SPE-190283-MS

An Experimental Study of Enhanced Oil Recovery EOR Using a Green

Nano-Suspension

Bing Wei, Li Qinzhi, Yanyuan Wang, Ke Gao, Wanfen Pu, and Lin Sun, Southwest Petroleum University

Copyright 2018, Society of Petroleum Engineers

This paper was prepared for presentation at the SPE Improved Oil Recovery Conference held in Tulsa, Oklahoma, USA, 14-18 April 2018.

This paper was selected for presentation by an SPE program committee following review of information contained in an abstract submitted by the author(s). Contents
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Abstract
In this work, a novel nano-suspension (NS), which was mainly composed of a surface functionalized nano-
cellulose, was successfully developed for "green" chemical EOR use. The rheological analysis indicated
that this NS was a pseudo-plastic (shear-thinning) fluid and presented noticeable viscoelasticity. The oil
displacement behaviors of this NS were thoroughly examined using core flooding methods. The EOR
efficiency dependence of the NS on permeability, oil viscosity and injected volume was included. The
experimental results showed that the NS flooding (NSF) further improved the oil recovery by 3-17% on
the basis of water flooding. Furthermore, micro flow tests were conducted in a visual micro-model to study
its flow behaviors in porous media and EOR mechanisms. Through the micro-model, the displacement
behaviors and mechanisms including emulsification, dragging/squeezing and wettability alteration, were
visually observed. These properties promise this NS as a green displacement agent for chemical EOR.

Introduction
It has been well-known that for most of the oilfields in the world, about 65% of hydrocarbons still remain
unproduced even after natural drive and water flooding are exhausted. Given this issue, EOR technologies
especially chemical flooding, were quickly developed in the past decades to further mobilize these resources
(Wang et al. 2009, Dong, Ma, and Liu 2009, Koch and Mclaughlin 1970, Li et al. 2016, Jung et al.
2013, Delamaide and Corlay 1994, Wassmuth et al. 2009, Sandiford 1964, Wei, Li, and Kong 2016, Li,
Romero-Zerón, et al. 2017). However, it should be pointed out that the development of chemical flooding
is indeed constrained in recent years due to some technical factors. For example, the most widely utilized
polymer, HPAM, is detrimental to subterranean environment because of the toxic monomer. In addition,
the discharge of industrial oily wastewater is a risk to the environmental and ecological systems. Thus,
environmental acceptability will be one of the critical considerations and a primary criterion for screening
EOR technologies in the near future. In this case, alternative eco-friendly and reusable materials/processes
attract tremendous attention in the research community (Liu et al. 2016, Kong and Ohadi 2010, Yao et al.
2015, Santander, Rodrigues, and Rubio 2011).
Cellulose is the most abundant biopolymer on the earth and also a source for many sustainable materials.
When the cellulose is in nano-size, a number of unique properties such as large surface area, light weight and
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renewability, are subsequently generated (Kusanagi et al. 2015, Wen et al. 2016). For example, the three-
dimensional cellulose network due to the hydrogen bonds and entanglement lead to significant viscosity.
The exposed hydroxyl groups render nano-cellulose high reactivity for surface modification and grafting
(Liu et al. 2016, France, Hoare, and Cranston 2017, Quennouz et al. 2016, Iwamoto, Lee, and Endo 2014).
Therefore, nano-cellulose and derivatives have been widely used in industries including reinforcing agent,
sizing agent, drug delivery, etc. (Liu et al. 2017, Dimicmisic, Gane, and Paltakari 2013).
As a result of the aforementioned advantages, one of the research interests of nano-cellulose is directed
toward the development of displacement agent for EOR use (Wei et al. 2017, Kusanagi et al. 2015, Wei
et al. 2016). However, our results showed that nano-cellulose chains easily aggregated and flocculated
in saline water, which thus made the injection process problematic (Wågberg et al. 2008). To improve
the colloidal stability of nano-cellulose system, substantial works have been conducted, for example using
surfactant (Gardner et al. 2008). Nevertheless, the interactions between surfactant and nano-cellulose can
be hardly recognized and controlled (Li, Dai, et al. 2017). Therefore, in this work, surface-modification,
which simultaneously grafts AMPS and hydrophobic groups onto nano-cellulose, was introduced as shown
in Figure 1. This chemical modification imparts nano-cellulose distinctive features such as amphiphilicity
and surface-activity (Wen et al. 2016). In our previous reports, the structure and physical properties of
this NS have been thoroughly investigated including thermal stability, dispersity in electrolytes, wettability
alteration, emulsification, etc. Herein, the primary objective of this work was to examine the EOR efficiency
and mechanism of this NS as a green flooding agent through marco- and micro-scale experiments. The
effects of injected volume, permeability and oil viscosity in EOR performance were included. Particular
attention was given to the micro flow tests, which were conducted in a visual micro-model, to study its
displacement behaviors in porous media and EOR mechanisms.

Figure 1—Schematic representation of chemical modification of nano-cellulose

SPE-190283-MS 3

Experimental
Materials
The nano-suspension (NS) was supplied by Tianjin Woodelf Biotechnology Co., Ltd., China. The chemical
structure is shown in Figure 1. 0.3wt% of NS in 1 wt% of brine was prepared and used in this study. The
crude oils used in this work were kindly provided by Xinjiang Oilfield, China. The density and viscosity
of three crude oils were 0.873g/cm3 and 26.79 mPa·s (10 s−1), 0.880 g/cm3 and 112 mPa·s (10 s−1), 0.897g/
cm3 and 1542 mPa·s (10 s−1) at 25 °C, respectively. The porous media used were unconsolidated models,
which were packed with homogeneous glass beads. The basic properties of the sandpacks were summarized
in Table 1.

Table 1—The properties of these cores used in our experiments

Saturated oil
No. Pore volume (cm3) Oil saturation (%) Permeability (mD)
volume (cm3)

0-1 72 58.5 81.25 2857

0-2 70 59 84.29 2413

0-3 69 63 91.3 2518

0-4 50 42 84 2750

1-1 76 66 86.85 334

1-2 63 50 79.36 806

1-3 71 65 91.5 1305

1-4 69 69 91.3 2518

2-1 71 60 84.51 2829

2-2 69 63 91.30 2518

2-3 73 56 76.71 2763

Oil displacement tests

Figure 2 illustrates the experimental setup of oil displacement tests. The setup is mainly consisted of
constant-flooding pump, air bath, fluid transfer vessels, data acquisition system, and cylinder for effluent
collection. The porous media used in this section were unconsolidated models, which were packed with
homogeneous glass beads. To respect the initial reservoir conditions, the porous media was first saturated
with brine (1 wt%) to measure the pore volume (PV) and permeability (K) of the sandpack as listed in
Table 1. Crude oil was then injected to displace the brine in place and establish the initial oil saturation and
connate water. To simulate water flooding, 1 wt% of brine was subsequently injected to displace the oil in
place until no more oil was produced. As an EOR mode, the NS with the certain PV was injected followed
by a post water flooding stage. All the tests were conducted under ambient pressure and temperature. A
constant flow rate of 1 mL/min was used.
4 SPE-190283-MS

Figure 2—The experimental setup of the oil displacement tests

Micro-model flooding experiment

A visual micromodel (40 mm × 40 mm) was used in the microflow experiments. The experimental setup is
shown in Figure 3. The depth and width of the flow channels are approximately 60 and 80 μm, respectively.
The model was first saturated with the crude oil. Water flooding was then conducted at a constant injection
rate of 0.1 mL/min to displace the oil in place until no more oil was produced. After that, a 0.8 PV of NS
slug was injected to simulate chemical EOR stage followed by a post brine injection. The flow behaviors
of the fluids in the mode were recorded by a digital acquisition system. The viscosity of crude oil was 112
mPa·s (10 s−1) at 25 °C.

Figure 3—Simplified schematic diagram of the visual microflow setup

Results and discussion

Rheological behaviors of the NS
The rheological behaviors of the displacement systems are closely related to their performance in chemical
EOR process. Therefore, the rheology of this NS at a constant concentration (0.3 wt%) was systematically
examined in this section. The dependence of its rheological properties on shear rare, frequency and
temperature are presented in Figure 4. Figure 4A plots the steady viscosity of the NS as a function of shear
rate. It was observed that this NS was a shear-thinning fluid, which was consistent with other published
works. This result was thought to be caused by nano-cellulose chain interactions, which would be broken at
high shear strength (Liu et al. 2017). Moreover, it is interesting that the viscosity of this NS was improved
when salts were present due to the grafted hydrophobic groups. The storage and loss moduli of the NS
SPE-190283-MS 5

as a function of the imposed frequency were plotted in Figure 4B. It is clear that for the NS the storage
modulus is larger than loss modulus regardless of salts, indicating its gel-like behavior (Li et al. 2017). As
mentioned earlier, the addition of salts imposes a positive effect on the viscoelasticity of the NS. Figure 4c
and d show the variation of NS viscosity with temperature. Due to the enhanced interactions, the viscosity
of this NS initially increased with temperature increasing until 50°C was reached, after which slight decline
was observed.

Figure 4—Rheological properties of the NS (A)Viscosity versus shear rate; (B) Variation
of dynamic modulus (G" and G') of NS versus frequency (25°C); (C) Viscosity versus
temperature at 10s−1; (D) NS viscosity versus shear rate at different temperatures

Oil displacement tests

To study the EOR performance of this NS, 11 displacement tests in total were carried out in this work. The
effects of injected volume, permeability and oil viscosity on the EOR efficiency of this NS were discussed
as follows.

Effect of injected volume

Figure 5 shows the oil recovery factor as a function of the injected fluid pore volume (PV) for water flooding
and NSF stage. The NS slug sizes of 0.3, 0.5, 0.8 and 1.2 PV were used. Table 2 summarizes the results
of the oil displacement tests. It can be seen that the oil recovery factors of water flooding in these tests are
approximately 50% of OOIP (original oil in place) after 4 PV of water injection. As an EOR mode, the
NSF can further improve the oil recovery efficiency by 3%-7% on the basis of water flooding as indicated
in Table 2, suggesting the potential of this NS in EOR. Furthermore, the oil recovery factor of the NSF
generally increased with the increasing PV and the highest oil recovery factor was produced when a 0.8
PV of NS slug was used. Regarding the injection pressure as shown in Figure 5, water flooding produced
an ultra-low pressure, especially at the end of water flooding stage, while the injection pressure gradually
increased during NSF and then decreased during the post water injection. The pressure change suggests the
6 SPE-190283-MS

proper propagation of the NS through the sandpack. However, it must be pointed out that slight plugging
might occur during NSF, as revealed by the noticeably high injection pressure.

Figure 5—Oil recovery of NSF as a function of injected fluid volume (PV)

Table 2—Summary of the oil displacement tests

Oil viscosity
No. PV Permeability (mD) EOR (%)
(mPa·s/25°C)

0-1 0.3 2857 112 3.74

0-2 0.5 2413 112 3.54

0-3 0.8 2518 112 6.92

0-4 1.2 2750 112 6.55

1-1 0.8 334 112 3.44

1-2 0.8 808 112 4.7

1-3 0.8 1305 112 8.97

1-4 0.8 2518 112 6.92

2-1 0.8 2829 26.79 3.21

2-2 0.8 2518 112 6.92

2-3 0.8 2852 1542 16.79

Effect of porous media permeability

Figure 6 shows the effect of porous media permeability on the EOR efficiency of NSF. In consistent with
the above observations, this NS can successfully travel through the sandpacks and improve the oil recovery
after water flooding within the evaluated permeability range. The oil recovery factor of NSF increased with
the permeability until 8.97% of OOIP was achieved at 1305mD, after which the oil recovery factor was
prone to drop as shown in Figure 6. This result is believed to be caused by the matching between the size
of nano-cellulose in NS and pore size of sandpack. This part of work is in progress in our group and will
be presented in a future work.
SPE-190283-MS 7

Figure 6—Oil recovery factor of NSF as a function of permeability

Effect of oil viscosity

Figure 7 plots the oil recovery factor and pressure during fluid injection as a function of displaced oil
viscosity. In this section, three crude oils provided by an oilfield with the viscosities of 26.79, 112 and
1542mP·s were used. As shown in Figure 7, NSF notably promoted the oil recovery factor from 3.21-16.76
%, demonstrating its superior EOR efficiency. It is noteworthy that the EOR efficiency of NSF for the heavy
oil (1542mP·s) is extremely high compared to the other two oils. This result is due to a fact that viscous
fingering during displacement varies exponentially with mobility ratio, thus water flooding usually leads
to a very low sweep efficiency for heavy oil reservoirs. During NSF, the particles of nano-cellulose can
partially plug some chief channels and divert the subsequent displacing fluids to the oil-bearing zones.

Figure 7—Oil recovery factor of NSF as a function of oil viscosity

Visual microflow tests

After the above static and macro-scale displacement tests, a visual microflow experiment was conducted
in this section for the intent of observing the distributions of NS and oil at pore scale and deeply
gaining the displacement mechanisms of NSF. The specifications of this micro model have been
provided in the section mentioned above. Figures 8-10 present the collected images during NSF to
illustrate the significant mechanisms. Through microflow experiments, three leading mechanisms including
emulsification, squeezing/drag and wettability alternation were clearly observed during NSF.
The surface activity of NS caused by the grafted AMPS and ASA can noticeably reduce the interfacial
tension (IFT) between oil phase and water phase, and thus disperse oil into water phase forming emulsions
8 SPE-190283-MS

(Li, Wei et al. 2017). As anticipated, the emulsifying behaviors of NS were clearly observed during NSF
along the flow orientation as shown in Figure 8. Therefore, emulsification effect is believed to be one of
the leading mechanisms of NSF.

Figure 8—Emulsification effect of NSF

Figure 9 shows the distributions of NS and residual oil during NSF. Oil mobilization caused by NSF was
visually observed in Figure 9. Moreover, a close examination indicated that the residue oil was first stretched
to long cylindrical droplets under the effects of dragging and/or squeezing of NS. These stretched oil droplets
were then dragged forwards forming an "oil bridge" channel through pore throat. This mechanism might
be associated with the viscoelastic properties as polymer.

Figure 9—Squeezing/dragging effects

SPE-190283-MS 9

Figure 10 illustrates the change of surface wettability during NSF. It is widely believed that wettability
alteration of solid surface is the predominant mechanism for some chemical EOR processes such as
surfactant flooding and other nanofluid injection especially for carbonate. As shown in Figure 10, the surface
wettability of the model was converted towards water wetness. The mechanism behind is as follows: The
nano-cellulose colloids can "wedge spread" on the rock surface and thus roll up the oil film adsorbed on
the surface as a result of amphiphilic property and electrostatic effect (Li, Wei et al. 2017). Although the
visual microflow observations can't completely represent all the EOR mechanisms involved in NSF, some
typical mechanisms were easily recognized.

Figure 10—Wettability alteration of surface during NSF

Conclusion
We have developed a green NS through surface grafting (AMPS and hydrophobic groups) for chemical
enhanced oil recovery (EOR) application. The EOR efficiency and mechanisms of NSF were investigated in
this work through oil displacement tests and visual microflow tests. Based on the experimental observations,
some main conclusions can be drawn as follows.
1. The rheological analysis indicated that after chemical modification, the stability of this NS in
electrolytes has been improved. This NS presented pseudo-plastic (shear-thinning) and viscoelastic
behaviors.
2. With regard to the oil displacement behaviors, we found that this NS possessed an appropriate
injectivity in 300-2800mD sandpacks. As an EOR mode, the NSF further improved the oil recovery
by 3-17% after water flooding. The magnitude of EOR was proven to be largely dependent on oil
viscosity and permeability.
3. The flow behaviors of this NS were visually observed in the micro-model, through which the EOR
mechanisms including emulsification, dragging, squeezing, and wettability alteration were identified.

Acknowledgments
This work was financially supported by the National Key Basic Research Program of China (No.
2015CB250904) and PetroChina Innovation Foundation (2015D-5006-0212). The authors gratefully
acknowledge the support of Youth Science and Technology Innovation Team of SWPU (2017CXTD04).

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