CHAPTER 1

INTRODUCTION

1.1 Background of Study

Generally, oil recovery occurs through two main processes, which are
primary recovery and secondary recovery. Primary recovery commonly comes from
natural drives;, which are rock and liquid expansion drive, depletion drive, gas cap
drive, water drive, and gravity drainage drive. Meanwhile, secondary recovery refers
to the introduction of additional energy into the reservoir. One of most common
technique in secondary recovery is water injection or waterflooding. Briefly, tThe
purpose of this waterflooding is to maintain the reservoir pressure and displace the
remaining oil in the reservoir. Satter et al., (2008) mentioned that waterflooding
technique has been widely used widely mainly due to several reasons, which are
wide availability of water, inexpensive, and lower capital investment and operating
costs. Ordinarily, maximum total oil recoveryed oil after primarily and secondary
stage is 40% to 60% (Farouq and Thomas, 1996). The remaining oil is trapped
mostly because of the heterogeneity of reservoir, unfavorable wettability and
capillary trappinged. To recover this This remaining oil, is the aim of advanced
methods, which have become known as enhanced oil recovery (EOR) methods to
produceis necessary.

About more than 60% worlds oil reserves are held in carbonate reservoirs
(Sheng et al., 2010). It is noted that oil recovery in these reservoirs is lower and this
is because of ascribed by two leading factors thatfactors that are fractured reservoir
and oil-wet rock. Therefore, many researches conducted have been conducted
focusing on wettability alteration of the rock and apparently, there is an increasing
interest in using chemical to alter wettability of the rocks for this purpose. Adding
chemical agents such as surfactants can modify the wettability of carbonate rock
system from oil-wet to more water-wet condition (Mohammadi et al., 2014).
Wettability alteration of rock by surfactants was studied and the usage of ionic
surfactants has been considered as feasible method for the recovery of oil reservoirs
by modifying the wettability of rock surface from oil-wet to water-wet.

In 2010, Chabert et al perceived 80 % of carbonate reservoir are classified as

neutral to oil-wet due to the positive zeta potential of the rock surface. The
adsorption of polar organic component that presents in crude oil might change the
original water-wet calcite surfaces into to be oil-wet. Cationic surfactant was
observed to have performed better than anionic surfactant in changing wettability of
carbonate rock from oil-wet to more water-wet. This is due to the formation of ion
pairs between the cationic heads of the surfactants molecules and the acidic
components of the crude oil absorbed on the surface of carbonate rock (Austad et al.,
1997). However, in contrast according to Salehi et al., (2008) anionic surfactant
molecules form a monolayer on the surface of carbonate rock through hydrophobic
interaction of the tails of the surfactants molecules with the absorbed crude oil
components on the rock surfaces. In addition, the interaction of hydrophobic
interaction are much weaker than ion pair interaction, this explains why cationic
surfactants have better performance performed better than anionic surfactants in
altering carbonate rocks wettability to a more water-wet state.

Nanotechnology is developing in oil and gas industry due to its potential to

solve or manage several problems in the petroleum industries. EOR is one of the
potential areas of nanotechnology application. Nanoparticles haves the ability to alter
certain factors in the formations and in oil properties and this can be an
advantageadvantageous to enhance oil recovery (Ogolo et al., 2012). The author He
also reported that the wettability of a formation could be changed by applications of
nanoparticles. Several studies have been conducted and the applications of
nanoparticles to change rock wettability and its subsequent effects on oil recovery
have been documented by several authors (Karimi et al., 2012, Ogolo et al., 2012,
and Hendraningrat et al., 2013). Nanoparticles can enhance the recovery through two
major mechanisms, which are via interfacial tension reduction and or wettability
alterations (Roustaei et al., 2012). In 2013, Hendraningrat et al. stated that the
displacement mechanism by nanoparticles is called as structural disjoining pressure
mechanism. Brownian motion and electrostatic repulsion between the nanoparticles
are the energies that drive this mechanism in which smaller size nanoparticles would
cause a bigger . He also mentioned that, the repulsion force would be bigger when
nanoparticles are smaller. Structural disjoining pressure is associated to the fluids
ability to spread along the surface of a substrate due to the imbalance of the
interfacial forces among solid, oil phase and aqueous phase, which is the nanofluids.
The interfacial forces will cause the nanofluids contact angle to decrease and the
result is called as wedge film and this wedge film will act to separate formation
fluids such as oil from the formation surface (Liu et al., 2012).

Nanoparticles haves high energy surface energy and therefore the adsorption
of nanoparticles on a solid surface can considerably change the surface energy and
subsequently change the wettability of the rocks. In this research, the introduction of
nanofluids to alter the wettability of carbonate rock will beis studied by experimental
approach in which the experiment is also covering the . The stability of nanofluids
and the effect of nanofluids on IFT are also will be studied.

1.2 Problem Statement

 Current world oil production mostly comes from mature fields and over the
past decades, oil-based companiesy are maximizing the oil production from these
fields. However, stagnant oil production and unimpressive recovery by primary and
secondary recovery have madecaused the situation to be more precarious (Roustaei
et al, 2012). Enhanced oil recovery (EOR) technologies are necessary to meet the
energy demand in many more years to come.

There is a huge interest to enhance recovery from the carbonate rock system
by considering the remaining amount of oil in place. The addition of some chemical
agents such as surfactants and nanoparticles into the injecting water can modify the
wettability of the rock surface. In spite of all reported studiesy, the performance of
aluminium oxide nanoparticles and zirconium oxide nanoparticles in cationic
surfactant to alter wettability of oil-wet dolomite to more oil-wet condition has not
been performed yet and still at their infancynot yet well studied.

Therefore, this research is done carried out to investigate and identify the
types of nanoparticles that areis effective as wettability modifiers. The challenging
part in this study is to understand the mechanisms involved in this alteration.
Parameters such as nanofluids concentrations, and stability of the colloids are very
important and will beis studiedinvestigated in order to achieve an optimized
condition in this study.

1.3 Objectives of Study

The objectives of this research are as follows:

 I. To study the stability of nano solution and the quantities of
nanoparticles deposition during the transport through
dolomite rock.
II. To investigate the wettability alteration of dolomite rock
system after introduction of nano solution.
III. To study the effect of wettability alteration on the oil
recovery.

1.4 Scopes of Work

The research scopes are as follows:

I. Preparation of nano solution by dispersing nanoparticles in cationic

surfactant with presence of sodium chloride.
II. Investigation of the stability of the nano solution by conducting Zzeta
potential, sedimentation test and transport of nanoparticles through porous
media will be conducted to determine the nano solution stability.
III. Investigation of the effect of nanoparticles on IFT reduction by conducting
Iinterfacial tension (IFT) before and after addition of nanoparticles into the
solution. will be measured to determine the effect of nanoparticles on IFT
reduction
IV. Evaluation of the adsorption mechanism of CTAB on dolomite rock by
performing Kkinetic adsorption study of the surfactant surfactant.will be
determined to identify the adsorption mechanism of CTAB on dolomite rock.
 V. Alteration of Rrocks wettability alteration will be conducted under static
condition.
VI. Evaluation of the wettability of the rocks by Qquantitative method will be
used to measure the wettability of the rocks by measuring the contact angle at
ambient condition.
VII. Investigation of the effectiveness of nano solution to act as enhanced oil
recovery agent by conducting an Ooil displacement experiment will be
conducted in sand pack model at ambient condition. to determine the
effectiveness of nano solution to act as enhanced oil recovery agent.

1.5 Significant of Study

Discovering new field is very challenging and most carbonate rock system is
oil-wet and the recovery from these reservoirs is relatively low. Hence, optimizing
oil production from the existing well is one of the best way. However, unfavorable
wettability from these reservoirs may become a great challenge. Therefore, by
altering wettability of carbonate oil reservoir, may accelerate the spontaneous water
imbibition into matrix block can be accelerated and thus increasing the oil recovery
during waterflooding. Besides that, the ability of nanoparticles to alter certain factors
can be taken advantagestand as an excellent option of to the enhanced oil recovery.
 CHAPTER 5

CONCLUSION AND RECOMENDATION

5.1 Conclusion

Favorable wettability of the reservoir rock can enhance the oil

recovery from the reservoir. Wettability alteration by using
chemical and nanoparticles has gain a lot of attention from many
researchers and in this study, application of CTAB surfactant and
nanoparticles to alter wettability of oil-wet dolomite rock was
studied. From the screening process, it was found that Al 2O3 and
ZrO2 wereas the top two from nine other nanoparticles in altering
oil-wet dolomite rock to more water-wet condition and therefore
they were subjected for further testing. Few conclusions can be
drawn from this study are:
1. The stability of Al2O3 and ZrO2 nano solution were studied and
it was found that for both nanoparticles employed, the most
stable mass concentration of nanoparticles was at 0.5 wt %.
The zeta potential for 0.5 wt % Al 2O3 nano solution and ZrO2
nano solution was +17.4 mV and +10.9 mV respectively. In
comparison, Al2O3 nano solution was discovered to be more
stable than ZrO2 nano solution. Supplementary to that, in
nanoparticles transport test, the amount of Al2O3
nanoparticles that can be recovered was 55 % meanwhile
ZrO2 nanoparticles recovery was 52.5%. The higher recovery
of Al2O3 shows a higher stability of the colloidal.
2. Wettability alteration of oil-wet dolomite rock was determined by
measuring the contact angle of the water droplet on the rock
surface. CTAB can alter the wettability of oil-wet dolomite rock to
water-wet condition and dispersion of nanoparticles into the CTAB
surfactant can enhanced the alteration to a stronger water wet
condition. At below CMC value, the water droplet contact angle
decreased with the increase of surfactant concentration. At above
CMC value, the reduction of contact angle was not significant with
the increase of surfactant concentration. The highest contact angle
reduction occured at surfactant concentration of 0.2 wt % with
contact angle of water droplet was decreased to 68 . The results also
found that, the reduction of contact angle can be improved by treatment with addition
of nanoparticles into the surfactant. The highest contact angle reduction of the
dolomite rock after treatment with Al2O3 nano solution and ZrO2 nano
solution was at mass concentration of 0.5 wt %. The wettability
alteration by Al2O3 nano solution was found to be better than ZrO 2
nano solution.
3. Oil displacement test results shows the effectiveness of
nanoparticles to act as enhanced oil recovery agent. The oil
recovery by CTAB surfactant was 14.1% from the remaining oil
trapped in the reservoir. Nonetheless, for the sand pack model that
was treated with Al2O3 nano solution and ZrO2 nano solution shows a
higher recovery. The additional oil recovery by Al 2O3 nano solution
was 20 % and 16.7 % for ZrO2 nano solution from the remaining oil
trapped after secondary recovery. Through contact angle test result,
alteration of wettability by Al2O3 was greater than ZrO2, thus the oil
recovery by Al2O3 was higher than ZrO2. Generally, it can be
concluded that Al2O3 nanoparticles can perform better than ZrO2.
5.2 Recommendation

There are many part in this study need to be improved in order toto
obtain good results and worthy for further investigations. The following
are few recommendations for the future works:

To study the effect of pH on stability of nanoparticles and transport

of nanoparticles through the porous media.
To study the effect of ionic strength on nanoparticles stability by
using different type of salt at different concentration.
To study the isotherm adsorption of the surfactant on the dolomite
rock.
To study the effect of salinity on wettability alteration and oil
recovery during secondary and tertiary recovery.
To study the microscopic displacement of oil after injection of
nanoparticles by using micro model.