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Journal of Industrial and Engineering Chemistry

journal homepage: www.elsevier.com/locate/jiec

Amphiphilically modified chitosan copolymer for enhanced

oil recovery in harsh reservoir condition
Wan-Fen Pu a,b,*, Rui Liu a,b,**, Qin Peng c, Dai-Jun Du b, Qi-Ning Zhao d
a
State Key Laboratory of Oil and Gas Reservoir Geology and Exploitation, Southwest Petroleum University, Chengdu 610500, China
b
Petroleum Engineering Institute, Southwest Petroleum University, Chengdu 610500, China
c
Northwest Sichuan Gas Purification Plant, PetroChina Southwest Oil & GasField Co., Ltd, Jiangyou 621700, China
d
School of Geoscience and Technology, Southwest Petroleum University, Chengdu 610500, China

A R T I C L E I N F O A B S T R A C T

Article history: A novel amphiphilically grafting natural chitosan copolymer (PAMCS) was prepared by using one step
Received 17 February 2016 water-free radical polymerization strategy and the basic parameters for PAMCS were systematically
Received in revised form 19 March 2016 characterized. The rigid D-glucosamine unit, intermolecular association and hydrogen bonding
Accepted 20 March 2016
synergistically endowed PAMCS solution with rheological properties, super-high salt resistance and
Available online xxx
temperature tolerance in harsh reservoir condition. PAMCS solution exhibited viscoelastic behavior
and formulated the unique displacement mechanism in comparison to that for partially hydrolyzed
Keywords:
polyacrylamide. Moreover, the mass concentration, injective rate and polymer solution slug related to oil
Amphiphilically modified chitosan
copolymer
recovery efficiency for PAMCS were investigated from the economic point.
Rheological properties ß 2016 The Korean Society of Industrial and Engineering Chemistry. Published by Elsevier B.V. All rights
Super-high salt resistance reserved.
Temperature tolerance
Polymer flooding

Introduction HPAM [4–6]. Furthermore, the mechanical shear stress is accom-

Almost 70% crude oil of the Original Oil in Place (OOIP) is left in
the subterranean formation after water flooding because of the
unfavorable water/oil ratio resulting in the severe water break-
through and the rapid increase of water cut [1,2]. It is the target of
chemical flooding for enhanced oil recovery (EOR). Partially
hydrolyzed polyacrylamide (HPAM) has been widely used as a
water-soluble polymer in chemical EOR process due to its
favorable solubility and the capability of adjusting displacing fluid
mobility in the mild reservoir condition [3]. With the develop-
ments exploring to deeper, and the harsh reservoirs, HPAM faces
with considerable challenges. The linear flexible chains deform
extremely at upgraded temperature, and the negative charges
carried by carboxyl groups are forced by cationic ions in high
salinity condition, resulting in the fragile thickening efficiency for
* Corresponding author at: Petroleum Engineering
Institute, Southwest
Petroleum University, Xindu Avenue No. 8, Chengdu 610500, China.
Tel.: +86 13880551801.
** Corresponding author at: Petroleum Engineering Institute, Southwest
Petroleum University, Xindu Avenue No. 8, Chengdu 610500, China.
Tel.: +86 15928967990.
E-mail addresses: pwf58@163.com (W.-F. Pu),
breakthroughliu@163.com (R. Liu).
panied with the lifetime of polymer solution from the injectors to
the produces, which is associated with the irreversible shear
degradation and impairs its viscosifying power.
Many researchers proposed that hydrophobically associative
polymers where HPAM is modified with a small proportion of
hydrophobic moieties, can somewhat improve its linear flexible
chains [7–10]. Above the critical associative concentration (CAC),
hydrophobic groups interact between polymer chains to form a
transient network resulting in the desirable rheology modifiers
with versatile of applications. Controlling the hydrophobic inter-
molecular association to manipulate the strength of topological
structure could guarantee polymer solution benign stability in
harsh condition [11,12]. Owing to the particular shearing thinning
and thixotropic properties, and high interfacial activities because
of the presence of hydrophobic groups [13], the potential of those
polymers in EOR applications has been of great interest in
petroleum industry.
Given the plunging crude oil price worldwide, the strategy to
manipulate chemical flooding system at lower cost with higher oil
recovery efficiency has attracted intense attention. Considerable
interest has been generated in modulating smart polymers based
on availably natural polymers, such as polysaccharides [14–18].
Chitosan is formed by extensive deacetylation of chitin that is a
typical polysaccharide outranked only by cellulose [19], comprising

http://dx.doi.org/10.1016/j.jiec.2016.03.034
1226-086X/ß 2016 The Korean Society of Industrial and Engineering Chemistry. Published by Elsevier B.V. All rights reserved.

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a large proportion of D-glucosamine units as well as a small
proportion of N-acetyl-glucosamine units. It is renewable and eco-
friendly that has been extensively investigated for macroscopic
materials [20], nanocarriers [21], genetic engineering [22] and
biomedical areas [23]. With the versatile number of structures
and possible configurations, the general modification notion cove-
red reactions with hydrophilic groups to increase water solubility
and with hydrophobic groups to facilitate the self-assembly into the
intelligent structures of modified copolymer [19,24–26]. Moreover,
the D-glucosamine unit of chitosan is a rigid structure of six member
heterocyclic ring [27], which might provide robust steric effect to
resist high temperature degradation. However, the reports on
synthesis of amphiphilically modified chitosan that are used as a
chemical flooding agent for EOR are rare.
According to Mandal et al. [28,29], significant works remain
indispensable for economic implementation of chemical EOR
process due to the fact that the composition of crude and reservoir
geological conditions vary from field to field, and the effect
flooding agent on the crude oil and rock matrix is naturally
complex. Thus, in this work, hydrophilic monomers and hydro-
phobic monomer surface grafting modified chitosan, namely
PAMCS was prepared (Fig. 1a) by a simple water-free radical
polymerization technique. IR, 1H NMR spectra and SEM experi-
ment have been done to characterize the structure of PAMCS. We
have investigated the comprehensive properties for PAMCS
solution, such as viscosified power, rheological performance, salt
resistance, temperature tolerance and long-term stability in harsh
condition. Moreover, a series of displacement experiments were
carried out to investigate the oil recovery potential for PAMCS.
Fig. 1. Schematic representation of the surfactant free synthesis of (a) amphiphilically modified chitosan (PAMCS), (b) the 3D structure of one fragment of PAMCS and (c) the
structure of HPAM.
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Experimental
Materials
Chitosan (AR) purchased from Alfa Aesar (UA), the degree of
deacetylation was 85.6%, and the weight-average molecular weight
(Mw) was 2.5  104 g/mol. Acrylamide (AM, CP) and acrylic acid (AA,
AR) were purchased from Chengdu KeLong Chemical Reagent Co.
Ltd., (China). AM was used after purification and AA was used
without further purification. 2, 20 -azobis (2-amidinopropane)
dihydrochloride (AIBA, 99.99%) purchased from Alfa Aesar was
used as received. 2-acrylamido-dodecyl sulfonate (AMC12S) was
prepared in the laboratory according to the literature [30]. HPAM,
one of the most widely used polymers that employed in oilfields for
oil recovery, was purchased from SNF Floerger Group (France), trade
name AN926: Mw 8.3  106 g/mol, hydrolysis degree 23.6%. Its
structure was listed in Fig. 1c. Crude oil and formation water were
obtained from a certain block in Dagang Oilfield (China). Sandstone
cores used for core flooding test were outcrop cores, which shared
similar geologic features as the selected block as they are at the same
tectonic level. The formation averaged temperature is 90 8C and
averaged total salinity 20,813 mg/L with the averaged water
permeability (Kw) of 100 mD. The formation water was filtered
twice to remove undissolved particles and the composition of the
formation water is listed in Table 1. The viscosity and density of
crude oil are 8.7 mPa s and 0.88 g/cm3 at the reservoir condition. The
SARA fractions of crude oil are as follows: saturated hydrocarbon
51.21%, aromatic hydrocarbon 19.07%, resin 29.46% and asphaltene
0.26%. The paraffin content is 18.15%. All supplementary materials
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Table 1 solution viscosity. Rheological experiments were carried out with a

Inorganic composition of formation water.
Salinity Ion items Total
concentration
K+ + Na+ Ca2+ + Mg2+ Cl SO2
4 HCO
3 strikes a good balance between torque sensitivity and response in
mg/L 7797 267 12,124 0 610 20,813
such as inorganic salt (AR) were used as received. Water was double
deionized with a Millipore Milli-Q system to produce the 18 MV
deionized water.
Synthesis of PAMCS
The desired amount of chitosan powders was dissolved in AA
aqueous solution, and then some quality of AM and AMC12S were
added into the solution with magnetic stirring, the pH of mixture
solution was moderately tuned by a small amount of sodium
hydroxide. The mixture was poured into a reactor, and the reactor
was sealed after N2 protection for 30 min. We noted that the
weakly acidic condition of aqueous solution guarantees dissolva-
bility of chitosan (see Fig. S1 in the Supporting Information).
Hydrophobic monomer (AMC12S) more preferentially grafted to
the –NH2 sites of chitosan, simultaneously, hydrophilic monomers
(AM, AA) more preferentially grafted to the –OH groups of chitosan
by using a cationic azo initiator (AIBA). The water-free radical
polymerization was carried out to synthesize amphiphilically
modified chitosan copolymer abbreviated PAMCS under the
reaction temperature of 45 8C at the adiabatic condition for 6 h.
The light yellow granules, after being purified repeatedly with
ethanol, were dried at 60 8C under vacuum for approximately
12 h.
Characterizations
The structure of PAMCS was characterized by IR and 1H NMR.
The intrinsic viscosity ([h]) of PAMCS was determined by an
automatic capillary viscometer (Ubbelohds type) in 1.0 mol/L NaCl
aqueous solution at ambient temperature. The gyration and Mw of
PAMCS were measured in water/methanol mixture (3/7 v/v)
containing 1.0 mol/L NaCl utilizing classical light scattering
equipped with a multiangle spectrometer (AMTEC Model MM1)
at 633 nm. The morphologies of polymer solution samples were
obtained by environment scanning electron microscope (Philips,
Model, SEM XL 30).
Comprehensive solution performance
PAMCS and HPAM solution was prepared by dissolution of a
known amount of polymer powder in water or salinity solution,
the procedure is consistent with the literature [3]. The apparent
viscosity of samples was determined by a Brookfield DV-III
rheometer equipped with different size of spindles depending on
Haake RS600 controlled-stress rheometer equipped with a cone
pH plate geometry (angle 18, diameter 35 mm). Frequency sweeps in
the range of 0.01–10 Hz were applied at low strain. A strain of 0.6%
7.01 linear zone. Polymer samples were slowly placed between the plates
and were allowed to equilibrate for 1 h prior to each round sweep. To
evaluate the long period stability of polymer in the high temperature
and high salinity reservoir, polymer samples prepared by injected
water was aged at 90 8C in anaerobic condition.
Rheological performance in porous media and Polymer flooding for
EOR
Core flooding experiments were carried out to investigate the
viscoelastic performance of polymer solution in porous media and
formulate the optimized injective rate of polymer flooding for EOR.
The schematic diagram of the experimental apparatus is shown in
Fig. S2. The method and procedure to measure the basic
parameters of sandstone cores, including pore volume (PV),
porosity (F), oil saturation (So) and Kw; and to investigate the
effective viscosity [31], the resistance factor (fr) and the residual
resistance factor (frr) of polymer in the porous media [32], were
fully addressed in the Supporting Information. Additionally, the
procedure of polymer flooding for EOR was available in the
Supporting Information.
Table 2 outlines the sandstone cores parameters for each
displacement test.
Results and discussion
Optimal synthesis condition of polymerization
Apparent viscosity of PAMCS samples related to the variation of
synthesis condition is identified by a single variable method (see Fig.
S3 in the Supporting Information). The optimal synthesis condition
for the PAMCS is as follows: the AIBA concentration is 0.12 wt%; pH
value of the solution is 5.5; the chitosan concentration is 1.2 wt%;
the feed ratio of AA/AM in weight is 25/75; and the total feed
monomer is 10–12.5 wt%. The resulted copolymer PAMCS was
prepared that the apparent viscosity is 196.3 mPa s at 1750 mg/L.
Characterization
Fig. 2 and Fig. S4 show the IR and 1H NMR characterizations for
chitosan, AMC12S and PAMCS. Detailed information on character-
izations of chitosan, AMC12S and PAMCS, and detailed methods
[33–35], and figures (Figs. S5–S7) on basic parameters for PAMCS
[critical overlap concentration (c*) and CAC] and HPAM (c*), are
available in the Supporting Information. The mean diameter for
PAMCS and HPAM in 1.0 mol/L NaCl solution is 286 nm and
341 nm, respectively. The c* of HPAM is 658 mg/L. The Mw, c* and
CAC of PAMCS is 7.6  106 g/mol, 743 mg/L and 958 mg/L, res-
pectively.

Table 2
Basic parameters of cores.

Core no. D (cm) L (cm) Kw (mD) F (%) Core no. D (cm) L (cm) Kw (mD) F (%) So (%)

1 3.82 7.58 79.2 14.3 8 3.86 7.64 109.3 17.2 –

2 3.85 7.57 86.6 15.7 9 3.89 7.71 95.6 16.4 –/
3 3.81 7.68 119.1 16.8 10 3.86 7.72 103.5 16.1 54.3
4 3.91 7.69 122.7 17.3 11 3.88 7.68 109.7 15.7 56.8
5 3.84 7.71 98.5 15.2 12 3.91 7.69 97.6 16.6 60.7
6 3.85 7.72 103.6 16.1 13 3.90 7.73 89.7 14.4 61.5
7 3.87 7.63 101.3 15.1 14 3.87 7.64 112.1 16.3 59.1

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Fig. 2. IR spectrum of chitosan, AMC12S and PAMCS (a), and (b) 1H NMR spectrum of PAMCS.

The typical morphologies for chitosan, HPAM and PAMCS
specimens were observed through SEM, which are shown in
Fig. 3. The network morphology of chitosan in the weakly acidic
solution is observed, indicating that polymer based on surface
modified chitosan would have versatile performance. The mor-
phology of HPAM is irregular and rough due to the disordered
aggregation of polymer chains, whereas, the regular and the trunk
of the network structure for PAMCS solution is observed owing to
the intermolecular association of hydrophobic groups to form
hydrophobic domains and hydrogen bonding of D -glucosamine
units of polymer chains. We consider this morphology constructed
by amphiphilically modified the rigid chitosan might have unique
rheological performance and displacement properties.
Comprehensive properties
Thickening efficiency for PAMCS and HPAM as a function of
polymer mass concentration in deionized water is shown in
Fig. 4. In dilute regime, PAMCS and HPAM display viscosified
behavior of directly proportional linear relationship, and HPAM
has the larger thickening efficiency in comparison to that for
PAMCS. In semidilute regime, both PAMCS and HPAM exhibit
classical behavior of power law fluid. Above the CAC, an upward
curvature in the apparent viscosity for PAMCS can be observed due
to the intermolecular association of hydrophobic groups to form
hydrophobic domains and hydrogen bonding of PAMCS chains to
construct transitory three dimensional networks. We noted that
both the viscosity of PAMCS and HPAM with polymer concentra-
tion ranging from 1000 to 1500 mg/L is comparable. Intermolecu-
lar association and hydrogen bonding of PAMCS chains makes
more thickening efficiency than that for HPAM when polymer
concentration surpasses 1750 mg/L.
The variation of the dynamic elastic modulus (G0 ), the viscous
modulus (G00 ) and crossing point (Gc), which were dependent on
frequency is shown in Fig. 5. For all the specimens, the lg G0 (lg G00 )
shows linear behavior to lg Hz. In the case of chitosan, G00 is larger
than G0 within the whole frequency region, suggesting chitosan
solution is the classic plastic fluid. As for PAMCS and HPAM, G0 is
less than G00 in the low-frequency region, indicating viscous
modulus plays a dominating role. G0 and G00 increase gradually as
the rise in the frequency. As for PAMCS and HPAM, above the
critical frequency at which curves G0 and G00 cross each other (Gc),
and the elastic modulus plays a dominating role. The characteristic
time tc corresponding to the crossing point Gc can quantify
disassociate lifetime [32]. According to the data, the tc for PAMCS
and HPAM is 16.7 s and 3.3 s, respectively. The longer tc for PAMCS
verifies the amphiphilically modified chitosan structure makes
more contributions to elastic efficiency and relaxation time, and
thus, PAMCS has better viscoelastic properties than HPAM.
Fig. 6 shows the effect of salt type and concentration on the
apparent viscosity of PAMCS and HPAM solution. The thickening
capability for HPAM mainly lies in electrostatic repulsion of
hydrophilic chains. By addition of a small amount of salt, polymer
chain shrinks due to the electrostatic screening by cations, which
sharply decreases polymer viscosity [3]. The effect of salt on the
apparent viscosity of hydrophobically associative polyacrylamides
solution can be interpreted as two mechanisms: electrostatic
screening and hydrophobic microdomain being induced by cations
that deeply related to the hydrodynamic size of polymer solution
[12] (see Fig. S8 in the Supporting Information). Upon addition of a
small amount of salt, the shielding capacity of the cations is the
dominated effect. It results in the decrease of polymer hydrody-
namic size, which is accompanied with a reduction in apparent
viscosity. With increasing salt concentration, the formation of

Fig. 3. SEM morphologies of (a) chitosan with mass concentration of 5000 mg/L in weakly acidic solution, (b) HPAM with mass concentration of 2000 mg/L in deionized water
and (c) PAMCS with mass concentration of 2000 mg/L in deionized water.

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1400
1200
Apparent viscosity (mPa.s)
1000
800
600
400
200
0
0 500 1000 1500 2000 2500
polymer concentration (mg/L)
Fig. 4. Apparent viscosity as a function of polymer concentration for PAMCS and
HPAM (deionized water, shear rate 7.34 s1, T = 25 8C).
hydrophobic microdomain enhanced by salt results in a stronger
dynamic network (the larger hydrodynamic size), which domina-
teselectrostatic repulsion and makes contribution to the apparent
viscosity. With further increase in salt concentration, the formation of
hydrophobic microdomain is compacted by higher strength of cation
and the entire transient network is divided into smaller ones. The
apparent viscosity of HPAM solution is lower 20 mPas with the salt
concentration of 60,000 mg/L. However, the apparent viscosity of
PAMCS solution is 144 mPa s at the corresponding NaCl concentra-
tion, 100 mPa s at the CaCl2/MgCl2 concentration of 500 mg/L, and
129 mPa s in the Dagang formation water, respectively.
Fig. 7a shows the influence of temperature on the viscosity of
PAMCS and HPAM solution prepared with deionized and formation
water. In deionized water, the viscosity for PAMCS and HPAM
specimens at the 90 8C are 110 mPa s with viscosity retention rate
56% and 83.4 mPa s with viscosity retention rate 42.3%, respectively.
The upgrade temperature and harsh formation water cooperatively
downgrade the apparent viscosity. Only 12 mPa s of apparent
viscosity for HPAM solution is observed, whereas, the apparent
viscosity for PAMCS solution is 83 mPa s under the same condition.
The apparent viscosity of PAMCS and HPAM with concentration
of 1750 mg/L in formation water was measured at different times
after aging at 90 8C (deoxidation environment), as depicted in Fig. 7b.
Apparent viscosity for PAMCS solution reaches 56.9 mPa s with
viscosity retention rate of 44%, while it is only 7.9 mPa s with
viscosity retention rate of 21.5% for HPAM solution. PAMCS
possesses better temperature resistance, confirming that interaction
between hydrophobic groups and the D-glucosamine groups provide
steric hindrance for the PAMCS chains that weakens the influence of
temperature on shrinkage degree of the polymer chain.
Fig. 6. Apparent viscosity as a function of salt concentration of (a) NaCl, (b) CaCl2/MgCl2 and (c) diluted formation water (polymer concentration 2000 mg/L).
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5
1
Storage (G') or Loss (G'') modulus (Pa)
0.1
G' PAMCS
G'' PAMCS
G' HPAM
G'' HPAM
G' chitosan
G'' chitosan
3000 3500 4000
0.01
0.01 0.1 1 10
f (Hz)
Fig. 5. Storage (G0 ) and loss (G00 ) modulus as a function of frequency for PAMCS
(2000 mg/L), HPAM (2000 mg/L) and chitosan (5000 mg/L, in weakly acidic
solution).
Rheological properties in porous media
Fig. 8 shows the injectivity for polymer solution with the
variation of mass concentration. The injective pressure rises with
the increase polymer slug due to the mobile control capability for
polymer to water phase and the adsorption of polymer coils onto
the rock to reduce the water phase permeability [36]. It reaches
stable when polymer slug is breakthrough from the outlet of the
core. The stable injective pressure for 1750 mg/L and 2000 mg/L
HPAM flooding is 0.11 MPa and 0.13 MPa, respectively, indicating
that HPAM with both mass concentrations can pass through pores
and throats. However, the relatively small stable injective pressure
and chase water flooding pressure imply the limited efficiency for
HPAM flooding. The similar injectivity for PAMCS flooding at the
lower PAMCS mass concentration is observed. Increasing PAMCS
concentration to 1500 mg/L, the relatively higher injective
pressure and chase water pressure suggest that the displacement
agent has been more effective in controlling mobility and
selectively absorbs onto the rock to adjust water phase perme-
ability in comparison to that for HPAM. We noted that higher
polymer concentration (1750 mg/L) results in polymer coils
blocking effective pores and failing to propagate through the
core.fr quantifies the mobility capability of polymer solution by
increasing water viscosity and decreasing porous permeability;
and frr is defined as the degree of permeability reduction of porous
media after polymer flooding [37,38]. fr and frr constructed by
HPAM and PAMCS solution at the Dagang formation cores are
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Fig. 7. Apparent viscosity of polymer samples versus (a) temperature (polymer concentration 2000 mg/L, shear rate 7.34 s1) and (b) aging times after aging at 90 8C
(formation water, polymer concentration 1750 mg/L, shear rate 7.34 s1).

0.14 0.6

0.12 0.5

0.10
0.4
Pressure (MPa)

Pressure (MPa)
0.08
0.3
0.06
0.2
0.04
0.1
0.02
0.0
0.00
0.0 0.5 1.0 1.5 2.0 2.5 3.0 3.5 0.0 0.5 1.0 1.5 2.0 2.5 3.0 3.5
(a) Injection Volume PV (b) Injection Volume PV

Fig. 8. The injective performance for HPAM and PAMCS solution in the porous media (Dagang formation water, 90 8C).

listed in Table 3. Comparing to HPAM, intermolecular hydrophobic constructed effective viscosity of 15.5 mPa s at the polymer mass
association and hydrogen bonding endow PAMCS with higher fr concentration of 2000 mg/L; the optimized injective rate for
and frr at the economic polymer concentration. The result is PAMCS solution is close 1.2 mL/min, which formulated effective
consistent with other reports on the flow characters for hydro- viscosity of 24.7 mPa s at the polymer mass concentration of
phobically modified polyacrylamides [39–41]. 1500 mg/L. Moreover, the data further confirms that the associa-
The structure of a porous media can be seen as variation tive property and disassociated character related to flooded
openings and confined throats through which polymer chains
must undergo variation of shear stress. It is well known that
polymers based on HPAM exhibit viscoelastic fluid behavior 30
(pseudoplastic fluids at the lower shear rate and pseudoplastic core 8
fluids at the moderate shear rate) [3,37]. Therefore, it is significant PAMCS
HPAM
to design desirable injective rate to implement polymer flooding.
chitosan
Effective viscosity (mPa.s)

According to the effective viscosity of polymer solution as a

function of shear rate in porous media (see Fig. 9), the optimized 20
injective rate for HPAM solution is close 0.9 mL/min, which
core 7

10
Table 3
fr and frr formed by polymer solution.
core 9
Core no. Kw (mD) Polymer Polymer fr frr
type concentration
(mg/L)
0
1 79.2 HPAM 1750 8.46 2.62 10 100 400
2 86.6 2000 14.1 3.94
3 119.1 PAMCS 1000 15.43 3.38 shear rate γ (s-1)
4 122.7 1250 17.76 5.76
Fig. 9. Effective viscosity for PAMCS solution (1500 mg/L), HPAM solution
5 98.5 1500 23.63 7.89
(2000 mg/L) and chitosan solution (5000 mg/L, weakly acidic solution) as a
6 103.6 1750 – –
function of shear rate in porous media.

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Fig. 10. Effect of PV for polymer solution on oil recovery efficiency (a)–(e), and (f) oil recovery as a function PAMCS solution slug.

velocity endow PAMCS reversible supermolecular network, thus,
PAMCS solution can navigate though the porous media without
undergoing severe mechanical degradation.
Polymer flooding for EOR
In this part, we further investigated the optimized polymer
parameter (favorable polymer concentration and injective rate) on
oil recovery. As a contrast experiment, we formulated HPAM
flooding and studied its oil recovery efficiency. In the case of cores
10# to 14#, the initial oil in OOIP for water flooding is recovered
when the water cut was close 98%. 0.3 PV HPAM flooding with the
polymer concentration of 2000 mg/L is injected into the high water
cut core and the injective pressure increases to some extent (see
Fig. 10a). 17.2% oil recovery is obtained after 0.3 PV HPAM flooding
(including the chase water flooding). Whereas, the corresponding
oil recovery efficiency (16.7%) is reached by 0.2 PV PAMCS flooding
(polymer concentration 1500 mg/L). We speculate that the
increase in polymer slug PV might further upgrade the oil recovery
potential for PAMCS flooding.
The tests on core 12# and core 13# confirm that increasing the
PAMCS solution slug would increase the polymer flooding
efficiency to an amount, with 21.6% OOIP for 0.25 PV PAMCS
flooding, and 25.1% OOIP for 0.3 PV PAMCS flooding, respectively.
However, further increasing polymer slug to 0.35 PV, the
accumulative oil recovery is inconspicuous (core 14#, Fig. 10e).
We curved the plotting of the oil recovery potential as a function of
polymer slug from 0.2 PV and 0.35 PV at the identical polymer
concentration of 1500 mg/L, as shown in Fig. 10f. It is the negative
exponential curve, which indicates that 0.3 PV PAMCS solution
with polymer concentration of 1500 mg/L might be an economic
flooding system for the harsh Dagang reservoir.
Conclusions
In this study, a novel copolymer PAMCS was synthesized and its
displacement properties in harsh reservoir condition was systemati-
cally investigated. By grafting hydrophilic chains and hydrophobic
chains onto the group sites of chitosan, PAMCS displayed shear-
responsive and viscoelastic properties in comparison to that of

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the raw chitosan. The rigid D-glucosamine, intermolecular association
as well as hydrogen bonding synergistically endowed PAMCS
solution with high salt resistance, desirable temperature tolerance
and the long-time aging stability. Core flooding experiments
indicated that PAMCS solution with the mass concentration of
1500 mg/L would have the benign injectivity in the Dagang oilfield
sandstone cores, and the fr and frr was 23.63 and 7.89, respectively.
Moreover, both the injected rate and the economic slug for PAMCS
solution were manipulated and the results indicated that 25.1% OOIP
was recovered by employing 0.3 PV PAMCS solution with the injected
rate of 1.2 mL/min after water flooding with the water cut of 98%.
Owing to the fact that reservoir conditions such as geological factor,
salinity and temperature are varied from oilfield to oilfield, the
adaptability of PAMCS to various harsh reservoirs in comparison to
that of other salt-resistant and temperature-tolerant polymers
should be further investigated.
Acknowledgments
We are grateful to the Open Fund (PLN1417) by State Key
Laboratory of Oil and Gas Reservoir Geology and Exploitation
(Southwest Petroleum University) for financial support of this
work. The authors express sincere appreciation to editor professor
Jin Woong Kim and to the reviewers for their constructive
comments.
Appendix A. Supplementary data
Supplementary data associated with this article can be found, in
the online version, at doi:10.1016/j.jiec.2016.03.034.
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