microscope at different magnification levels. We used Nikon ECLIPSE E200 microscope in our investigations, which has the photomicrography capability. Tables 2 and S1 present the solution components, which are used in this study, and the nanoparticles properties respectively

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MICROMODEL TESTS In these experiments, a glass micromodel with the simple squared structure is used to simulate oil production in the presence of nanoparticles. Glass micromodel is a transparent porous medium, which helps researchers to study the fluid flow as well as phase displacement mechanisms in the pore scale. Using the micromodels leads researchers to understand the EOR processes in the pore scale and direct observation of fluid flow in the porous media. The visibility of the fluid flow through the medium is the main advantage of these models compared to the core samples which are obtained from core drilling. As regards, use of the glass micromodels can be considered as the cornerstone of the fundamental studies, theoretical development of transport phenomena, and quantitative and qualitative observations in these systems. There are many other advantages of using these micromodels, namely creating different porous patterns, short time testing, repeatable tests, and less demand on reservoir core samples and injection fluids. Figure 1 shows the schematic view of the experimental setup. This apparatus consists of a Quizix injection pump which can inject at very low rates. A camera is set above the micromodel to take images at the specified time intervals. The oil recovery and recovery mechanism are determined from the analysis of the taken pictures. In all of the conducted experiments, the injection rate was set on 800 micro cc per minute, which simulates laminar fluid flow in the porous media appropriately, and the time interval of camera shoot was set on one minute. Physical properties of the glass micromodel are presented in table S2. Before each flooding, the glass micromodel was washed with distilled water, dried, and then saturated with the test brine to achieve the water-wet condition of the glass micromodel. After that, the micromodel was flooded with the solution No.2 (see Table 2) to become fully saturated.

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At this stage, the glass micromodel is oil wet while it contains some connate water. It is worthy of mentioning that having a clean glass is important as contamination would be problematic from wettability concerns and adsorption process points of view [37]. To prevent such problems, in addition to considering the fluid distribution near the glass wall, which might be a clue, the contact angles are measured for each wettability alteration step to insure that the desired wettability is gained. The analysis of the test brine, which is gathered from the same reservoir with the oil sample, is given in table S3. Brine, brine with SiO2 nanoparticles, brine with NiO nanoparticles, and brine with Fe3O4 nanoparticles were flooded to the glass micromodel. To make the comparison between the effectiveness of the nanoparticles feasible, the concentration was set to 2000 ppm as the reference value. To investigate the optimal concentration of iron oxide nanoparticles, two more flooding (brine with Fe3O4 nanoparticles (5000 ppm) and brine with Fe3O4 nanoparticles (10000 ppm)) were conducted. Finally, flooding of brine and brine with SiO2 nanoparticles (2000 ppm) were repeated with the difference that the saturating solution of the glass micromodel was changed to solution No.1. The last two injections were performed to understand the effect of the composition of the synthetic solution on the recovery. The oil recovery was recorded as the percentage of the initial oil in place (IOIP) during different displacement stages. Polyethylene tubing with an ID of 2.0 mm was connected to the outlet of the glass micromodel. The produced oil volume was calculated from the length of oil slugs in the tube and the ID of the tube. The water content in the emulsion was assessed under a microscope, and the oil production volume was corrected accordingly.

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ANALYSIS OF THE EXPERIMENTAL RESULTS Figure 2 shows asphaltene adsorption onto the iron oxide nanoparticles surface in solution No.1 containing 0.5 wt. % of iron oxide nanoparticles. As it is shown, the asphaltene molecules have totally surrounded the nanoparticles. Figure 3 and 4 show the less magnified view of asphaltene aggregation in solutions No.1 in the presence of the iron oxide nanoparticles and without it respectively. Absorbing the asphaltene contents onto the nanoparticles surface prevents them from accumulation on the porous media surface and suspends asphaltene molecules in the oil bulk. Even though the nanoparticles have reduced the asphaltene particles movement towards the porous media surface by absorbing them; however, these nanoparticles cannot prevent such movements completely. It can be concluded that the presence of nanoparticles have prevented asphaltene flocculation. However, absence of nanoparticles has caused that asphaltene particles aggregate together easily and form some large molecules on the glass slide surface. Figure 5 illustrates how the presence of the nanoparticles in solution No.2 has prevented asphaltene flocculation. Furthermore, the presence of n-heptane in the solution caused much more asphaltene adsorption onto the nanoparticles surface, and, therefore, asphaltene and nanoparticles settled down uniformly without any flocculation. On the other hand, figure 6 shows how severe asphaltene flocculation might happen in the presence of n-heptane and lack of nanoparticles. Figure 7 depicts the comparison between the obtained oil recovery using water injection and three metal oxide nanofluids injection scenarios. The concentration of nanoparticles in each nanofluid is 2000 ppm.

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Since both of the injected and produced fluids are almost incompressible, the primary recovery points are located along a unit-slope line. Theoretically, after breakthrough time, oil recovery cannot be increased by water injection. However, there are some fundamental phenomena involved in the interaction of nanofluids with their surrounding environment, which might cause some slightly different results from our expectation. Owing to the presence of the nanoparticles, viscosity of the injection fluid increases, mobility ratio between injection and production fluids decreases, interfacial tension decreases, and the wettability of glass micromodel changes from water-wet towards much more oil-wet. Hence, accounting all the aforementioned phenomena, even after breakthrough time, some increase in the oil recovery percentage would be observed. Setting the obtained oil recovery using water injection as the bottom line, the nanofluids flooding based on SiO2, NiO, and Fe3O4 have improved the oil recovery 22.6%, 14.6 and 8.1 respectively. Consider figures 8 and 9, according to these pictures which are taken during nanofluid flooding, the wettability alteration form oil-wet to water-wet and interfacial tension (IFT) reduction are as effective as the improve oil recovery mechanisms. In these two figures, the existence of nanoparticles in the injection fluid have caused enhancement in the oil phase continuity (IFT reduction) and also swapped the wall adjacent phase (i.e. oil with water). Mechanisms which nanoparticles recover operational performance are rock wettability alteration, IFT reduction, oil viscosity reduction, mobility ratio reduction, and permeability alterations. For EOR drives, the nanoparticles are mainly metal or metal oxide particles. Such nanoparticles are considered with i) large surface to volume ratio, ii) high degree of suspension, and iii) huge absorption capacity and being catalytically highly active. The particles could make asphaltene suspended in the oil, inhibit them from being precipitated, and also remove asphaltene precipitation from the porous media surface using its thermal catalytic role. Thus,

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nanoparticles functionality could be shared into two simultaneous actions of i) their high absorptivity subsequent from their ultra-small size, which could rapidly absorb the suspended asphaltene particles, and ii) their improved thermal possessions, which ease the mitigation of asphaltene precipitation. The first fact advances oil mobility and prevents asphaltene aggregation and precipitation. Parameters swaying on asphaltene adsorption include contact time, asphaltene initial saturation, asphaltene particle size, water content, temperature, and other existing molecules; furthermore, the second fact is a process, which results in in-situ heavy oil upgrading by the asphaltenes removal through catalytic oxidation. To investigate the effect of iron oxide nanoparticles on the oil recovery, its nanofluid is flooded with another two different concentrations, 5000 ppm and 10000 ppm. Results of this investigation are shown in figure 10. The more the nanoparticle concentration, the more the oil recovery. However, changing the concentration of the nanoparticle from 5000 ppm to 10000 ppm had negligible improvement on the oil recovery. Therefore, 5000 ppm could be considered as the optimal concentration for iron oxide nanoparticle. In Figure 11, the comparison between four different flooding conditions is illustrated. The four conditions include injection of water and nanofluid (2000 ppm of SiO2 nanoparticles) into the saturated glass micromodel, which was saturated once with solution No.1 and once with solution No.2. For the glass micromodel saturated with solution No.1, the oil recovery for water and nanofluid flooding turned out to be 28% and 38.1%, respectively. While, 29.6% and 19.9% recoveries were measured the glass micromodel saturated with solution No.2. Asphaltene particles cover the two fluids surfaces more rapidly by increasing the n-paraffin content of the oil phase, and, more precisely, n-paraffin acts as the asphaltene particles instability factor. Therefore, increasing normal paraffin means transferring much more asphaltene to the fluid surface. The

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addition of nanoparticles caused asphaltene particles to be absorbed by their surface; it, as a result, retards the aggregation of its large molecules. It implies that nanoparticles reduced the asphaltene precipitation but not completely. Overall, the obtained results highlight the capability of the nanoparticles in heavy oil recovery especially in the presence of n-heptane. CONCLUSION According to the experimental measurements accompanied with floods and images which are taken during the experiments, the followings could be concluded: 

The presence of iron oxide nanoparticles in the solution results in the adsorption of the asphaltene particles onto the nanoparticles surface. This phenomenon significantly reduces the asphaltene flocculation in the porous media and its subsequent damages.



In solutions with high n-heptane content, asphaltene precipitation is much more severe compared to the same solution with lower n-heptane content. In presence of the nanoparticles, this phenomenon is reverse. That is, in the presence of nanoparticles the high n-heptane content improves the asphaltene adsorption onto the nanoparticles which implies less asphaltene flocculation and precipitation.



Considering the nanoparticles in the injected water would insure the oil recovery increase. In addition, simultaneous participation of nanoparticle and n-heptane in the injection fluid (synthetic solution) leads to gain remarkably better recovery, which is in contrast with the mere participation of n-heptane without any nanoparticle.



It is visually understood that the main mechanisms, which make nanoparticles promising candidates for EOR purposes, are IFT reduction and porous media wettability alteration.

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The most effective metal oxide nanoparticle in displacing the oil and improving its recovery turned out to be the SiO2 with 2000 ppm concentration. NiO and Fe3O4 nanoparticles took the subsequent places.



Although increasing the concentration of the nanoparticles improves the ultimate oil recovery, the optimum concentration is always desirable. The optimum concentration for Fe3O4 is experimentally determined to be 5000 ppm.

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FIGURES

Figure 1. Schematic view of glass micromodel setup

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Nanoparticles Asphaltene

Figure 2. Asphaltene adsorption onto the iron oxide nanoparticles

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Figure 3. Asphaltene flocculation in solution No.1 in the presence of nanoparticles (400× magnified)

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Figure 4. Asphaltene flocculation in solution No.1 without nanoparticle (400× magnified)

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Figure 5. Asphaltene flocculation in solution No.2 in the presence of nanoparticle (400× magnified)

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Figure 6. Asphaltene flocculation in solution No.2 without nanoparticle (400× magnified)

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60 50

Recovery factor (%)

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40 30 20 10 0 0

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Pore Volume Injected SiO2 NanoParticles Fe3O4 NanoParticles

NiO NanoParticles Water flooding

Figure 7. Comparison of recovery factors due to flooding of water and three different metal oxide nanofluids

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Figure 8. A pore scale view of the micromodel while water flooding

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Figure 9. A pore scale view of the micromodel during nanofluid flooding

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Recovery factor (%)

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50 45 40 35 30 25 20 15 10 5 0 0

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Pore Volume 0%

2000 ppm

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Figure 10. Oil recovery factor versus injected pore volume in presence of different concentrations of iron oxide nanoparticle

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60 50

Recovery factor (%)

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40 30 20 10 0 0

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Pore Volume 40% Heptane-60% Toluen 40% Heptane-60% Toluen+SiO2 NanoParticles

100% Toluen 100% Toluen+SiO2 NanoParticles

Figure 11. Oil recovery factor versus injected pore volume of brine and 2000 ppm SiO2 nanofluid into the glass micromodel saturated once with the synthetic solution No.1 and once with solution No.2.

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TABLES Table 1. Properties of crude oil Property

Value

Method

°API

21.49

ASTM D 40452

Asphaltenes %wt

11

IP 143

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Table2. Components of the two different solutions in the experiments Solution

Asphaltene

n-heptane %

Toluene %

No. 1

5 wt %

0 Vol %

100 Vol %

No. 2

5 wt %

40 Vol %

60 Vol %

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AUTHOR INFORMATION Corresponding Author * Corresponding author: Seyed Ehsan Eshraghi Postal address: Institute of Petroleum Engineering-College of Engineering of Tehran UniversityNorth Kargar St.-Tehran- Iran- P.O Box: 113654563 Email address: [email protected] Phone number: +989378438094 Fax number: +982188632976 Notes The authors declare no competing financial interest. SUPPORTING INFORMATION AVAILABLE Some information, including nanoparticle properties, physical properties of the glass micromodel, and reservoir brine analysis, which is gathered from the same reservoir with the oil sample, are available in the supporting information, which could be useful for detailed study. This information is available free of charge via the Internet at http://pubs.acs.org/.

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[11] Iglauer, S., Ferno, M., Shearing, P., Blunt, M. J., Comparison of residual oil cluster distribution, morphology and saturation in oil-wet and water-wet sandstone, J. Colloid Interface Sci. 2012, 375, 175-182. [12] Mohammadi, A. H.; Eslamimanesh, A.; Richon, D. Monodisperse thermodynamic model based on chemical Flory−Hu Ggins polymer solution theories for predicting asphaltene precipitation. Ind. Eng. Chem. Res. 2012, 51, 4041−4055. [13] DeBoer, R. B.; Leerlooyer, K.; Eigner, M. R. P.; van Bergen, A. R. D. Screening of Crude Oils for Asphalt Precipitation: Theory, Practice, and the Selection of Inhibitors. SPE Prod. Facil. 1995, 10, 55–61. [14] Firoozabadi, A. Thermodynamics of hydrocarbon reservoirs; McGraw-Hill: New York, 1999. [15] Hemmati-Sarapardeh, A.; Alipour-Yeganeh-Marand, R.; Naseri, A.; Safiabadi, A.; Gharagheizi, F.; Ilani-Kashkouli, P.; Mohammadi, A.H. Asphaltene precipitation due to natural depletion of reservoir: Determination using a SARA fraction based intelligent model. Fluid Phase Equilib. 2013, 354, 177−184. [16] Andersen, S. I.; Speight, J. G. Thermodynamic models for asphaltene solubility and precipitation. J. Pet. Sci. Eng. 1999, 22, 53−66. [17] Vuong, L.T. “A Simple and Accurate Experimental Technique for Measurement of the Onset of Asphaltene Deposition from Petroleum Reservoir Fluids”. MSc Thesis, Chemical Eng. Department, University of Illinois, 1985. [18] Waxman, M.H., Deeds, C.T., Closmann, P.J., “Thermal Alterations of Asphaltenes in Peace River Tars”. Paper SPE 9510 presented at the 1980 SPE Annual Fall Technical Conference and Exhibition, Dallas, Sept. 1980, 21-24.

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[19] Swanson, J. A Contribution to the Physical Chemistry of the Asphalts. J. Phys. Chem, 1942, 46, 141 – 150. [20] Minssieux, L. “Core Damage from Crude Asphaltene Deposition. Presented at the International Symposium on Oilfield Chemistry”. Houston, 18-21 February 1997, SPE-37250-MS. [21] Galoppini, G.; Tambini M. “Asphaltene Deposition Monitoring and Removal Treatments: An Experience Deep Wells”. Aberdeen, 15-17 March 1994, SPE 27622-MS. [22] Darabi, H.; Sepehrnoori, K.; Kalaei, M.H. “Modeling of Wettability Alteration Due to Asphaltene Deposition in Oil Reservoirs”. Texas, 8-10 October 2012, SPE 159554-MS. [23] Nassar, N. N.; Hassan, A.; Pereira-Almao, P. Application of Nanotechnology for Heavy Oil Upgrading: Catalytic Steam Gasification/Cracking of Asphaltenes. Energy Fuels, 2011; 25, 156670. [24] Husein M. Nanoparticles in Heavy Oil. Department of Chemical & Petroleum Engineering, Alberta Ingenuity Center for In-Situ Energy (AICISE), ACAMP Energy Seminar. 2010. [25] Nassar, N. N.; Hassan, A.; Pereira-Almao, P. Comparative oxidation of adsorbed asphaltenes onto transition metal oxide nanoparticles. Colloids Surf., A. 2011, 384, 145-149. [26] Nassar, N. N.; Hassan, A.; Pereira-Almao, P. Effect of the Particle Size on Asphaltene Adsorption and Catalytic Oxidation onto Alumina Particles. Energy Fuels. 2011, 25, 3961–3965. [27] Nassar, N. N. Asphaltene Adsorption onto Alumina Nanoparticles: Kinetics and Thermodynamic Studies. Energy Fuels. 2010, 24, 4116-4122. [28] Nassar, N. N.; Hassan, A.; Pereira-Almao, P. Thermogravimetric studies on catalytic effect of metal oxide nanoparticles on asphaltene pyrolysis under inert conditions, J. Therm. Anal. Calorim. 2012, 110, 1327-133.

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[29] Haindade, Z.; Bihani, A.B.; Javeri, S.; Jere, C. “Enhancing Flow Assurance Using Co-Ni Nanoparticles for Dewaxing Of Production Tubing”. Noordwijk, 12-14 June 2012, SPE 157119MS. [30] Greff, J.H.; Babadagli, T. Catalytic Effects of Nano-Size Metal Ions in Breaking Asphaltene Molecules during Thermal Recovery of Heavy-Oil. SPE 146604-MS, 2011. [31] HamediShokrlu, Y.; Babadagli, T. In-Situ Upgrading of Heavy Oil/Bitumen during Steam Injection by Use of Metal Nanoparticles: A Study on In-Situ Catalysis and Catalyst Transportation. SPE 146661-PA, 2013. [32] Greff, J.H.; Babadagli, T. Use of Nano-Metal Particles as Catalyst under Electromagnetic Heating for Viscosity Reduction of Heavy Oil. SPE 14720-MS, 2011. [33] Ogolo, N.A.; Olafuyi, O.A.; Onyekonwu, M.O. Enhanced Oil Recovery Using Nanoparticles. SPE 160847-MS, 2012. [34] Haroun, M.; AlHassan, S.; Ansari, A.; Al Kindy, N.; AbouSayed, N.; Ali, B.; Sarma, H. Smart Nano-EOR Process for Abu Dhabi Carbonate Reservoirs. SPE 162386-MS, 2012. [35] Nassar, N.N.; Hassan, A.; Carbognani, L.; Lopez-Linares, F.; Pereira-Almao. P. Iron Oxide Nanoparticles for Rapid Adsorption and Enhanced Catalytic Oxidation of Thermally Cracked Asphaltenes. Energy Fuel, 2012, 95, 257-262. [36] Abu Tarboush, J.B.; Husein, M. M. Adsorption of Asphaltenes from Heavy Oil onto in situ Prepared NiO Nanoparticles. J. Colloid Interface Sci., 2012, 378, 64-69. [37] Iglauer, S.; Salamah, A.; Sarmadivaleh, M.; Liu, K.; Phan, Chi. Contamination of silica surfaces: Impact on water–CO2–quartz and glass contact angle measurements. Int. J. Greenhouse Gas Control. 2014, 22, 325–328.

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197x91mm (300 x 300 DPI)

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