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Carbon Nanotubes laced Superabsorbent Polymer for Enhanced Oil Recovery

Technology

Conference Paper · November 2015

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 Proceedings of AMPE, 14-15 2015, Karachi, Pakistan

Carbon Nanotubes laced Superabsorbent Polymer for Enhanced Oil Recovery

Technology
Muhammad Mohsin Yousufi1, Saud Hashmi *2
1Department of Petroleum Engineering, NED University of Engineering and Technology,
University Rd, Karachi 75270, Pakistan, moshyousufi@hotmail.com
2Department of Chemical Engineering, NED University of Engineering & Technology, University

Road, Karachi 75270, Pakistan,

*
Corresponding Author : Saud Hashmi
*
Email : saudhashmi@neduet.edu.pk

Abstract
Hybrid nano-composite hydrogel of super absorbent polymer (SAP) containing Carboxylated Multi-
Walled Carbon Nanotubes (CMWCNTs) was synthesized to enhance the properties of the polymer in
reservoir conditions having a low pH value and high temperature. The hybrid hydrogels were tested at
different temperatures and pH values and comparison between super absorbent polymers with
CMWCNTs and without them were made to observe the osmotic changes in the material as well as
increase in the swelling efficiency by the addition of CMWCNTs. It was clearly evidence that the addition
of CMWCNT significantly enhanced the swelling capability as well as the mechanical stability of the
hybrid hydrogel. FTIR (Fourier Transform Infrared Spectroscopy) analysis was done for characterization
of the hydrogel and FESEM (Field Emission Scanning Electron Microscope) was conducted to study the
surface morphology.

1. Introduction In order to do so chemicals, surfactants,

An oil reservoir generally produces around 10%
of the reserves present via its natural drive
mechanism (primary recovery). An additional
25%-30% is recovered by pressurizing
(secondary recovery) the reservoir through
water and gas injection. However there is still
50%-70% of crude oil left inside for production.
[1] This is where Enhanced Oil Recovery
(tertiary recovery) comes into action, as the oil
in place is stuck and requires mobility
enhancement or a change in the interfacial
tension for it to move out of the pore spaces,
this way an additional 20%-30% recovery is
obtained.
thermal injections are conducted through an
injection well. Polymer flooding being one of
the Enhanced Oil Recovery methods has been in
use for more than 40 years. Being effective in
recovery of un-swept oil by improving the
mobility ratio. Up to 5%-30% has been obtained
by it various cases throughout the world. It is
cheaper than water flooding due to decreased
water production and increased oil production.
Superabsorbent polymers are capable of
absorbing huge volumes of water. SAP have
been used as plugging agent by Chinese oil
companies in enhanced oil recovery methods.
Water volume in the crude due to long period
 Proceedings of AMPE, 14-15 2015, Karachi, Pakistan

of water flooding increased, reducing the oil working in an environment having pH value less
productivity. Higher water content in the crude than 2.9. [2, 3, 4]
oil can become a cause of increased corrosion,
sand production, emulsion formation and
disposal, etc. [2, 8]

Figure 1b. SAP with 1% CMWCNT in swelled

Figure 1a SAP-CNT 1% & SAP-CNT 2% state
Gas consisting of carbon dioxide can lower the This is where the carbon nanotubes have been
pH value below 2.9, which is normally added at
taken into consideration because of their
a high pressure. Many oil reservoirs in the world
use seawater to help produce oil. It is injected surface area enhancing properties along with
into the reservoir in order to push the oil to the being highly stable. A hybrid polymer absorbent
production wells. The pH of oilfield waters was considered to increase the efficiency as
usually is controlled by the CO2/bicarbonate well as the swelling capacity which might be
system. [3] suitable for use in Enhance Oil Recovery.
Such water can corrode steel of the bottom
hole assembly, in the case of the reservoir the
mineral present in it which can lead to
formation damage and hence decrease in
injection and production courtesy of the
pressure drop at the production well.
2. Experimental Section
Being non-Newtonian, polymers are prone to
2.1. Materials
salinity and high temperature causing a decline
Acrylic acid (AA, Dae-Jung), MBA (Sigma Aldrich)
in the properties as well as degradation unless
reinforced by a certain composite. Hence were used as purchased, Acrylamide (AM,
lowering the swelling capacity and eligibility for Mitsubishi) was recrystallized from Methanol,
 Proceedings of AMPE, 14-15 2015, Karachi, Pakistan

KPS and NaOH (Dae-Jung) were used as

received. CMWCNTs were from Sigma Aldrich. Sample Content
Name
All the solutions were prepared in double SAP-CNT Acrylic Acryla Potassi MBA CMWCNT
distilled water. 1% acid mide um (Methylen (Carboxyl
15gm 15gm persul ebisacryla ated
in in phate mide) Multi-
2.2. Synthesis 7.5gm 13.5g (initiat 0.015gm walled
of m of or) in 4g of Carbon
water, distille 0.2gm distilled Nanotube
The sonicated 1gm solutions of CMWCNT (in neutra d in 4gm water. s)
the specified percentages respectively) were lized water. of (0.023 sonicated
via distille mole % 1% in 1gm
mixed with the solutions of NaOH d ratio with of
up to water monomer) distilled
methylenebisacrylamide (MBA), acrylamide,
75% water
and acrylic acid (neutralized partially NaOH up
SAP-CNT Acrylic Acryla Potass MBA CMWCNT
to 75% in a cold bath) in a flask placed on a 2% acid mide ium (Methylene (Carboxyl
magnetic stirrer. With the temperature set at 15gm 15gm persul bisacrylamid ated
in in phate e) 0.015gm Multi-
131˚Fahrenheit along with Nitrogen gas being 7.5gm 13.5g (initiat in 4g of walled
introduced to keep the atmosphere inert. of m of or) distilled Carbon
water, distille 0.2gm water. Nanotube
neutra d in 4gm (0.023 mole s)
Initiator (Potassium persulphate) was added for lized water of % ratio with sonicated
the purpose radical formation. With the via distille monomer) 2% in
NaOH d 1gm of
passage of time the viscosity increased and up to water distilled
75% water
eventually after a period of 20 minutes the gel
SAP Acryli Acryla Potassium MBA
formed rapidly. The gel was allowed to cool c acid mide persulphat (Methyle
15gm 15gm e nebisacryl
down for a while, then was cut down into small in in (initiator) amide)
pieces and was placed in an oven at 140˚ 7.5gm 13.5g 0.2gm in 0.015gm
of m of 4gm of in 4g of
Fahrenheit for 24 hours. water, distill distilled distilled
neutr ed water water.
Afterwards the tiny gel pieces assumed the alized water. (0.023
via mole %
form of crystals and were milled in a hammer- NaOH ratio with
up to monomer
type-mini-grinder to obtain a powder form. [4] 75% )
The ratio of MBA with the monomer was 0.23 Table 1. (Contents for the synthesis)
mole% for the purpose of having maximum
capacity in the polymer. Table 1. Indicates the
content used for the synthesis of both the Structural Characterization and
samples. Morphological Observation
Variable pressure field emission scanning
electron microscopy (FESEM; Zeiss Supra 40VP)
was used to study the dispersion of CMWCNTs
into the fractured gel and the polymers
interaction with the CMWCNTs.

Fourier transform infrared spectroscopy (FTIR,

Perkin-Elmer Spectrum One, USA) was used to
study the characterization of the sample. (9)
 Proceedings of AMPE, 14-15 2015, Karachi, Pakistan

FTIR Analysis
From the FTIR analysis it was interpreted that
the absorption peaks at 3421.07cm-1 belong to
O-H stretch, H-bonded being of the functional
group consisting of alcohol and phenol. The
frequency at 2929.67cm-1 belongs to the alkane
unit (C-H stretch), 2361.7 cm-1 wave number
having C ≡ N stretching. 1670.48cm-1 shows
evidence of the functional group of alkenes
from the -C=C- stretch bond, 1457.49cm-1
attributed C-H bend bond of alkanes,
1169.66cm-1 highlighted C-H wag (-CH2X) a
bond of the alkyl halide group, C-N stretch bond
from 1023.13cm-1 wave number showed the
existence of aliphatic amines. Alkyl halides
being represented by the C-Br stretch bond
with the peak at 669.19cm-1. Figure 5b shows
the FTIR analysis of SAP 2.
FESEM Analysis:
Field Emission Scanning Electron Microscope
was used for a better resolution of the surface
morphology. The working distances at which
the beam was focused were 3.6mm and 4.0mm.
The figure 2b. having 4.0mm of working
distance shows a dispersed image of a fractured
gel which clearly illustrates the uniform
dispersion of CMWCNTs into the hydrogel
network, no accumulations were formed.
Whereas the figure 2c. with 3.6mm working
distance shows a more focused image of the
polymer being wrapped around the MWCNT’s
surface, which has increased its thickness.

The 2361.7cm-1 wave number indicates that the

molecule peak at 2361.7 cm-1 shows C=N group
stretching [6], the polymer chains being
wrapped around the CMWCNT due to the
presence of amide group in both the samples. Figure 2b. FESEM image showing dispersion of
During swelling CMWCNTs aren’t released into CMWCNTs into the gel
the fluid because of this interaction.

Figure 2c. Focused image of the wrapping of

Figure 2a. FTIR Analysis of SAP 2
polymer around the CMWCNTs
 Proceedings of AMPE, 14-15 2015, Karachi, Pakistan

3. Results and Discussion

3.1 Dynamic Swelling Test
The compositional effect of CMWCNT on the
swelling behavior of hybrid hydrogel at various
saline conditions and at different temperature
ranges is the main objective of this study. The
gravimetric method was used to evaluate the
swelling kinetics of the hydrogels. For this
purpose hybrid hydrogel was displaced in the
saline water at different temperatures. After Figure 3a. Weight gain at 0.5%
each minute the SAPs were filtered out via a
100 mesh screen, the weight was noted and
was again displaced into the solution.
The degree of swelling at different times can be
calculated from the equation:

W (%) = (mt − m0/mt) × 100

Where mt and m0 are the weights of the

hydrogels at the predetermined time and at
time 0 (xerogel), respectively.

3.1.1. Swelling Average Weight Gain:

Figure 3b. Weight gain at 1%
The average weight gain difference between
the SAP-CNT 1% and SAP-CNT 2% is significantly
prominent ranging from 18grams to 3grams.
The salinity of 0.5% at temperature 150˚F favors
SAP-CNT 2%, showing a significant absorption
increase in comparison to that at ambient
condition. Although at 1% salinity the capacity 3.1.2. Relationship between Weight Gain and
decreases for both the SAPs SAP-CNT 1% has a Temperature
15 gram loss in comparison to the prior. The Maximum weight gain with time in which it is
SAP-CNT 2% has loss of only 2grams.However achieved depends upon the temperature. The
the weight loss at 150˚Fahrenheit at this salinity higher the temperature the faster is the
was significant for the 2% CMWCNT mixed SAP
transmission towards the peak capacity
(in comparison to the ambient) which was of
attainment. However the storage capacity
15grams. Figures 3a and 3b depict the
observations discussed. decreases with increase in the temperature it
can be moderated via increase in the CMWCNT
percentage. Table 3a shows the impact of
temperature on the absorption rate.

Salinit Temperatu SAP-CNT
y re 1%
% ˚F (gm.)
0.5 90 75.06
0.5 150 65.2
1 90 58.08
1 150 53.19
Table 3a. Maximum Weight Gain in Swelling
3.2. Comparison in weight gain at different
salinities between SAP and SAP-CNT
The weight gain difference between SAP and
SAP-CNT is prominent. The results when
comparing the maximum weight between the
two in distilled water shows a swelling increase
of 17 grams in the SAP-CNT. When measuring in
a 1% saline constituency a notable weight boost
of 61.61grams was observed by the SAP-CNT.
Confirming the enhancement in swelling
capacity by addition of CMWCNTs in the
polymer system. Figure 3c illustrates the
difference.
100
90
80
70
60
Weight [gm]
50
40
30
20
10
0
0 1
Salinity [%]
Figure 3c. Comparison between SAP & SAP-CNT
3.2. Effect of pH on Swelling:
Five solutions of different pH were taken for
scrutinizing the performance of SAP at different
pH conditions since the reservoir fluid is
generally acidic in nature and can be below the
pH level of 2.9 therefore testing was done in a
at different pH values especially below 2.9 ph.
The SAP-CNT showed the highest absorption
rate in acidic medium contrary to the SAP this is
because in the case of SAP at lower PH swelling
capacity decreases as the sodium carboxylate
Proceedings of AMPE, 14-15 2015, Karachi, Pakistan
group on the polymer network is protonated.
Tim SAP-CNT Tim
e 2% e The polymer shrinks and become hydrophobic,
(sec. (gm.) (sec. as a result decreases the degree of ionization
) ) hence decreasing the swelling ratio. Whereas a
540 78.18 300
180 85 180 reverse behavior was observed for SAP-CNT,
300 71.61 120 there could be two possibilities either; we have
120 58.11 180 excessive carboxylate (COO) and hydroxyl (OH)
groups present in the system (due to
CMWCNT), leading to electrostatic attraction in
the system. The carboxylate/hydroxyl groups
have electrostatic interaction with carbonyl
groups (COONa), addition of HCl could
protonate the carboxylic group leading to
electrostatic repulsion between Na+ ions. Hence
enhancing the swelling capacity. The second
possibility could be that on the addition of HCl
in the system the Cl- ions bond with Na+ ions of
the carbonyl group due to which excessive
COO-¬ groups form an electrostatic repulsion
with one another causing enhancement in the
swelling capacity. [7]
SAP
SAP-CNT2%
Figure 3d. Effect of pH on Swelling
In case of SAP-CNT 1% the swelling dropped at
a pH value of 8.31 however its rate of
absorption increased at 12 ph.
4. Conclusion:
It is clear from the study conducted that SAPs
have a major role play in the field of Enhanced
Oil Recovery and can be applicable to further
usage in the oil and gas sector. The CMWCNTs
increase the swelling capability as well as
stabilize the performance in low pH conditions
and moderate the absorption capacity at high
 Proceedings of AMPE, 14-15 2015, Karachi, Pakistan

temperatures with the increase in the

percentage of the CCMWNT. The process of
absorption is safe since no carbon nanotubes
are released in the environment.
5. References
[1] EOR Methods, Chandran Udumbasseri,
Technical Consultant.
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[9] Saud Hashmi, Amin GhavamiNejad,
Francis O. Obiweluozor,
Mohammad Vatankhah-Varnoosfaderani,
and Florian J. Stadler, Supramolecular
Interaction Controlled Diffusion Mechanism and
Improved Mechanical Behavior of Hybrid
Hydrogel Systems of Zwitterions and CNT,
dx.doi.org/10.1021/ma301366h |
Macromolecules 2012, 45, 9804−9815,
pubs.acs.org/Macromolecules

[2] A.Z. Abidina, T. Puspasaria, W.A. Nugrohoa,

“Polymers for Enhanced Oil Recovery
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16

[3] Produced Water Properties, Petrowiki,

published by SPE International.
http://petrowiki.org/Produced_water_properti
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[4] A. A. S. Al-Rossies, B. D. Al-Anazi and A. M.

Paiaman, “Effect of pH-values on the contact
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(2010)

[5] E. M. A. Hydrogel: Preparation,

characterization

[6] Preparation and characterization of

Poly-o-anisidine Sn(lV) tungstate & Poly-o-
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[7] Giuseppe Cirillo, Silke Hampel, Umile

Gianfranco Spizzirri,
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