SPE-188174-MS

Green EOR Utilizing Well-Defined Nano-Cellulose Based Nano-Fluids from

Flask to Field

Bing Wei, Qinzhi Li, Hao Li, Laiming Lu, and Wanfen Pu, Southwest Petroleum University

Copyright 2017, Society of Petroleum Engineers

This paper was prepared for presentation at the Abu Dhabi International Petroleum Exhibition & Conference held in Abu Dhabi, UAE, 13-16 November 2017.

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
of the paper have not been reviewed by the Society of Petroleum Engineers and are subject to correction by the author(s). The material does not necessarily reflect
any position of the Society of Petroleum Engineers, its officers, or members. Electronic reproduction, distribution, or storage of any part of this paper without the written
consent of the Society of Petroleum Engineers is prohibited. Permission to reproduce in print is restricted to an abstract of not more than 300 words; illustrations may
not be copied. The abstract must contain conspicuous acknowledgment of SPE copyright.

Abstract
The environmental issues of the traditional oilfield chemistries are challenging the Enhanced Oil Recovery
(EOR) industry. Therefore, eco-friendly chemical EOR methods must be quickly developed. In this work,
an abundant natural polymer on earth, nano-cellulose, was extracted from the plant-based materials and then
introduced to EOR. On the basis of the original nano-cellulose, a series of surface-grafting were performed
for the interest to make it more favorable for EOR application, thus generating the well-defined nano-
cellulose based nano-fluids. The EOR related properties including morphology, thermal stability, rheology,
etc., were first studied. The displacement responses of the nano-fluids were then collected. Thereafter, these
nano-fluids were introduced to foam EOR as foam film stabilizers. The results showed that the nano-fluids
exhibited superior thermal resistance, salt tolerance and viscoelastic properties after surface-grafting. As
a result of the amphiphilic nature, the stabilities of surfactant foam in the absence and presence of crude
oil were significantly improved by using the tested nano-fluids and 12% of incremental oil recovery was
obtained in this stabilized foam flooding. When this nano-fluid was used alone to displace the oil in place,
6% of incremental oil recovery was produced after 0.4 PV nano-fluid slug was injected. The experimental
findings obtained from this work promised the nano-cellulose based nano-fluids as green agents in chemical
EOR.

Introduction
Only a small fraction of the crude oil in place can be produced from a reservoir using its initial pressure.
In reality, a common practice in petroleum production is to inject external water to further displace the
remaining oil after natural depletion, i.e. , waterflooding. Despite the use of this mature technology, a large
part of the oil is still unproduced even after waterflooding is exhausted. In this case, EOR techniques,
which can further improve the oil recovery based on waterflooding, must be used in order to stabilize
the decreased oil production. In the past decades, numerous EOR methods have been developed at either
academic or industrial level. On the basis of the differentiations in the injected agents, the EOR methods
can be categorized into chemical flooding (polymer, surfactant, alkali, solvent, etc.), thermal methods,
gas injection, and microbial methods. Of the aforementioned available methods, polymer flooding is the
most intensively utilized EOR method to date in oilfields especially in China due to the availability in
2 SPE-188174-MS

large quantities of polymer with customized properties (molecular weight, degree of hydrolysis, etc.)
coupled with relatively mature technologies. However, it should be pointed out that the widely used
polymer today, partially hydrolyzed polyacrylamide (HPAM), is highly sensitive to the reservoir conditions
(chemical, thermal, and mechanical degradations), which thus leads the injected polymer solutions to
lose the viscosity during injection and propagation in porous media (Wei, Romero-Zerón, and Rodrigue
2014b, Wei, Romero-Zerón, and Rodrigue 2014c, Wei, Romero-Zerón, and Rodrigue 2014a). Furthermore,
the residual acrylamide monomers contained in the products and degraded HPAM are detrimental to
subterranean environment. Therefore, alternative materials that are stable and eco-friendly should be quickly
developed.
To meet this technological trend, a natural polymer, nano-cellulose, was successfully introduced to EOR
area by our group (Wei et al. 2016, Li et al. 2016). Cellulose is one of the most abundant biopolymers
on earth and widely contained in wood, cotton, hemp and other renewable origins (Eichhorn et al. 2010,
Habibi, Lucia, and Rojas 2010, Wang, Lin, and Song 2012, Sathvika et al. 2015). When cellulose is in
nano size, many unique properties are therefore created, for example, high strength, chemical accessibility,
large surface area, etc., which accordingly cause the increasing attentions in the research community
(Janardhnan and Sain 2006, Klemm et al. 2006). A number of reports on the topics of nano-cellulose have
been published in the last years. The rheological properties of the nano-cellulose colloids were reported by
Liu, et al. They found that the viscoelasticity of NC strongly depended on the fraction and shear rate and
the viscosity vs shear rate curves were divided into two regions due to the rearrangement of chains (Liu et
al. 2011). Molnes et al. investigated the effect of electrolytes on the rheological properties and dispersity
of nanocrystal cellulose (NCC). Appropriate injectivity of NCC dispersion in sandstone porous media was
observed (Molnes et al. 2016). The feasibility of cellulose nanofiber (CNF) suspension in EOR and profile
modification were assessed by Kusanagi et al. (Kusanagi et al. 2015). The experimental data confirmed
that CNF suspension can reduce water mobility as a result of viscosity and subsequently access the low
permeability zone. In our previous works, the potential of the original nano-cellulose in EOR has been
generally evaluated. To further improve its properties towards EOR use, surface-grafting was successively
conducted, thus producing well-defined nano-cellulose based nano-fluids. The primary objective of this
work was to present the differentiations of these nano-fluids in terms of the bulk properties and EOR
behaviors as foam film stabilizers and sole displacing agent.

Experimental

Materials
The original nano-cellulose sample was provided by Tianjin Woodelf Biotechnology Co., Ltd., China.
Based on the origin, AMPS (2-acrylamido-2-methylpropane sulfonic acid) was first loaded onto nano-
cellulose and accordingly produced NC-KY. Then, the hydrophobic groups were grafted onto the NC-KY
to prepare NC-KYSS. The chemical structures of the three samples are shown in Fig. 1. The SEM images
are presented in Fig. 2. Nonionic surfactant alkyl polyglycoside (APG, 98%) was purchased from Chengdu
Kelong Chemicals Inc., China and used as received.
SPE-188174-MS 3

Figure 1—The chemical structures of the three NC samples (Wei, Li, et al. 2017, Li et al. 2017)
4 SPE-188174-MS

Figure 2—SEM images of the samples

Thermogravimetric analysis
Thermogravimetric tests were conducted with a DSC823 TGA/SDTA851e analyzer (Mettler-Toledo Crop.,
Switzerland). Approximately, 7 mg of the nano-cellulose samples were loaded and then heated from 25 to
400°C at a constant heating rate of 10 °C/min under nitrogen atmosphere.

Rheological analysis
The viscosities of the nano-fluids were measured at 25°C with an Anton Paar MCR 302 rheometer equipped
with a CC27 measuring system. A small amplitude oscillatory was also conducted with this rheometer to
determine the elastic (G') and viscous (G") moduli as a function of angular frequency. A small strain of
0.5% was used for all the tests to ensure the linear viscoelastic region.

Foaming behaviors
The foaming performance of the APG/NC systems and the stability of the prepared foam with and
without crude oil were assessed using Waring blender method. 100 ml of foaming solutions were agitated
mechanically at 6000 rpm for 1 min. The prepared foam was then transferred to graduated cylinders. Then,
the behaviors of the foams were assessed by determining some critical parameters.

Displacement tests
To study the flow behaviors in porous media and EOR efficiency of the tested nano-fluids, a five-spot visual
micromodel was designed and assembled in our lab. The simplified diagram of the setup was illustrated in
Fig. 3 (Wei, Lu, et al. 2017, Wei, Li, et al. 2017). The model contains a stainless steel tank (15×15×1cm)
and an organic transparent glass. Homogenous 80-mesh glass beads were used to pack the model. The
brine solution was first injected into the model to measure the pore volume and the crude oil was then
pumped to establish the initial oil saturation (Sor) until no additional water was observed at the production
end. Waterflooding was conducted and terminated when the water cut reached 98%. Afterwards, as an EOR
mode, a chemical slug was injected into the water flooded model to further improve the oil recovery. In this
work, the nano-cellulose fluids were recommended to EOR application in the forms of foam flooding (film
stabilizer) and nano-fluid flooding. Therefore, the chemcial slugs were subsequently prepared and injected
into the model. The propagations of the displacing phase and displaced phase were observed visually
through the transparent glass. The images captured were further analyzed using a coded MatLab program.
SPE-188174-MS 5

Figure 3—Simplied diagram of the experimental setup

Results and discussion

The thermal stabilities of the three nano-cellulose samples under the elevated temperature were investigated
using TG. The curves of TG/DTG obtained are presented in Fig. 4. It is shown that the TG curves were
subject to three regions. The first region of the mass loss, corresponding to the temperature from 25 to
250°C, was caused by the evaporation of the inter and intramolecular moisture. The second region, which
represented the thermal decomposition or pyrolysis of the nano-cellulose, occurred around 325°C as shown
on the DTG curves. The last region beginning from 350°C might be due to the carbonization of the samples.
Due to the incorporation of the functional groups (AMPS and hydrophobic chains), the resistance of the
nano-cellulose to temperature was slightly improved as proven by the thermal decomposition results. This
is highly crucial to this material if it is used to obstruct steam channeling with surfactant foam as a film
stabilizer.

Figure 4—Thermal decomposition of the nano-cellulose samples (Li et al. 2016)

6 SPE-188174-MS

The shear viscosities of the three nano-fluids at 10 s-1 as a function of mass concentration were plotted in
Fig. 5. The viscosity of the nano-fluid gradually increased with the concentration, which was consistent with
the behaviors of other polymers as HPAM. After grafting treatments, the viscosity of the nano-cellulose was
detracted especially for NC-KYSS, caused by the enlarged molecular space induced by the loaded groups.
Nevertheless, a significant thickening power was observed for NC-KYSS as indicated in Fig. 5. Figure 5
also shows that all the three nano-cellulose fluids are pronounced pseudo-plastic fluids, i.e., the viscosity
decreases quickly upon shear rate.

Figure 5—Viscosity of the three nano-fluids versus mass concentration and shear rate

Figure 6 shows the G' (storage modulus) and G" (loss modulus) profiles of the three nano-cellulose with
the imposed oscillation frequency. As shown in Fig. 6, the magnitudes of G' for NC and NC-KY were higher
than G" in the tested frequency, proving the gel behavior of these nano-fluids. In contrast, for NC-KYSS,
a viscous feature was observed at the lower frequency. The phase transition occurred at the frequency of
approximately 10 Hz, after which a gel nature dominated. These results were ascribed to the incorporation
of the hydrophobic chains.
SPE-188174-MS 7

Figure 6—Viscoelastic properties of the nano-cellulose fluids

The nano-cellulose fluids were first proposed to stabilize foam film for foam EOR. In this work, the
formulation of 0.2 wt% APG and 0.1 wt% nano-cellulose was used to prepare foam by mechanical blending.
Figure 7 shows the foam decay profiles of the four systems in the absence and presence of oil. In the bulk
tests, the criterion of half decay time, which was defined as the time that the first half foam volume lasts,
was frequently used to quantify the stability of the prepared foam. Normally, long half decay time represents
high foam stability and vice versa. As shown in Fig. 7, the incorporation of the nano-cellulose fluids notably
extended the foam life counting from generation to completely vanish. Thus, the half decay times of these
nano-fluids enhanced foams were improved as indicated in Fig. 7. The enhancement was more significant
when oil was present, as revealed by the profiles shown in the right (Fig. 7). These profiles also demonstrated
that oil was detrimental to foam stability. After nano-fluids stabilization, the half decay time or stability
of the foam was considerably promoted. Figure 8 shows the images of the four foam systems without and
with oil. The foam morphology was visually observed from Fig. 8. Of the three evaluated nano-cellulose
samples, NC-KYSS seemed more efficient in stabilizing APG foam film in contrast to NC and NC-KY due
to the amphiphilic nature. Therefore, this sample was chosen for the displacement tests.
8 SPE-188174-MS

Figure 7—Volume decay profiles of the APG foam and NC stabilized foam in the absence and presence of oil

Figure 8—Morphology of the foam systems in the absence (top) and presence (bottom) of oil

The experimental setup of the displacement tests is illustrated in Fig. 3. The displacement dynamics of the
sole NC-KYSS fluid flooding are shown in Fig. 9. In the homogenous sandpack model, the waterflooding
oil recovery was nearly 46% OOIP (original oil in place) at 4 PV of brine. Then, a 0.4 PV of NC-KYSS
fluid slug was injected into the model to simulate EOR followed by a post waterflooding. It was shown that
this nano-fluid was able to further improve the oil recovery after waterflooding. In our work, approximately
6% OOIP was produced and the water cut was reduced by 5% simultaneously, verifying the potential of
this nano-fluid in EOR. Figure 10 shows the micromodel images captured during the displacement tests.
From these images, the reduction of the oil saturation of the sandpack model can be visually observed.
Through pixel reading, the oil recovery efficiencies of the waterflooding, nano-fluid flooding and post
waterflooding were quantitatively determined as shown in Fig. 11. The results proved that the macroscopic
SPE-188174-MS 9

sweep and microscopic displacement efficiencies of the nano-fluid flooding were increased by 9.2% and
1.3%, respectively, based on waterflooding.

Figure 9—Displacement dynamics of the NC-KYSS fluid flooding (0.3 wt%)

Figure 10—Matlab released images of the nano-fluid flooding

10 SPE-188174-MS

Figure 11—Oil recovery efficiencies of the nano-fluid flooding

This nano-fluid (NC-KYSS) was then introduced to foam flooding as a foam film stabilizer. It is briefly
agreed that the flow behaviors and EOR efficiency of foam are highly governed by foam stability. The film
stabilizing effect of NC-KYSS fluid particularly when oil is present has been conclusively proven above.
In this section, this type of foam was employed as the EOR mode compared with APG foam. Figure 12
shows the responses of oil production to water and foam injections. It was observed that in the first three
PV, the oil recovery profiles were fairly similar, and the most significant variation occurred in the post
waterflooding stage, suggesting the superior stability of this foam. Relative to the APG foam flooding, 12%
OOIP of additional oil recovery was produced after the APG foam film was stabilized by NC-KYSS. Figure
13 presented the MatLab released images illustrating the displacement process. Using the same method as
that used above, the oil recovery efficiencies were obtained as shown in Fig. 14. After stabilizing film with
this nano-fluid, the EOR efficiencies of the foam flooding at both micro and macro scales were noticeably
improved.

Figure 12—Displacement dynamics of the foam flooding

SPE-188174-MS 11

Figure 13—Matlab released images of the foam flooding

Figure 14—Oil recovery efficiencies of the foam flooding

12 SPE-188174-MS

The bench scale evaluations of the nano-cellulose based nano-fluids including surface modification, EOR
relevant chemical and physical properties, flow behaviors, and EOR performance have been completed
in our group in the past three years. Moreover, the oil recovery mechanisms from micro to macro-scale
were also elucidated. To ready the field scale use, a small pilot plant with the productivity of 2 tons/d (NC
hydrogel) was built as shown in Fig. 15.

Figure 15—Nano-cellulose pilot plants

Conclusion
Due to the less possibility of new reserves supply, the play of EOR in the global oil production is of
increasing significance. However, the current oilfield chemistries are potentially contaminative to the
subterranean environment; thus, eco-friendly chemicals must be quickly developed. As an emerging natural
material, nano-cellulose attracts numerous attentions in different industrial areas. In our works, a series
of surface-grafting was conducted to render nano-cellulose potentials for EOR use. This paper confirmed
that these well-defined nano-cellulose fluids are promising in chemical EOR as green injectants. The flask
investigations have been completed and pilot test will be focused next.

Acknowledgement
The authors gratefully acknowledge the financial support of the National Key Basic Research Program
of China (2015CB250904) and PetroChina Innovation Foundation (2015D-5006-0212). The authors also
thank the anonymous reviewers for the valuable comments.

References
Eichhorn, S.J., Dufresne, A., Aranguren, M., et al. 2010. Review: current international research into cellulose nanofibres
and nanocomposites. Journal of Materials Science, 45 (1): 1-33.
Habibi, Y., Lucia, L.A., Rojas, O.J. 2010. Cellulose Nanocrystals: Chemistry, Self-Assembly, And Applications. Chemical
Review, 110 (6): 3479-3500.
Janardhnan, S., Sain, M. 2006. Isolation of cellulose microfibrils-An enzymatic approach. Bioresources, 1 (2): 176-188.
Klemm, D., Schumann, D., Kramer, F., et al. 2006. Nanocelluloses as Innovative Polymers in Research and Application.
Advances in Polymer Science, 205: 49-96.
Kusanagi, K., Murata, S., Gio, Y., et al. 2015. Application of Cellulose Nanofiber as Environment-Friendly Polymer for
Oil Development. Paper SPE 176456 presented at SPE/IATMI Asia Pacific Oil & Gas Conference and Exhibition,
Nusa Dua, Bali, Indonesia.
Li, Q.Z., Wei, B., Xue, Y., et al. 2016. Improving the physical properties of nano-cellulose through chemical grafting for
potential use in enhancing oil recovery. Journal of Bioresources and Bioproducts, 4 (1): 186-191.
Li, Q.Z., Wei, B., Lu, L.M., et al. 2017. Investigation of physical properties and displacement mechanisms of surface-
grafted nano-cellulose fluids for enhanced oil recovery. Fuel, 207: 352-364.
SPE-188174-MS 13

Liu, D., Chen, X., Yue, Y., et al. 2011. Structure and rheology of nanocrystalline cellulose. Carbohydrate Polymers, 84
(1): 316-322.
Molnes, S.N., Torrijos, I.P., Strand, S., et al. 2016. Sandstone injectivity and salt stability of cellulose nanocrystals (CNC)
dispersions-Premises for use of CNC in enhanced oil recovery. Industrial Crops & Products, 93: 152-160.
Sathvika, T., Manasi., Rajesh, V., et al. 2015. Microwave assisted immobilization of yeast in cellulose biopolymer as a
green adsorbent for the sequestration of chromium. Chemical Engineering Journal, 279: 38–46.
Wang, Z., Lin, W., Song, W. 2012. Liquid product from hydrothermal treatment of cellulose by direct GC/MS analysis.
Applied Energy, 97 (9): 56–60
Wei, B., Li, H., Li, Q.Z., et al. 2017. Stabilization of Foam Lamella Using Novel Surface-Grafted Nanocellulose-Based
Nanofluids. Langmuir, 33: 5127-5139.
Wei, B., Lu, L.M., Li, Q.Z., et al. 2017. Mechanistic Study of Oil/Brine/Solid Interfacial Behaviors during Low-Salinity
Waterflooding Using Visual and Quantitative Methods. Energy & Fuels 31 (6): 6615-6624.
Wei, B., Romero-Zerón, L., Rodrigue, D. 2014a. Mechanical properties and flow behavior of polymers for enhanced oil
recovery. Journal of Macromolecular Science, Part B: Physics, 53 (4): 625-644.
Wei, B., Romero-Zerón, L., Rodrigue, D. 2014b. Novel self-assembling polymeric system based on a hydrophobic
modified copolymer: Formulation, rheological characterization, and performance in enhanced heavy oil recovery.
Polymers for Advanced Technologies, 25 (7): 732-741.
Wei, B., Romero-Zerón, L., Rodrigue, D. 2014c. Evaluation of Two New Self-assembly Polymeric Systems for Enhanced
Heavy Oil Recovery. Industrial and Engeering Chemistry Research, 53 (43): 16600-16611.
Wei, B., Li, Q.Z., Jin, F.Y., et al. 2016. The Potential of a Novel Nano-fluid in Enhancing Oil Recovery. Energy & Fuels
30 (4): 2882-2891.