201600036
of the PPNs promotes the effectiveness of the PPNs as viscosity modifiers, as the maximum viscosity enhancement is
achieved at longer residence times in the reservoirs. This can
be up to 30 days, and the released polymer maintained its activity. Under conditions of high salinity (total dissolved
solids = 178 082 mg L@1), temperatures up to 90 8C, and shear
rates up to 1000 s@1, PPNs have shown superior properties,
such as elastic modulus, shear rate behavior, viscosity loss,
and sand adsorption over PAM, whereas the areal sweep efficiency of PPNs is similar to that of PAM and higher than
that of conventional water flooding. All of this makes PPNs
promising candidates for polymer-enhanced oil recovery.
Introduction
As alternative energy sources have not yet achieved the necessary level to meet the worldQs energy demand, it has
become increasingly important to find an efficient way to enhance the recovery of the oil that remains in oil reservoirs.
Water flooding is one of the methods used most widely for
oil recovery; however, its sweep efficiency is not very high
because of water channeling phenomena. As a first alternative, polymer flooding has been used to overcome the poor
efficiency of water flooding and, because of the increased
viscosity of the aqueous phase,[1, 2] polymer flooding yields
a considerably enhanced oil recovery (EOR).[3, 4] Aqueous
solutions of high-molecular-weight polyacrylamide (PAM)
and its partially hydrolyzed form (HPAM; > 1 X 106 g mol@1)
as thickening agents are the most widely used displacing
fluids to modify the mobility ratio of water to oil because of
the viscosity enhancement of the injected water.[5] This viscosity enhancement results from the high molecular weights
of the polymers and repulsion between the negative charges
along the polymer chains that causes their expansion and increases their hydrodynamic volume in water solution. Therefore, these solutions can push oil to the production wells
before the water channeling phenomenon occurs in the underground reservoirs.[6] However, there are many limitations
of the use of PAM and HPAM in conventional polymer
flooding processes, such as the chemical, thermal, mechanical, shearing, and biological degradation of polymer chains
during the EOR process.[7, 8] The most important polymer
degradation seems to be the chemical one. As there are different types of salts in formation water in oil reservoirs, the
Energy Technol. 2016, 4, 1035 1046
1035
through pumps, chokes, and valves has been reported recently.[12, 13] All these effects cause a decrease in the PAM and
HPAM viscosity-enhancement function.
To improve the corresponding polymer solution properties
and to increase the EOR performance, numerous studies associated with attempts to alter the chemical structure of
PAM for polymer flooding process have been undertaken.[1418] These attempts are summarized as a replacement of
acrylamide (AM) moieties with more resistant non-ionic
monomers (for example N-vinyl pyrrolidone; NVP)[14] or
more resistant anionic monomers (e.g., 2-acrylamido-2-methylpropane sulfonic acid; AMPS)[15] that suppress cation
shielding and the precipitation of acrylate moieties in the
polymer chains; the synthesis of comb-polymers to create
steric hindrance between polymer chains and prevent the full
collapse of the hydrodynamic radius (e.g., a polypropylene-gpolyethylene comb-type copolymer);[16] the synthesis of hydrophobically associated polymers for intermolecular association and subsequent viscosity enhancement;[17] and the copolymerization of AM monomers with a thermo-sensitive comonomer to increase the viscosity of the aqueous solution at
high temperatures and salinities.[18] Clearly, the reported efforts are focused on the development of new chemical structures of polymers for EOR applications. On one hand, this
results in the development of complicated synthesis procedures that are difficult to scale up and, on the other hand,
the good performance of the PAM structures already used
widely in polymer flooding on a commercial level can hardly
be overcome.
In this work, we report on a diverse approach that allows
us to take advantage of the good performance of PAM in
flooding processes and simultaneously to overcome the main
drawback of limited stability toward the harsh environment
in the reservoirs. A new method to synthesize coreshell-protected PAM nanostructures (PPNs) by superficial copolymerization with styrene has been developed based on already patented preliminary efforts.[19, 20] Following this procedure,
a polystyrene-rich copolymer forms a protective nanolayer
shell around the PAM chains. This new synthetic method has
been applied to obtain PPNs with different copolymer shell
thicknesses. The stability against degradation and the performance of the nanostructures as a flooding medium in
EOR process were investigated in a simulated harsh environment (high temperature, salinity, and shearing). The efficiency of the coreshell nanostructures was compared to that of
the unprotected PAM polymer.
The advantages of these structures as a medium for polymer flooding are clear. On one hand, the hydrophobic shell
protects the PAM active polymer chains from premature
degradation during the injection and flow processes until
they reach the target. After the contact with oil phase that
dissolves the polystyrene (PSt) shell, a triggered release of
PAM chains, which act as rheological modifiers, occurs. Finally, as PPNs are water insoluble, their aqueous dispersions
are injected into the reservoirs with a significantly lower viscosity (close to the viscosity of water) than the polymer solution used commonly as a flooding medium. This allows the
Energy Technol. 2016, 4, 1035 1046
use of water-flooding equipment for their injection into reservoirs, which ensures a much lower cost than that of traditional polymer flooding.
1036
Figure 2. Particle size distribution of a) LT-PPN, b) HT-PPN, and c) PAM samples (measured by DLS).
dDLS [nm]
dcore [nm]
Thshell [nm]
dcore/dout
LT-PPN
HT-PPN
72.5
78.4
61.4 : 1
61.6 : 1
10.83 : 1
23.95 : 1
0.85 : 0.5
0.72 : 0.5
0.0027
0.0065
separate phases that come from the constituents. Strong interactions between the two polymers are clear from the
slight shifts of the Tg values noted for the PPNs with respect
to the neat polymers and by the constricted glass transition
regions.
1037
1
10
20
30
HT-PPN0.2
HT-PPN0.3
60 8C
LT-PPN0.2
LT-PPN0.3
HT-PPN0.2
HT-PPN0.3
1.01
1.00
0.98
1.02
1.00
1.03
0.99
1.05
1.09
1.06
1.01
1.01
0.85
0.79
0.83
0.81
0.89
0.78
0.89
0.80
0.84
0.84
0.81
0.80
0.90
0.77
0.84
0.87
1.11
1.07
1.08
1.09
chains. It is clear that the Poly(AM-co-St) chains were released in 1518 h, which depends on the shell thickness and
concentration (Figure 4). The samples with thicker shells released & 10 % less, whereas more concentrated dispersions
released a slightly higher amount of Poly(AM-co-St). Notably, the maximum release of the Poly(AM-co-St) chains was
below 100 % at room temperature, likely because of the incomplete removal of the polystyrene shell. On one hand,
these results indicate that by controlling the shell thickness
and the PPNs content, the release time can be set carefully
according to the necessity and depth of different reservoirs.
However, this behavior allows the introduction of PPNs dispersions into the deeper areas of reservoirs, in which the release of Poly(AM-co-St) allows the water-pushing phase to
become more viscous to displace the remaining oil.
The dissolution test was performed at 30, 60, and 90 8C
using synthetic seawater with total dissolved solids (TDS) of
178,082 mg L@1 (Table S1) to study the effect of temperature
on the release of the Poly(AM-co-St) chains (Figure 5).
The results, presented in Figure 5 as the change in the kinematic viscosity with time at different temperatures, reveal
that PPNs release Poly(AM-co-St) in three different behavior regions: 1) at the initial release time (ti), the coreshell
dispersion had a low viscosity (nmin); 2) at an increased exposure time, the viscosity was enhanced because of polystyrene
dissolution in the oil phase, which reached the maximum
value (nmax) at the critical time (tmax); and 3) after the
Poly(AM-co-St) discharge was complete, the viscosity
became stable. This means that the release of the Poly(AMco-St) chains starts after contact with the oil phase, which is
necessary to dissolve the shell, and reaches its maximum
values after certain period of time, tmax. This critical time depends on temperature, shell thickness, and PPNs concentration in the dispersion. The influence of the PPNs shell thickness is evidenced by a comparison of Figure 5 a and b. nmax
and the release slope between nmin and nmax decrease with increased shell thickness at a constant temperature and concentration, which indicates a decrease of the rate of
Poly(AM-co-St) release because of the increase of polystyrene dissolution resistance to the oil phase. A comparison of
Figure 5 a and c for low shell thickness and Figure 5 b and d
for high shell thickness shows that the effect of increased
PPN concentration is clear: it induced an increase of nmax
and the slope because of the increased number of active
polymer chains. Finally, the temperature increase induced
a higher rate of Poly(AM-co-St) release and a higher nmax
1038
Figure 5. Time-dependent kinematic viscosity of a) LT-PPN0.2, b) HT-PPN0.2, c) LT-PPN0.3, and d) HT-PPN0.3 at 30, 60, and 90 8C (TDS = 178 082 mg L@1).
and different temperatures (30, 60, and 90 8C) in the simulated seawater (TDS = 178 082 mg L@1), and the results are pre-
Sample
LT-PPN0.2
HT-PPN0.2
LT-PPN0.3
HT-PPN0.3
1
15
30
1
15
30
1
15
30
1
15
30
15.00
14.90
14.92
13.74
13.70
13.71
15.98
15.92
15.92
13.98
13.99
13.97
15.40
15.38
15.32
14.54
14.50
14.31
16.10
15.98
15.81
15.00
14.76
14.23
16.20
15.76
14.89
14.64
14.23
14.01
17.75
16.54
15.14
16.04
15.87
15.32
1039
Figure 6. Viscosity loss of PPNs dispersions after mechanical mixing for one
week at different speeds in synthetic seawater (TDS = 178,082 mg L@1) at
90 8C; inset: Viscosity loss of PAM solution (CPAM = 0.2 wt %).
T [8C]
LT-PPN0.3
HT-PPN0.3
PAM
30
60
90
0.24
0.26
0.27
0.32
0.43
0.64
0.37
0.50
0.69
0.9
1.1
1.7
0.27
0.30
0.33
According to the presented characterization, the LTPPN0.3 sample could be a good choice for the EOR process.
It seems that the high polymer concentration and low shell
thickness of LT-PPN0.3 leads to a fast response, maximum
viscosity enhancement and thermal stability, and very good
mechanical stability. To confirm that LT-PPN0.3 has an improved performance with respect to PAM, the elastic modulus and comparative steady-shear rheological behavior of LTPPN0.3 were determined.
The viscoelastic properties of the polymer used in the
flooding process influence the macroscopic and microscopic
sweep efficiency and oil recovery strongly. That is, under
high shear-rate conditions, the water-soluble high-molecularweight polymers have a shear-thinning viscosity reduction
because of the uncoiled and disentangled chains that are
aligned and elongated in the fluid-flow shear field. This
effect is decreased for polymers with a higher elastic modulus G that are more effective to displace residual oil in the
core with a pore configuration and important capillary forces
because of a higher flow resistance (pressure drop) through
porous media.[30, 31]
The variation of elastic and loss moduli as a function of
temperature for released Poly(AM-co-St) from LT-PPN0.3
and for PAM solutions is shown in Figure 7. The loss modulus (G) of the LT-PPN0.3 solution remains unchanged,
whereas the elastic modulus (G) increases with increasing
temperature to result in a higher difference at higher temperatures, which indicates that elastic behavior predominates in
the entire investigated temperature range. If we compare the
viscoelasticity of LT-PPN0.3 with that of unprotected PAM,
LT-PPN0.3 presents a highly superior behavior to unprotected PAM, for which G and G decrease with increasing temperature.
The comparative steady-shear rheological results of PAM
aqueous solutions and Poly(AM-co-St) released from LT-
1040
Figure 7. Effect of heat treatment on the loss and elastic moduli of LT-PPN0.3
(TDS = 178 082 mg L@1, CPAM = 0.2 wt %).
Flooding medium
water
PAM
LT-PPN0.2
HT-PPN0.2
LT-PPN0.3
HT-PPN0.3
40
60
60
65
68
72
1041
Figure 9. The distribution of the oil at beginning and breakthrough time; a) Saturated micromodel for water and PAM flooding; b) Breakthrough time for water
flooding; c) Breakthrough time for PAM flooding; d) Saturated micromodel for LT-PPN0.3 flooding, after the injection of 0.1 PV, leaving for 24 h and the injection of another 0.1 PV; and e) Breakthrough time for LT-PPN0.3 flooding; T = 30 8C, flow rate = 0.0008 mL min@1 (residence time = 1250 min),
TDS = 178 082 mg L@1, CPAM = 0.2 wt %.
Conclusions
Protected polyacrylamide nanostructures (PPNs) were synthesized by two-step, one-pot inverse emulsion polymerization of an aqueous acrylamide solution, dispersed in cyclohexane, onto which polystyrene was copolymerized to form
a protective hydrophobic shell. After contact with the oil
phase in a reservoir, the protective shell will dissolve slowly
to allow controlled release of active poly(acrylamide-co-styrene) (Poly(AM-co-St)) polymer that causes an increase of
the viscosity of the aqueous dispersion to displace the remaining oil in the reservoir. Analysis of the chemical composition and particle size distribution measurements confirmed
the coreshell morphology, which had an average core size
of 61 nm and two shell sizes of 11 and 24 nm.
The protected polyacrylamide (PAM) nanostructures show
a time-dependent release behavior that, after contact with
the remaining oil in the deeper areas of reservoirs, results in
penetration of the polymer and increased viscosity of the
water-displacing phase. The viscosity variation of Poly(AMco-St) as an active polymer released from the PPNs shows
three regions: 1) at a short residence time, the PPNs present
a low viscosity similar to kinematic viscosity of displacing
water, 2) an increase of the residence time leads to viscosity
enhancement, and 3) after the critical residence time, stable
1042
Figure 10. a) IFT and contact angle measurement for crude oil against polymer/brine; b) Oil recovery of LT-PPN0.3 and c) oil recovery of PAM solutions versus
the injected volume of displacing fluid in carbonate, fracture carbonate, and sandstone core plugs, T = 30 8C, TDS = 178 082 mg L@1, CPAM = 0.2 wt %.
1043
Abbreviations
AMPS: 2-acrylamid-2-methylpropane sulfonate; AM: acrylamide; APS: ammonium persulfate; DLS: dynamic light
scattering; DSC: differential scanning calorimetry; EOR: enhanced oil recovery; HLB: hydrophiliclipophilic balance;
HPAM: partially hydrolyzed polyacrylamide; LT-PPN: protected polyacrylamide with low shell thickness; HT-PPN:
protected polyacrylamide with high shell thicknesses; NVP:
N-vinyl pyrrolidone; PAM: polyacrylamide; Poly(AM-co-St):
polyacrylamide-co-polystyrene; PPN: protected polyacrylamide nanostructure; SANS: small-angle neutron scattering;
SAXS: small-angle X-ray scattering; TDS: total dissolved
solids.
Experimental Section
Materials
Acrylamide (AM, + 99.0 %), ammonium persulfate (APS,
+ 99.9 %), xylene (+ 99.5 %), toluene (+ 99.0 %), ethanol (+
99.0 %), and cyclohexane (+ 99.9 %) were used as received from
SigmaAldrich Company. A mixture of sorbitan monolaurate
Span20 and monooleate Span80 emulsifiers (Merck Co.), with
a hydrophiliclipophilic balance (HLB) of 8.6 and 4.3, respectively, was used without further purification. Styrene monomer
(+ 99.9 %, Merck Co.) was treated with 1 m NaOH aqueous solution to remove the inhibitor and was distilled under reduced
pressure under a N2 atmosphere before polymerization. Doubledistilled water used for the preparation of emulsion was deprived
of oxygen by heating to boiling point and cooling under a stream
of nitrogen.
1044
To determine the size of the core and of the shell of the PPNs,
a combination of the equivalent hard sphere radius method provided by Chu et al.[21] and the results of SAXS experiments (performed by using an Anton PaarSAXSess mc2 Small- & Wideangle X-ray scattering system) was used. Details of how the size
of the core and the size of the shell of the PPN nanostructures
were determined are given in Figures S2 and S3.
DSC (TGA/DSC 3 + , Thermogravimetric Analyzer with a small
furnace, METTLER TOLEDO Co.) was performed on samples
of approximately 510 mg placed in closed Al pans. The analyses
were performed under a N2 flow of 20 mL min@1 at a heating rate
of 10 8C min@1 from 50 to 220 8C. Two scans were obtained for
each sample and the data were analyzed using the second-scan
curve. The Tg of the materials was obtained from the first derivative of the DSC curves.
The molecular weight of PAM nanoparticles before copolymerization with the PSt was calculated using the MarkHouwink
equation [Eq. (1)]:
hAIntr
mL
g
6:31 > 10@3 ? Mw0:8
g
mol
in which [h]Intr is the intrinsic viscosity, determined from the intercept value of a linear regression of the relationship between
the reduced viscosity and polymer concentration.[34] The viscosity
of each of the polymer solutions at different concentrations was
measured three times by using an Ubbelohde capillary viscometer (constant factor = 0.01024 mm2 s@2). Details of the procedure
are presented in the Supporting Information. The molecular
weight of the polymer nanoparticles was determined to be
& 7 000 000 Da.
1045
D1::Dm 3
0 /
L
8n3 :C: D
ss s sl sl cosq
1046