3.

Materials and Methodology

3.1. Materials

In this project water has been gathered from the Persian Gulf to prepare nanofluids and has been
identified as having different ionic concentrations and salt composition as shown in Table 3.
Crude oil took from Gachsaran reservoir with API and viscosity of 31.14 and 87 cp,
respectively, and different components as shown in Table 4, used for IFT, contact angle,
imbibition. In Asmari formation in Khuzestan a sample of carbonate rock was obtained and used
for the experiments. The XRD analysis in the Fig.8 shows that the carbonate rock samples
contain 61% dolomite, 39% calcite and no clay. For preparing stable nano-fluids, TiO 2 nano-
particles in 10, 20 and 30 nm sizes were used for IFT, contact angle and adsorption experiments.
for 10, 20 and 30 nm nanoparticles, a Specific Surface Area (SSA) equal to 200–240, 45–60 and
10–35 m2/g, respectively, and the nanoparticles that are used in all three sizes are 99% pure.
Stable TiO2 nanofluid is shown in Fig.9 and TEM images of the nanoparticle is shown in Fig.10.
Fe3O4@quartz nanocomposite were prepared and used for imbibition test under effect of
ultrasonic wave.

Figure 8: XRD analysis of the Asmari carbonate rock.

 Table 1: Composition of Gachsaran crude oil.
Table 2: Analysis of the seawater.

C11 C12+ Total

0.00 0.08 0.73 0.72 2.22 1.10 1.10 8.66 9.32 6.60 7.14 5.36 5.01 651.9 100
Total hardness [ppm] 8700
Sodium absorption Ratio 34.2
Sodium percent solution 64
Total cations [mEq/lit] 495.37
C10

Potassium [mEq/lit] 2.37

C9

Sodium [mEq/lit] 319

C8

Magnesium [mEq/lit] 78
Calcium [mEq/lit] 96
C7

Total anions [mEq/lit] 470.6

Saturation pressure of reservoir fluid @ 60.6 °C = 14.04 MPa.
C6

Sulfate[mEq/lit] 143.6
nC5

Chloride [mEq/lit] 324

iC5

Bicarbonate [mEq/lit] 3
Specific gravity of C12+ @ 15.55 °C = 0.9369.

PH 7.67
iC4 nC4

TDS [mg/lit] 33194

Molecular weight of C12+ = 380 g/gmol.
C3

Molecular weight = 247 g/gmol.

C2

a b c
C1
Component
Molar %
Figure 9: TEM images of TiO2 nanoparticles with different sizes: (a) 10 nm (b) 20 nm and (c) 30 nm.

Figure 10: stability of TiO2 nanoparticles at 10 nm particle sizes and different concentrations.
3.2. Preparation and Characteristics of Fe3O4@quartz Nanocomposite

Initially, Euodia hortensis leaf extract was prepared by adding 50 gm of dried leaf powdered of
the plant to 250 mL double distillated water in 500 mL flask and well mixed. The preparation of
extract was using magnetic heating stirrer at 70 °C for 30 min. The obtained extract was
centrifuged in 7000 rpm and filtered then filtrate was kept at refrigerator to use further.
Afterwards in order to synthesize the NCs, 5 gm FeCl3·6H2O was mixed with 100 mL of the
aqueous Euodia hortensis extract and 12 gm natural quartz powder (Mineral soil) at pH 10 (as
adjusted using Na2CO3 0.1 M) in a 250 mL conical flask. The mixing was continued along with
the vigorous shaking until gradually changing the color of the mixture to dark indicating the
formation of Fe3O4@quartz NCs. The well shacked mixture then filtered and centrifuged at
7000 rpm for 30 min and obtained precipitation washed with n-hexane and absolute ethanol to
remove possible impurities. Finally, the dried and cleaned synthesized nanocomposite was
collected and characterized as ready to be used for EOR applications. In addition, the technique
of scanning electron microscope (SEM) was used to describe the shape and size of
nanocomposite Fe3O4@ quartz. To determine the accuracy of the synthesized nanocomposite. In
addition, the mineralogy of prepared nanomaterials is analyzed using X-ray diffraction (XRD)
and Fourier Transform Infrared Spectroscopy (FTIR).

Figure 9: schematic diagram of Fe3O4@quartz nanocomposite preparation process.

3.3. IFT Measurement

The pendant drop tools were used for IFT calculation. All that is required is a needle, a camera,
and a light source. All tests at reservoir temperature 75 ◦C and ambient pressure were performed.
Nanofluids have been conducted with diluted seawater base in interfacial tension studies. At 4
stages of 5, 10, 15, and 20, the seawater has been diluted. TiO 2 nanoparticles with 250, 500 and
1000 ppm concentrations in 10, 20 and 30 nm particle sizes have been spread for each sample of
diluted seawater. Results of 36 experiments were reported of interfacial tension in this respect. A
drop of the liquid was formed at the end of the stainless steel needle into the bulk phase. Then, a
2-megapixel CCD HD camera used to take an image of the drop, after getting the image software
used to calculate the IFT. Interfacial tension can be calculated by evaluating the droplet
geometry and the difference in phase density. Hansen and Rødsrud (1991) define complete
derivation of the equations as shown in the following equation:

∆ ρ g R20
γ= - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - (3)
β

Where ∆ρ is the difference of mass density between the drop and the medium around, is the
gravitational constant, R0 is the radius of the droplet, β is the shape factor.

Figure 11: Schematic diagram of IFT measurement . (a) high pressure HP and high tempearature HT
pendant drop IFT400 apparatus, and (b) crude oil droplet (Ali et al. 2020).
3.4. Contact Angle Measurement

Sessile drop method was used in this work to determine the contact angles between crude oil
drops and nanofluid in different concentrations on the surface of the carbonate rock. For this
purpose, according to Ali et al. (2019) From the carbonate rock sample, slim plates of about 2
mm are trimmed and polished to become completely smooth, then the prepared thin sections are
purified by toluene and distilled water to eliminate any surface contamination. Alvarez-Berrios et
al. (2018) aged carbonate slim plates for 3 days in crude oil at 70 °C. Then, thin samples were
taken out from the crude oil and put in an oven until they were dried. The aged carbonate core
sections were immersed into different concentrations of nanofluid for 2 days in a container at 75
°C and ambient pressure. After that, a curved syringe needle was then injected into an oil drop
onto the carbonate plate. Then, a camera took photos of oil droplets. The contact angles can be
determined using the appropriate software from the photographs of the oil droplets.

Figure 12: Schematic illustration of the sessile drop method for contact angle measurements (Ali et al.
2019, p. 10).

3.5. Core Preparation

Before the carbonate cores sample saturated with crude oil, a 5 μm membrane was used to filter
crude oil to remove impurities. The core was dried for one day in an oven at 75 °C and then
cooled down for 30 minutes in a dryer. The cores were then balanced and the initial weights
recorded which was 198.918 gr. Using a vacuum pressure saturating device, oil saturation was
established. First, the cores in the vacuum pressure tank were vacuumed for 12 h and then, the oil
with density of 0.904 gr/cc was inhaled into the vacuum pressure tank after being vacuumed for
30 minutes by another vacuum pump. A hand pump applied 20 MPa pressure into the tank and
the core was saturated continuously for 12 hours. The saturate core weight became 205.117 gr.
The cores were finally removed and the excess oil was cleaned and the OOIP was 6.85 cc.

3.6. Imbibition Test

Spontaneous imbibition tests were performed in Amott cell using a method of measuring the
volume of oil directly through the scale of the glass tube to calculate the oil recovery. Different
concentrations of nanofluids were used with presence of the ultrasonic waves. All imbibition
tests were conducted at temperature of 75 ℃. The cores were vertically positioned in the Amott
cells and immersed in several nanofluid concentrations. Then, the cell placed in the ultrasonic
bath filled with water around the cell below its neck. In order to calculate the rate of
imbibition and imbibition recoveries of several systems the crude oil volume displaced by the
spontaneous imbibition was obtained from the scale of the tube on the device every 24 hr. To
perform ultrasonic experiments, such cells are put in a bath filled with water around the cell
below its neck.

Figure 13: Schematic diagram of ultrasonic imbibition test.

3.7. Nanoparticles Adsorption on Carbonate Rock

The spectrophotometric test was used to calculate TiO 2 NPs adsorption with sizes of 10, 20 and
30 nm at temperature of 75 °C. For this reason, the maximum nanoparticle adsorption
wavelength was measured, where the nanofluid concentrations is linearly correlated with light
absorption. Then, The maximum absorbance obtained for the respective NPs concentration, at
maximum wavelength the calibration chart was drown with respect of the absorption rate and the
NPs concentration. After all of this, 8 gr of grinded rock samples (adsorbent) were dispersed in
40 ml of each nanofluid (adsorbate) at 75 °C and nanofluids have been tested by spectroscopy
adsorption at different times. Finally, the amount of NPs absorption calculated from the
following equation:

V (Ci −Ce )
q=
m

Where, Ci and Ce are the initial and final equilibrium concentration of the fluid released from the
rock (mg/L), respectively. V is the volume of the fluid (L), and m the mass of the grinded rock
(g).