Journal of Petroleum Science and Engineering 111 (2013) 128 138

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Journal of Petroleum Science and Engineering

journal homepage: www.elsevier.com/locate/petrol

A coreood investigation of nanouid enhanced oil recovery

Luky Hendraningrat n, Shidong Li, Ole Torster
Department of Petroleum Engineering and Applied Geophysics, Norwegian University of Science and Technology, NTNU, NO-7491, Trondheim, Norway

art ic l e i nf o
Article history: Received 31 January 2013 Accepted 10 July 2013 Available online 1 August 2013 Keywords: Enhanced oil recovery Silica nanoparticle Nanouids Structural disjoining pressure Berea sandstone

a b s t r a c t
Recently nanoparticles have become an attractive agent for improved and enhanced oil recovery (IOR & EOR) at laboratory scale. Most researchers have observed promising results and increased ultimate oil recovery by injecting nanoparticle suspension (nanouid) in laboratory experiments. The objective of this study is to reveal nanouid possibility for EOR in low to high-permeability sandstone (ss) rocks and investigate suitable concentration. In this study, parameters involved in the structural disjoining pressure mechanism, such as lowering interfacial tensions (IFT) and altering wettability, were studied. Laboratory coreood experiments were performed in water-wet Berea ss core plugs with permeability in range 9400 mD using different concentrations of nanouids. A crude oil from a eld in the North Sea was employed and three nanouid concentrations 0.01, 0.05 and 0.1 wt% were synthesized with synthetic brine. We observed that IFT decreased when hydrophilic nanoparticles were introduced to brine. The IFT decreases as nanouid concentration increases and this indicates a potential for EOR. Increasing hydrophilic nanoparticles will also decrease contact angle of aqueous phase and increase water wetness. We have also observed that the higher the concentrations of nanouids, the more the impairment of porosity and permeability in Berea core plugs. Despite that increasing nanouid concentration shows decreasing IFT and altering wettability, our results indicate that additional recovery is not guaranteed. The processes and results are outlined and also further detailed in the paper to reveal the possible application of nanouid EOR as a future or an alternative EOR method. & 2013 Elsevier B.V. All rights reserved.

1. Introduction Most of the oil elds around the world have reached or will reach soon the phase where the production rate is nearing the decline period. Hence, the current main challenge is how to delay the abandonment by extracting more oil economically. The latest worldwide industries innovation trends are miniaturization and nanotechnology materials. Nanotechnology is dened as the construction of functional materials, devices, and systems by controlling matter at the nanoscale level (one-billionth meter), and the exploitation of their novel properties and phenomena that emerge at that scale (Das et al., 2008). A nanoparticle, as a part of nanotechnology, has size typically less than 100 nm. It is composed of two entities: the core and a thin shell (Das et al., 2008). The core and shell may have underlying structures and may be composed of more than one entity. The molecular shell has three separate regions: tail group, hydrocarbon chain and active head group, although one or more of these may be absent in a specic case (see Fig. 1). A hydrocarbon chain may be long, as in a polymer, or completely absent, as in an ion,

protecting the nanoparticle (Das et al., 2008). The shell may also be an extended solid, such as silicon dioxide (SiO2), that we used in this study. The chemical nature of a shell will determine the solubility of nanoparticles such as lipophobic and hydrophilic nanoparticles (LHP) dissolved in polar solvent such as water, and hydrophobic and lipophilic nanoparticle (HLP) dissolved in nonpolar solvents such as toluene. Nanouid is dened as nanoparticle that has an average size less than 100 nm, suspended in traditional heat transfer uid such as water, oil or ethylene glycol (Das et al., 2008). Nanouid technology, as a part of nanotechnology, is a new interdisciplinary area of great importance where nanoscience, nanotechnology, and thermal engineering come across. It has developed largely over the past decade and revealed its potential applications in oil and gas industries. Through continuously increasing publications addressed on the topic, it has motivated us to investigate the possibility of nanouids as a future or an alternative improved/enhanced oil recovery method. 2. Displacement mechanism Oil recovery possible mechanism using nanoparticles suspension has been experimentally investigated by Wasan and Nikolov (2003), Chengara et al. (2004), and Wasan et al. (2011) and called structural disjoining pressure mechanism. Later, Mc.Elfresh et al.

Corresponding author. Tel.: +47 735 94 94; fax: +47 739 44 472. E-mail addresses: luky.hendraningrat@ntnu.no, lucker83@gmail.com (L. Hendraningrat). 0920-4105/$ - see front matter & 2013 Elsevier B.V. All rights reserved. http://dx.doi.org/10.1016/j.petrol.2013.07.003

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Fig. 1. Illustration (not to scale) of nanoparticle schematic (from Das et al., 2008) and structural disjoining pressure gradient mechanism among solid, oil and nanouids as aqueous phase due to nanoparticles structuring in the wedge-lm (from Wasan et al., 2011).

Fig. 2. Residual oil inside pore network of glass micromodel under microscope 5 : (a) situation after imbibition process with brine and (b) situation after injecting nanouids 0.1 wt% as tertiary recovery process. Residual oil was decreasing after injecting nanouids at 0.2 cm3/min.

(2012) described the energies that drive this mechanism as Brownian motion and electrostatic repulsion between the nanoparticles. The electrostatic repulsion force between those particles will be bigger when nanoparticle size is smaller. When the amount of the nanoparticles is increasing, the force will increase. The presence of these nanoparticles in three-phase contact region has a tendency to create a wedge-lm structure. Structural disjoining pressure is correlated to the uids ability to spread along the surface of a substrate due to imbalance of the interfacial forces among solid, oil phase and aqueous phase (Chengara et al., 2004). The interfacial forces will cause aqueous phase (nanouid) contact angle () to decrease to 11 and the result is a wedge lm. This wedge lm will act to separate formation uid such as oil, parafn, water and gas from the formation surface (Mc.Elfresh et al., 2012). Driven by the aqueous pressure of the bulk liquid, the nanouid is able to spread along the surface as monolayer particles. Completely spreading occurs when the contact angle is zero. Wasan and Nikolov (2003) observed that the driving force for the spreading of the nanouids is the structural disjoining pressure (lm tension) gradient () directed towards the wedge from the bulk solution. The lm tension is high near the vertex because of the nanoparticle structuring in the wedge connement. It drives the nanouids to spread at the wedge tip as the lm tension increases towards the vertex of the wedge. They also investigated that spreading coefcient increases exponentially with a decrease in the lm thickness or decrease in the number of particle layers

inside the lm. As the lm thickness decreases towards the wedge vertex, the structural disjoining pressure increases. In our preliminary two-phase ow EOR study using transparent glass micromodel (porosity 44% and permeability 25 D) showed that nanouids 0.1 wt% could reduce residual oil saturation as shown in Fig. 2. However, this porous medium has very high porosity and permeability and does not represent common oil reservoir rocks. Previous coreood experiment using water-wet Berea ss with average porosity 23% and permeability 375 mD and synthetic oil with viscosity 2 mPas showed that nanouids with very low concentration 0.01 wt% could enhance oil recovery almost 2% points (Hendraningrat et al., 2012). Hence, the goal in this study is to broadly reveal the possibility of using nanouids as an EOR method in low to high-permeability rocks and investigate its suitable nanouid concentration.

3. Materials 3.1. Nanoparticle A LHP with single particle size 7 nm, dominantly most distributed in range 2140 nm and consists more than 99.8% of silicon dioxide (SiO2), has been used in this study. Other minor elements are aluminum oxide (Al2O3) r 0.05%, titanium dioxide (TiO2) r 0.03%, hydrogen chloride (HCl) r 0.025% and ferric oxide (Fe2O3) r 0.003%. It has acidity with the pH range from 3 to 5.

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Fig. 3. Nanoparticles characterization under SEM (magnication 4 50k times) with nanoparticles distribution analysis using nanosight (based on dynamic light scattering method).

Table 1 Fluid properties. Fluid Density (g/cm3) 1.022 1.012 1.015 1.017 0.826 Viscosity (mPa. s) 1.001 1.006 1.010 1.015 5.10 pH Temperature (1C) 21.4 21.7 21.2 20.0 22.0

Table 2 Dimensions and average petrophysical properties at initial condition. Berea ss no. Length (mm) Diameter Pore volume (mm) (cm3) 37.98 37.96 37.94 37.92 37.84 37.95 37.93 37.92 37.91 37.90 7.03 6.42 7.13 6.70 6.88 6.49 12.67 12.41 12.52 12.42 Porosity Avg. liq. permeability (%) (mD) 15.02 13.93 15.37 14.55 14.90 14.10 23.20 20.01 23.04 22.93 13 9 35 20 18 10 392 156 302 354

Brine, NaCl 3 wt% Nanouid 0.01 wt% Nanouid 0.05 wt% Nanouid 0.1 wt% Crude oil

6.76 6.26 6.16 5.25

The specic surface area of LHP is 300 m2/g. The LHP has been characterized under Zeiss Supra 55 VP low vacuum Scanning Electron Microscope (SEM) with a scale of 200 nm and nanoparticle distribution dispersed in brine through Nanosight measurement as shown in Fig. 3. 3.2. Fluids In this study, a degassed crude oil from a eld in North Sea has been employed. It has density and viscosity of 0.826 g/cm3 and 5.10 mPas, respectively. Synthetic reservoir brine was made as a base uid solution between sodium chloride (NaCl) 3.0 wt% and deionized water. The density of brine was 1.02 g/cm3, viscosity 1.0 mPas and pH 6.76 at 21.4 1C. The density and viscosity were measured using pycnometer and Brookeld viscometer, respectively. This brine was also used as dispersed uid for these nanoparticles. The reason is that brine is present in oil reservoirs and easily available in offshore elds. The most important LHP nanoparticles can easily be dispersed in water-based uid such as brine. Nanouids with various weight concentrations 0.01, 0.05 and 0.1 wt% were synthesized using high speed magnetic stirring for 34 min and continued with sonicator at 40100% amplitude for 35 min. Table 1 shows uid properties measurement of brine and various nanouid concentrations at ambient condition. 3.3. Porous medium Several water-wet Berea ss core plugs with the range of permeability from 9 to 400 mD were used in this study. First, core plugs were cleaned using toluene through soxhlet extraction apparatus at 6570 1C for 6 h. Cleaning with methanol through soxhlet extraction at similar condition and duration followed. The

L1 L2 L3 L4 L5 L6 H1 H2 H3 H4

40.83 40.73 41.05 40.75 41.04 40.08 48.34 48.09 48.12 48.02

L, low-permeability; H, high-permeability.

core plugs were heated in the oven at 70 1C for 6 h. The dry weight, length, diameter and porosity were measured. Helium porosimeter and liquid Hassler permeameter were used to measure porosity and permeability, respectively. The measured dimension and average petrophysical properties at initial condition are listed in Table 2. Pore size of core plugs has been observed under SEM. Crocker et al. (1983) have investigated that average pore size for Berea ss (porosity 19.2% and permeability 302 mD) is 18 mm. Based on our observation as shown in Fig. 4b, the pore size of lowmedium permeability seems to be at a glance less than 10 mm. Meanwhile, higher permeability pore size shows higher pore size around 2530 mm from Fig. 4d.

4. Method 4.1. Coreood setup The experiment aims to reveal nanouids possibility for EOR in low to high permeability of sandstone reservoir rocks and investigate suitable nanouid concentration. Hence various nanouids were injected as tertiary recovery mode after brine ooding at room temperature. The injection rate was kept constant at 0.2 cm3/min. Figs. 5 and 6 show experimental instruments and schematic of coreood setup, respectively. The pump injected

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Fig. 4. (a) Lowmedium permeability Berea ss with its pore size morphology under SEM (b); and (c) higher permeability Berea ss with its pore size morphology under SEM (d).

line before injecting another uid. The inuent owlines from vessels are connected to Hassler core holder. The sleeve pressure was set to 20 bar in the Hassler core holder. Oil owline at vessels outlet is separated from others vessels outlet to minimize early mixing of those uids. The differential pressure was recorded by precision pressure gauge (range 03 bar) that is connected to the PC monitor. The accumulator tubes were prepared to measure the efuent from core during ooding process. 4.2. Coreood procedure The core plug dimensions and dry weight were obtained. Then the core plugs were fully saturated with brine using a vacuum container for approx. 12 h at a pressure of 0.1 bar. The coreood instrument was setup as shown in Fig. 6. The sleeve pressure was set at 20 bar into core cell. There were single-phase and two-phase ow coreood experiments. Single-phase ow (brine/nanouid) was performed for porosity and permeability impairment with injection rate from 0.1 to 0.5 cm3/min. Meanwhile for two-phase ow, the drainage process was started by injecting degassed crude oil with rate from 0.2 to 1.0 cm3/min until surely no more brine produced. To reach this situation it required about 310 PV injection. The initial water saturation was established. As a rst imbibition process, brine was injected at constant rate 0.2 cm3/min approx. 35 PV until surely no more oil produced and thereby residual oil saturation was established. Then the injection was continued at constant rate

Fig. 5. Experimental instruments.

exxol D-60 as pump uid from bottle through 1/8 in. pipe to push the piston plate located inside the vessel. The piston plate is also useful to separate between different uids in the similar cylinder without mixing. There are three different vessels installed with piston plate in each vessel. Those vessels were lled up each with brine, crude oil and nanouid. Valves were installed at inlet and outlet of the vessel to regulate uid ow. There is a bypass owline to clean the

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Fig. 6. Schematic of experimental setup: (1) pump uid (exxol D-60), (2) injection line, (3) micro-pump, (4) valve, (5) pump uid in vessel-A, (6) piston plate, (7) brine in vessel-A, (8) oil in vessel-B, (9) nanouid in vessel-C, (10) oil line, (11) brine/nanouid line, (12) bypass valve, (13) hassler core cell, (14) core plug inside cell, (15) pressure gauge, (16) sleeve pressure, (17) connection cable, (18) computer, (19) accumulator. Table 3 Saturation process and EOR scenarios. Berea ss no. PV injected at drainage process Initial water saturation (%) 18.94 15.89 20.06 20.90 31.67 26.03 15.56 24.25 23.29 24.34 Initial oil saturation (%) 81.06 84.11 79.94 79.10 68.33 73.97 84.44 75.75 76.71 75.66 PV injected at imbibition process with brine Oil saturation after brine Injection (%) 35.98 53.74 34.36 34.70 25.81 37.75 41.04 29.01 27.57 37.43 Nanouids concentration for EOR scenario (wt%) 0.01 0.01 0.05 0.05 0.1 0.1 0.01 0.05 0.05 0.1

L1 L2 L3 L4 L5 L6 H1 H2 H3 H4

6.1 4.7 7.0 7.5 7.3 10.8 3.9 4.0 4.0 3.2

3.4 3.2 3.0 2.7 3.3 5.2 3.7 3.0 3.2 3.1

L, low-permeability; H, high-permeability.

spinning drop video tensiometer around 1 h at ambient condition (Fig. 7). The drop volume was in range 23 mL. The rotation speed was kept around 50006000 rpm. The formula to measure IFT is as follows (Than et al., 1988): s :2 :Dapp 3 8n3 J D L=D 1

Fig. 7. Crude oil drop shape from SVT20 spinning drop video tensiometer. Example drop for system crude oil-nanouid 0.05 wt% and crude oil.

where s is the interfacial tension (dyn/cm), is the density difference (g/cm3), is the rotational rate of the cylinder (s 1), Dapp is the measured drop diameter (cm), n is the refractive index of the heavy uid, D is the true diameter of the drop (D Dapp =n), JD is the correction factor and function of L/D, and L/D is the aspect ratio (e.g. the ratio of the drop length to its diameter). As an input data, refractive index was measured using refractometer Mettler Toledo for all aqueous phases and summarized in Table 4. The refractive index slightly increases as nanouid concentration increases. 4.4. Contact angle measurement

0.2 cm3/min approx. 34 PV of nanouid as tertiary recovery mode. There are three different nanouid concentrations 0.01; 0.05 and 0.1 wt%. The oil recovery performance and decreased residual oil saturation were evaluated. Table 3 shows how many PV were injected during drainage, imbibition process using brine ooding and nanouids EOR scenario. 4.3. Interfacial tension measurement The interfacial tension (IFT) between degassed crude oil and brine/nanouids as aqueous phase was measured by using SVT20

Contact angle, , is a quantitative measurement of the wetting characteristic of a solid by a liquid and dened geometrically as the angle formed by a liquid at the three-phase boundary where a liquid, gas (lighter) and solid intersect. Low value of indicates that the liquid spreads or wets. Otherwise high value indicates poor wetting. Treiber et al. (1971) dened contact angle in 3-phase system (water, oil and rock surface) as follows: water-wet in the range from 01 to 751, intermediate/neutral-wet in the range 7511051 and oil-wet in the range 10511801. A zero contact angle represents that the denser uid is completely wetting the solid.

L. Hendraningrat et al. / Journal of Petroleum Science and Engineering 111 (2013) 128 138 Table 4 Refractive Index for aqueous phase. Fluid Average (n) 1.33100 1.33624 1.33612 1.33646 1.33662 Temperature (1C) 20.1 19.9 20.2 20.8 20.5

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permeability of pre- and post-nanouid injection: q k P A ml L 3

Deionized water Brine, NaCl 3 wt% Nanouid 0.01 wt% Nanouid 0.05 wt% Nanouid 0.1 wt%

where k is the permeability of medium (m2), q is the owrate (m3/s), L is the length of pore medium from the inlet to the outlet (m), m is the viscosity of phase l(Pa s), P is the differential pressure between high pressure and low pressure (Pa) and A is the cross-sectional area to ow (m2). We dene average percentage liquid permeability impairment in this study as follows: kimp kpost kpre 100 kpre 4

5. Results and discussion 5.1. Effect of LHP silica nanouids on IFT and contact angle In this study, parameters involved in the disjoining pressure mechanism, such as lowering IFT and altering wettability, are studied. An assessment of the relationship between interfacial tension, wettability and oil recovery in lowmedium permeability water-wet Berea ss due to the presence of LHP silica nanoparticles is performed. Introducing silica LHP nanoparticles into the brineoil system was observed to give lower IFT and the decrease might be large enough to produce more oil. Buckley and Fan (2005) reported IFT impacts on capillary pressure, capillary number, adhesion tension, and the dimensionless time for imbibition. The capillary number increased with decrease of IFT and consequently some residual oil is mobilized. Fig. 9 shows IFT measurement of crude oil against brine/ nanouids at various concentrations. IFT of brinecrude oil system is 19.2 mN/m and is considered as a reference value. A LHP silica nanoparticle has the ability to decrease IFT at the oilbrine interface and the value was about half of the reference value at a concentration of 0.01 wt%. The interfacial tension is sensitive to nanouid concentration. As we can see, IFT decreases as nanouid concentration increases. We are unsure with the result when measuring at higher nanouid concentrations than 0.05 wt%. However, pH of LHP silica nanouids will decrease with increased concentrations of nanoparticles (see Table 1). The pH signicantly decreased from around 6 to 5 when nanouid concentration increased from 0.05 to 0.1 wt%. The effect of aqueous phases pH in IFT oilwater system has been investigated by Buckley and Fan

Fig. 8. Contact angle formation on polished synthetic silica between crude oil and brine/nanouids according to the Young formula.

In this experiment, contact angle was measured directly on polished synthetic silica using Goniometry KSV CAM instrument at room condition. The system consists of crude oil, brine/nanouids and polished synthetic silica (see Fig. 8). The measurement is based on the Young formula as follow: ss ssl sl: cos 2

where s describes interfacial tension components of phase, indices s and l stand for solid and liquid phases, ssl represents the interfacial tension between the two phases and is the contact angle corresponding to the angle between vectors sl and ssl. 4.5. Mineral analysis and entrapped particle observation The mineral element analysis was done on core plug P2 that has been taken from similar large slab of water-wet high-permeability Berea ss. The analysis was done using energy dispersive Xray spectroscopy (EDX). This method is based on the energy dispersed by X-ray beam and reects of surface localizations of the object mineral (Lake, 1989). There are two purposes of performing mineral analysis here: to characterize minerals including clay and nanoparticles in core plugs and to distinguish between nanoparticle and other mineral. To analyze porosity and permeability impairment, entrapped nanoparticles inside porous medium were observed in two different ways. Firstly, microscopic visualization under SEM was performed to see any nanoparticles retention inside core plug by cutting it, both in wet and dry conditions. Secondly, it was indicated from differential pressure log-jamming during singlephase coreood experiment. Permeability is an important property of the porous medium, and it is a measure of capacity of the medium to transmit uids. It is a tensor that in general is a function of pressure (Torster and Abtahi, 2003). Examination of permeability impairment was conducted by comparing the ow ability of brine into core plugs preand post-nanouid injection. By knowing all parameters, and recording P, Darcys equation was used to calculate the

Fig. 9. Interfacial tension and contact angle measurement for crude oil against brine with various nanouid concentrations at ambient condition.

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(2005). They reported below pH of 6, the trend showed that IFT would likely decrease for pH reduction from 6 to 3. Hence, it is expected that the IFT for 0.1 wt% will follow the decline trend. Owens and Archer (1971) reported that increasing the water wetness increases ultimate oil recovery. Morrow (1990) observed also that oil recovery decreased with decreasing water wetness. These results are consistent with the intuitive notion that strong wetting preference of the rock for water and associated strong capillary imbibition forces give the most efcient oil displacement (Morrow, 1990). However, Cooke et al. (1974) observed that increasing oil-wetness increases oil recovery. Morrow (1985) also observed that oil recovery was maximum for cores at intermediate wettability, which is probably related to disconnection and trapping of oil phase. Hence wettability has a vital role in crude oil production (Morrow, 1990) and determines the recovery efciency of displacement processes. Wettability affects both the distribution of hydrocarbon and aqueous phases within the rock matrix and dynamics of displacement processes (Fletcher, 2012). Contact angle is the most universal measurement of the surfaces wettability and an approach to measure reservoir wettability (Morrow, 1990). Figs. 9 and 10 show contact angle measurements of crude oil and brine/nanouids at various concentrations on polished synthetic silica. Nanoparticles reduce contact angle of aqueous phase and consequently result in small hysteresis. The trend showed that increased hydrophilic silica nanouid concentration will increase water wetness. The electrostatic repulsion force between the particles will be bigger when the amount of nanoparticle is huge. Driven by aqueous pressure of the bulk liquid, nanouid will spread along the solid surface and decrease contact angle.

that consists of minimum 1%, therefore we needed a specic mineral such as Aluminum (Al). As can be seen in Fig. 12a and b, mineral Al and K composition line increased signicantly when the area is shifted from red (suspected nanoparticles) to green (suspected non-nanoparticles). Therefore, we can be certain that red area is dominated with nanoparticles. In addition, element K is identied as a part of clay minerals.

5.3. Effect of nanouid concentration to porosity and permeability impairment Several separated injection scenarios for rock properties impairment purposes have been performed in two sister cores and summarized in Table 6. The second method to nd out this impairment was the differential pressure observation. It was recorded from core plugs P3 and P4 during single-phase ooding. Each of them was injected with different nanouid concentrations 0.01 wt% and 0.05 wt% as shown in Fig. 13. Brine 3 wt% NaCl was injected rst into both core plugs for 0.2 PV at constant injection rate 0.1 cm3/min. Then they were injected with nanouids at the same pore volume. At last, the brine was re-injected to observe any alteration after nanouid ooding by comparing with the prole before nanouids injection. It was observed that the average differential pressure almost does not change after injecting 0.2 PV nanouid 0.01 wt%. Otherwise, the average differential pressure increased 7 1 mbar after injecting around 0.2 PV nanouid 0.05 wt%. The noise that occurred around 2 mbar was due to pump stroke. The porosity impairment is dened here as differential between pre- and post-nanouid injection. All core plugs that were re-measured after nanouid injection showed porosity reduction even though they have been cleaned using soxhlet extraction with methanol and dried in heating cabinet. Based on our observation, porosity and permeability impairment is closely related with nanouid concentration and volume of injected nanouid. The higher nanouid concentration will increase the possibility of porosity and permeability impairment (see Tables 6 and 7).

5.2. Mineral analysis of Berea core plugs The most common types of clay mineral deposited in sandstone reservoirs are kaolinite, smectite, illite and chlorite (Grim, 1953). The chemical compositions of clay minerals are shown in Table 5. There are only illite and kaolinite that do not swell and they will not induce permeability impairment (Abbasi et al., 2011). Fig. 11a shows a random area of core P2 which consists of major clay and Fig. 11b shows element minerals from EDX spectrum. As we can see, there are some elements detected besides Si and O as matrix minerals: K, Fe, and Al. Based on Table 5, most of the clay minerals have element Al, but only illite has all of them. Therefore, the presence of K and Fe ensures that we have illite that is well-known as non-expanding clay. To distinguish between nanoparticle (LHP) and clay mineral, we took an image from core plug P4 as shown in Fig. 12. As mentioned in the Material section, this LHP was created from SiO2 Z 99.8%, Al2O3 r 0.05%, TiO2 r 0.03%, HCl r 0.025% and Fe2O3 r 0.003%. The EDX instrument could only interpret mineral

Table 5 Chemical compositions of common clay minerals in sandstone. Clay type Kaolinite Smectite Chlorite Illite Chemical compositions Al2Si2O5(OH)4 (Na,Ca)0.33(Al,Mg)2(Si4O10) NaClO2 or Mg(ClO2)2 (K,H3O)(Al,Mg,Fe)2(Si,Al)4O10[(OH)2,(H2O)]

Fig. 10. Contact angle measurement (ipped image) for crude oil against brine with various nanouid concentrations at ambient condition.

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Fig. 11. Surface morphology (a) and EDS spectrum (b) of core plug P2 for clay mineral characterization under SEM with magnitude 253 times.

Fig. 12. Surface morphology (a) and EDS spectrum (b) of core plug P4 to differ between nanoparticle and clay under SEM with magnitude 2000 times.

Table 6 Helium porosity measurement: comparison between pre- and post-nanouid injection. Berea ss no. Porosity Pre (%) P1 P2 P3 P4 18.68 18.75 19.23 20.64 Post (%) 16.67 16.63 18.69 20.37 Porosity impairment (%) Scenario

2.01 2.12 0.54 0.27

Injected Injected Injected Injected

3 PV nanouid 0.5 wt% @ Qinj 0.5 cm3/min 3 PV nanouid 0.1 wt% @ Qinj 0.5 cm3/min 0.2 PV nanouid 0.05 wt% @ QInj 0.1 cm3/min 0.2 PV nanouid 0.01 wt% @ Qinj 0.1 cm3/min

5.4. Differential pressure prole during two-phase coreood experiment The differential pressure was recorded by precision pressure gauge Keller PD-33X with range 03 bar. Unfortunately, differential pressure was stopped recording for all lowmedium permeability core plugs when it reached almost the maximum limit after around 0.5 PV. Fig. 14 shows the differential pressure for core plug L2 that has porosity 14% and permeability 9 mD. It was injected 3 PV with brine until no more oil was produced and continued with nanouid 0.01 wt % as tertiary mode at constant rate 0.2 cm3/min. Fig. 15 shows the differential pressure for core plug H2. Unlike L2, the pressure for H2 was completely recorded during ooding process. It has porosity 20% and permeability 156 mD. It was injected 3 PV with brine until no more oil produced and continued with nanouid 0.05 wt% as tertiary mode at constant rate 0.2 cm3/min. In the rst 0.5 PV brine ooding, 2-phase ow

existed and increased differential pressure was observed. Once brine breakthrough and only brine produced from core plugs, differential pressure goes down and stabilized at about 33 mbar. There was no more oil produced after 1 PV brine ooding and the injection was stopped at 3 PV. About 3 PV of nanouid injection in core plug H2. The differential pressure increased when nanouid was injected to this core plug. The reason may be that some nanoparticles adsorbed and blocked pore throats and thereby altered rock and uid properties including wettability and interfacial tension. Nanouid ooding needs around 1 PV to enhance oil recovery. The nal increase in oil recovery for core plug H2 is about 56% points. 5.5. Effect of LHP silica nanouids on oil recovery Effects of introducing LHP silica nanouids that altered wettability and interfacial tension on oil recovery have been

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investigated through laboratory coreood displacement test on several core plugs with lowmedium and high permeability and plotted in Figs. 16 and 17. All the results have been tabulated in Table 8. The oil recovery after brine injection is in the range 36 62% of OOIP for lowmedium permeability and the trend is increasing oil recovery with increased rock permeability. Meanwhile higher permeability core plugs have 5064% recovery of OOIP after brine ooding. Nanouids were injected around 3 PV at constant injection rate 0.2 cm3/min and around 0.51 PV were needed to start displacing more oil. Displacement efciency due to nanouids has been evaluated and summarized in Table 8. The displacement efciency of nanouids calculated here follows the formula below:    Sor2 ED 1 :100 Sor1 5

permeability, additional oil recovery due to nanouids is higher in high-permeability core plugs at given nanouid concentration. There was no additional oil recovery in lowmedium permeability reservoir and less oil recovery in high-permeability rocks when nanouid concentrations increased to 0.1 wt%. Based on the previous observation, this was caused by particles blocking the pore network rather than displacing more oil. Overall, the nanouid concentration at 0.05 wt% is the best among other concentrations in this study on oil recovery both for lowmedium and high-permeability water-wet Berea ss core plugs. In addition

where Sor1 represents the residual oil saturation after brine injection and Sor2 represents the residual oil saturation after nanouids for EOR. We observed that displacement efciency is higher when nanouid concentration is increased from 0.01 to 0.05 wt% both in lowmedium permeability and high-permeability core plugs. The residual oil saturation decreases when nanouid concentration is increased for low-permeability core plugs (Figs. 1820). The reduction of residual oil saturation was less than 5% points. Consequently, the ultimate oil recovery increases as the nanouid concentration increases from 0.01 to 0.05 wt% but the recovery is less than 70% oil recovery. Compared to lowmedium
Fig. 14. Oil recovery performance, differential pressure vs. injected PV of core L2: imbibition and EOR process with nanouids 0.01 wt% at constant injection rate 0.2 cm3/min.

Fig. 13. Differential pressure prole during brine and nanouid ooding from two sister core plugs P3 and P4 (single-phase).

Fig. 15. Oil recovery performance, differential pressure vs. injected PV of core H2: imbibition and EOR process with nanouids 0.05 wt%.

Table 7 Liquid permeability measurement: comparison between pre- and post-nanouid injection. Berea ss no. Avg. liq. permeability Pre ( 10 3 mm2) P1 P2 P3 P4 346.92 224.67 223.15 Post ( 10 3 mm2) 18.89 44.21 189.20 210.02 Avg. liq. permeability impairment (%) Scenario

87.99 15.80 5.90

Injected Injected Injected Injected

3 PV nanouid 0.5 wt%: Qinj 0.5 cm3/min 3 PV nanouid 0.1 wt%: Qinj 0.5 cm3/min 0.2 PV nanouid 0.05 wt%: Qinj 0.1 cm3/min 0.2 PV nanouid 0.01 wt%: Qinj 0.1 cm3/min

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137

its displacement efciency is also the highest for all types of permeability of the core plugs. In further, optimum nanouid concentration will be studied to get maximum oil recovery from nanouids EOR. Further works are necessary to establish the connection between these results and relative permeability curves. It is also necessary to perform experiments on core plugs with different wettabilities (neutral-wet and oil-wet). In addition, silica nanoparticles associated with appropriate surfactant are a possible next research step. Hopefully, surfactants will give smaller interfacial tension and remove uid such as oil, parafn and polymer

Fig. 18. Reducing residual oil saturation with nanouids 0.01 wt%. Both low medium and high-permeability core plugs decrease residual oil saturation.

Fig. 16. Oil recovery performance vs. injected PV for lowmedium permeability core plugs with various nanouid concentrations. Fig. 19. Reducing residual oil saturation with nanouids 0.05 wt%. Both low medium and high-permeability core plugs decrease residual oil saturation.

Fig. 17. Oil recovery performance vs. injected PV for high-permeability core plugs with various nanouid concentrations.

Fig. 20. Reducing residual oil saturation with nanouids 0.1 wt%. Only in the highpermeability core plug decreases residual oil saturation.

Table 8 Oil recovery due to brine and EOR with nanouids at various concentrations and displacement efciency at constant injection rate 0.2 cm3/min. Berea ss no. Oil saturation after brine injection (Sor1), % 35.98 53.74 34.36 34.70 25.81 37.75 41.04 29.01 27.57 37.43 Oil recovery after brine injection, % OOIP Nanouids injection for EOR scenario (wt%) 0.01 0.01 0.05 0.05 0.1 0.1 0.01 0.05 0.05 0.1 PV injected at EOR process with nanouids Oil saturation after nanouids Injection (Sor2), % Ultimate oil recovery after nanouids, % OOIP 58.25 37.96 63.16 59.15 62.23 48.96 56.07 67.02 68.75 54.79 Displacement efciency of nanouids, ED %

L1 L2 L3 L4 L5 L6 H1 H2 H3 H4

55.61 36.11 57.02 56.13 62.23 48.96 51.40 61.70 64.06 50.53

2.7 3.1 3.0 3.4 2.8 3.0 2.8 3.1 3.1 3.5

33.84 52.18 29.45 32.31 25.81 37.75 37.09 24.98 23.97 34.21

5.93 2.90 14.29 6.88 0.00 0.00 9.62 13.89 13.04 8.60

L, low-permeability; H, high-permeability.

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residues and thereby make the substrate water-wet as mentioned by Mc.Elfresh et al. (2012). 6. Conclusions Based on the experimental results, the following conclusions can be stated: 1. Lipophobic and hydrophilic nanoparticles (LHP) silica nanoparticle have the ability to reduce the interfacial tension between oil-aqueous system and contact angle of aqueous phase. The interfacial tension and contact angle decrease when nanouid concentration increases. 2. Based on the mineral element analysis, the core plugs might contain clay mineral type illite that is well-known as nonexpanding clay. Therefore, the interaction between brine/nanouid and clay is not the main cause of permeability and porosity impairment in this study. 3. The retention of nanoparticles during single-phase ooding water-wet Berea sandstone core plugs has been observed from differential pressure log-jamming and microscopic visualization under SEM. The retention of nanoparticles inside core plug induced porosity and permeability impairment. 4. Even though interfacial tension and contact angle decrease as nanouid concentration increases, there is no guarantee that additional oil recovery is obtained in lowmedium permeability water-wet Berea ss. Higher concentration (e.g. 0.1 wt% or more) has a tendency to block pore network and will not give additional oil recovery in low-permeability reservoir. 5. A LHP silica nanoparticles suspension seems potentially interesting for EOR in water-wet sandstone at certain nanouid concentration. Based on this particular study, the silica nanouids 0.05 wt% are the best in terms of oil recovery among other concentrations both for lowmedium and highpermeability water-wet Berea ss. Further studies should be started to evaluate the optimum nanouid concentration and to investigate the behavior of nanouid with surfactants at various wetting conditions. SI metric conversion factors mD 9.869233 E 04 mm2 inch 2.540000 E+00 cm cP 1.000000 E+00 mPa s dyn/cm 1.000000 E+00 mN/m bar 1.000000 E 02 kPa mbar 1.000000 E+01 kPa

Acknowledgments The authors would like to thank Dr. Suwarno, Bjrnar Engeset and PhD Candidate, Gema Sakti Raspati who have assisted during this experiment. We appreciate the assistance from laboratory engineer staff, Roger Over, who has prepared Berea ss core plugs.

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