SPE-169108-MS

New Water Soluble Anionic NVP Acrylamide Terpolymers for Use in Harsh
EOR Conditions
N. Gaillard, SPE, B. Giovannetti, SPE, C. Favero, SPE, SNF, J.-P. Caritey, SPE, Schlumberger, G. Dupuis, SPE,
A. Zaitoun, SPE, Poweltec

Copyright 2014, Society of Petroleum Engineers

This paper was prepared for presentation at the SPE Improved Oil Recovery Symposium held in Tulsa, Oklahoma, USA, 12–16 April 2014.

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
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Abstract

Water soluble anionic polymers are widely used as Mobility Control agents in EOR. However, their shear, salt, free radical
and thermal stability limit their domain of application. A joint industrial effort has led to new optimized polymer
compositions. The chemical structure has been designed to improve long term thermal and salt stability. The functional
groups on the polymer chain are acrylamide (AM), sodium acrylate (AA), sodium acrylamido-tertiary-butyl sulfonate
(ATBS) and N-vinyl pyrrolidone (NVP). The composition of the different groups was varied to produce different polymer
prototypes. The bulk gel polymerization process used to produce at industrial scale EOR polymers has been fine-tuned using
NMR structural analysis at different conversion rates. The best polymer candidates were submitted to stability tests. Thermal
stability was investigated with residual oxygen between 0 and 200ppb at temperature up to 120°C and salinity up to 70 g/L
TDS with high hardness. Results show that the joint presence of NVP and ATBS in specific amounts in the polymer structure
improves thermal and salt stability. Some of the polymers, whose chemical structure was optimized to maximize stability,
could withstand harsh reservoir conditions with little loss of viscosity for an aging time of at least 1 year. These species were
then submitted to coreflood experiments and showed good propagation properties in a 100-150 mD carbonate rock. Results
show that polymer flooding can be successful in reservoirs with high temperature and harsh salinity conditions. The thermal
resistant polymers can be used for polymer, surfactant polymer floods and are promising for alkaline surfactant polymer
systems as well. They may be beneficial to other oil and gas applications where heat and salt stability are needed. With this
technology, polymer viscosity is stable while it propagates through the reservoir and a favorable mobility ratio is maintained
from injectors to producers.

Introduction
In a context where the price of oil keeps above 80 USD/bbl, enhanced oil recovery (EOR) techniques are attractive. The use
of anionic polyacrylamide (HPAM) as water viscosifier remains one of the cheapest technologies with an extra-cost
estimated at 3-10 USD/bbl (Seright 2010, Wyatt 2008, Yuming et al. 2013). Many results from field pilots and full field
projects show the benefits of polymer injection for oil recovery (Morel et al. 2012, Delaplace et al. 2013, Al-Saadi et al.
2012, Pandey et al. 2012, Clemens et al. 2013, Moe Soe Let et al. 2012, Wang et al. 2006). The goal is to increase the
viscosity of the injected fluid, to improve the mobility control and the sweep efficiency in the reservoir (Sorbie 1991). It is
mandatory that the polymer remains stable for most of its transit through the reservoir in order to maintain sufficient viscosity
to efficiently displace oil. Polymer degradation has been observed in several cases at the production well with molecular
weight (Mw) losses up to 92% ((Zhang 1995, Wang et al. 2008, You et al. (2007) Putz et al. (1994)). Therefore a proper
sampling method is necessary to evaluate the level of polymer stability in the field because, in the presence of iron or H2S,
degradation can occur if oxygen is introduced into the water (Manichand et al. 2013). This type of degradation depicted as
“chemical degradation” generally occurs from surface facilities to the near wellbore area during the first days of polymer
injection until dissolved oxygen is totally consumed by the reservoir (Seright et al. 2010). This degradation can be prevented
by the addition of protective additives (Wellington 1983, Gaillard et al. 2010) and by building inerted facilities (Thomas et
al. 2013). Indeed, the absence of oxygen considerably limits chemical degradation even in presence of reducing contaminants
such as Fe++ or H2S (Shupe 1981, Yang and Treiber 1985, Seright et al. 2010).
2 SPE-169108-MS

HPAM may undergo additional conformational changes from early- to long-term propagation in the reservoir. Changes
include an increase in the level of hydrolysis of either the acrylamide or ATBS groups. (Zhang 1995, Wang et al., 2008, You
et al., 2007, Levitt et al. 2010, Levitt et al. 2008, Parker et al. 1993). High hydrolysis degree of the polymer backbone, in the
presence of divalent cations such as calcium and magnesium, will cause a drop in viscosity due to a bridging effect of Ca2+,
Mg2+, which could lead to precipitation (Moradi-Araghi and Doe 1987, Ryles 1988). Polyacrylamides can be modified with
functional monomers such as N-vinyl pyrrolidone (NVP) or ATBS to provide tolerance to divalent ions and protect from
hydrolysis at elevated temperatures (H.L. Hsieh et al. 1992). The addition of NVP to the polymer chain can protect
neighboring acrylamide groups from hydrolysis (Fernandez 2005, Doe 1987), as well as provide improved temperature
stabilities at 120°C for more than 180 days (Gaillard et al. 2010, Vermolen et al. 2011, Kulawardana et al. 2012). In the
presence of divalent ions, the fraction of NVP in the polymer chain should be 35-50 mol% to ensure stability. NVP has
lower reactivity than AM during the polymerization process, which can lead to drifts of composition as well as difficulty in
obtaining high Mw. Therefore, an over dosage, compared to standard HPAM, is required to achieve the target viscosity
(Gaillard et al. 2010).

Objectives. This paper gives the results of a two year joint industrial project between Schlumberger, Total, Poweltec and
SNF, with analytical support from the University of Pau and Pays de l’Adour. The objective was to optimize the chemistry of
the NVP copolymer focusing only on the industrial gel process used for the production of EOR grade dry polymers.
Understanding the factors enhancing polymer stability enabled us to improve the chemistry and structure of NVP based
polymers previously described in the paper from Gaillard et al. (2010), thereby finding a better compromise between stability
and cost. For the cost considerations, parameters taken into account were the cost per unit related to the use of expensive raw
materials, the cost per centipoise related to the dosage necessary to reach a viscosity target and the long term stability
performance. A relative cost efficiency (RCE) has been used to account for all those parameters and identify the most cost
effective candidate. The first part of our work studies the incorporation of various monomers during polymerization and the
improvement in the production process to limit composition drifting. Next, polymer stability was evaluated by aging tests
using two different brines for a period of one year at temperatures of 105°C, 120°C and up to 140°C under total anaerobic
conditions and in the presence of 200 ppb of oxygen. Best candidates were injected in core flood experiments to assess the
adsorption and injectivity under reservoir conditions.

Experimental procedures
Polymer solution preparation
Brines compositions used for polymer preparation are given in Table 1. All polymer solutions were prepared at 5000 ppm
using a mechanical stirrer.

Table 1: brine compositions

Salts 30K+3 Middle-East

NaCl 30 000 ppm 52 878 ppm
CaCl2,2 H2O 3 000 ppm 11 895 ppm
MgCl2, 6 H2O 15 079 ppm
TDS 33 000 ppm 79 852 ppm

Prior to coreflood experiments, each brine solution was filtered under vacuum through 0.22 µm Millipore™ to eliminate any
dust and/or insoluble particles. Polymer solutions were filtered by gravity through 4-7 µm Whatman™ filters. All brine and
polymer solutions were degassed under vacuum and kept under helium blanket to remove dissolved oxygen and prevent
bubble formation during injection.

Viscosity measurement
Polymer solution viscosities were measured using a Brookfield Model LVTTM viscometer equipped with a UL adaptor and a
double jacket connected to a thermostatic bath. All measurements were performed at room temperature. To ensure viscosity
was not affected by the presence of air when opening the ampoules or during measurement, ampoules were opened and
viscosity measured in an anaerobic chamber. Rheological profiles were obtained using a Bohlin Gemini (Fig. 1, left) with a
cone-plate geometry (2°, 6 cm). UL viscosity corresponds to the viscosity of 1000 ppm polymer in a brine composed of 1M
NaCl, measured with a Brookfield LVT with UL spindle rotating at 6 rpm, and at 25°C. UL viscosity is used as a shortcut to
estimate polymer molecular weight.
For coreflood experiments, solution viscosities were measured using an AR 1500 rheometer from TA Instrument equipped
with a Couette geometry (Fig. 1, right). The AR1500 rheometer is not equipped with a pressure cell so we were unable to
directly determine the viscosity of the polymer solution at the temperatures used for the coreflood experiments (105 and
120°C). Therefore, for each polymer, viscosity has been measured at shear rates from 1 to 100 s-1 and temperatures ranging
SPE-169108-MS 3

from 30 to 90°C. For each shear rate, viscosity versus temperature has been extrapolated to 105 and 120°C using an
Arrhenius plot. Relative viscosity of the polymer solution ηr was determined as:
𝜂 Equation 1
𝜂! =
𝜂!

where η is the absolute viscosity of the polymer solution and η0 is the viscosity of the brine.

Fig. 1- Bohlin Gemini cone plate rheometer (left); AR 1500 rheometer with Couette geometry (right)

Thermal stability
The preparation of the polymer samples for stability tests was carried out under total anaerobic conditions in a glove box
shown in Fig.2. The glove box is a Jacomex GP (concept) T-4, with a palladium catalyst to scavenge any traces of oxygen.
The method has been described by Seright et al. (2010). Oxygen measurements were performed using a Mettler Toledo
Model M700XTM meter equipped with two InPro 6950TM O2 sensors. The sensitivity of the probe is 0.1 ppb in the liquid
phase.

Fig. 2- Glove box used for thermal stability sample preparation.

All polymer solutions were transferred to stainless steel containers (150 mL) in the glove box. These containers were placed
in an oven at the desired temperature and aged for one year. The effect of thermal degradation on the polymer solution was
determined by measuring the viscosity of the solution periodically. The rheometer used in this case was a Brookfield
viscometer (LVT 085 mounted on UL adaptor at 6 rpm) at 25°C. Viscosities were measured in the anaerobic glove box to
ensure no oxygen was introduced during viscosity measurements. Measurements were performed at 25°C in order to have a
higher viscosity scale compared to 90-140°C.

Coreflood experiments
Experiments were performed at 105 and 120°C at 100% water saturation. The brine was synthetic sea water (30K+3 in
Table 1). Carbonate (Estaillade) cores were chosen to run the coreflood experiments. They present a bi-modal pore size
distribution with a micro-porosity having pore sizes ranging from 0.1 to 1 µm and a macro-porosity with pore sizes ranging
from 1 to 100 µm. Absolute core permeabilities were about 100 to 150 mD while porosities were about 31 ± 1 % with
approximately 13-14% of micro-porosity and 17-18% of macro-porosity.

The experimental setup includes an injection system composed of two constant flow rate piston pumps to inject brine
(Pharmacia P500) and polymer solution (Isco Teledyn 250D), an oven, a core holder (Hassler-cell), a capillary tube (internal
diameter d = 505 µm and length l = 2 m), a back pressure regulator device and a fraction collector. Injection lines (brine plus
polymer) were equipped with pre-heating spiral tubing while other spiral tubing was placed in a water bath outside the oven
4 SPE-169108-MS

in order to cool down the effluents prior to oxygen exposure. The core holder was equipped with pressure taps at each end to
measure the pressure drop across the core. The capillary tube is also equipped with its own pressure taps. Pressure
transducers are connected to an acquisition system for data collection and interpretation.

The coreflood experiments were designed to i) determine polymer adsorption and inaccessible pore volume; ii) check
polymer injectivity; iii) evaluate polymer stability under coreflood conditions; iv) determine rheological behavior of the
polymer solution in the core; and v) check for permeability impairment after polymer injection. The procedure included the
following steps:
- Measurement of the core dimensions (length, diameter, dry weight).
- Core saturation with brine under vacuum, weight measurement after saturation.
- Mount the core in the Hassler cell. Heat the oven to the desired temperature (105 or 120°C). Establish overburden
pressure (80 bars) and pore pressure (8 bars). Check for equipment integrity and pressure sensors response.
- Determination of absolute permeability by brine injection and pore volume determination by tracer injection (KI).
- Injection of two fronts of polymer at low concentration (C1) and low flow rate (2 mL/h) separated by a front of brine
through the core. Determination of polymer adsorption and inaccessible pore volume (IPV).
- Injection of the polymer solution at C1 with different flow rates. Evaluation of the injectivity and of the mobility
reduction (Rm) plot.
- Displacement of the polymer by brine at different flow rates. Determination of the permeability reduction (Rk) plot.
- Repeat the last two steps for polymer solution at concentration C2, C3 and C4.
Main parameters
The main parameters are, the adsorption (Γ), the inaccessible pore volume (IPV), the mobility reduction (Rm), the
permeability reduction (Rk) and the shear rate at the pore wall (𝛾! ).

- Adsorption and Inaccessible Pore Volume :

Adsorption is defined as the delay between the two fronts of polymers injected at low concentration (C1) according to:
𝑑𝑒𝑙𝑎𝑦  𝑏𝑒𝑡𝑤𝑒𝑒𝑛  𝑝𝑜𝑙𝑦𝑚𝑒𝑟  𝑓𝑟𝑜𝑛𝑡𝑠 ×𝐶
Γ= Equation 2
𝑚!"#$
where C corresponds to the polymer concentration in grams per liter and mcore is the weight of the core before saturation in
grams. Γ is generally expressed in micrograms of polymer adsorbed per gram of rock material.
The inaccessible pore volume (IPV) is defined as the delay between front of tracer and the second front of polymer according
to Equation 3:
𝑑𝑒𝑙𝑎𝑦  𝑏𝑒𝑡𝑤𝑒𝑒𝑛  𝑡𝑟𝑎𝑐𝑒𝑟  𝑎𝑛𝑑  2!"  𝑝𝑜𝑙𝑦𝑚𝑒𝑟  𝑓𝑟𝑜𝑛𝑡
IPV = ×100 Equation 3
𝑃𝑉
where PV is the pore volume. IPV is expressed in percentage of pore volume.

- Mobility and Permeability Reduction :

The mobility reduction (Rm) is the apparent viscosity of polymer solution flowing through a porous media. It can be easily
determined from pressure drop measurement:
∆𝑃
𝑅𝑚 = Equation 4
∆𝑃!
Where ΔP is the pressure drop measured during the injection of the polymer solution in the core at a given shear rate and
saturation. ΔP0 is the reference pressure drop generated by the flow of brine through the core before the injection of the
polymer solution under the same flow rate and saturation conditions.
The permeability reduction (Rk) corresponds to the reduction of permeability of the core to brine after injection of a polymer
solution. It corresponds to the ratio of the pressure drop generated by the brine while flowing through the core after (ΔPf) and
before (ΔP0) injection of polymer solution. As mentioned previously, ΔPf and ΔP0 have to be measured under the same flow
rate and saturation conditions.
∆𝑃!
𝑅𝑘 = Equation 5
∆𝑃!
SPE-169108-MS 5

In the literature, Rm and Rk are also called RF (Resistance Factor) and RRF (Residual Resistance Factor) respectively.

- Shear rate at the pore wall :

The effective shear rate at the pore wall (𝛾! ) is determined as
4𝑄
𝛾! = 𝛼 Equation 6
𝑟! 𝑆ϕ
where Q is the flow rate, S is the core section¸ φ is the porosity, α is a corrective parameter to take into account the
specificities of the complex geometry of the real porous media in comparison to a simple capillary model (Chauveteau 1982)
and rp is the pore radius. rp is defined from Equation 7:

8𝐾
𝑟! = 𝛽 Equation 7
ϕ

where K is the permeability to brine and β is a corrective parameter. Since 𝛾! depends only on the ratio 𝛼 𝛽 (see equations 6
and 7), β has been taken arbitrally equal to 1. The value of 𝛼 𝛽 has been determined from injection data of ultra pure xanthan
gum through the same core material following the method of Chauveteau. The method consists in superposing ηr and Rm
plots to obtain same onset of shear-thinning regime. For this particular core material, 𝛼 𝛽 has been found equal to 25.

Stability of NVP polymers: comparison between Acrylic Acid (AA) and ATBS
As previously mentioned, the cost of polymer is strongly impacted by the NVP content. Therefore, two NVP-copolymers
have been compared. The cost per unit can be reduced simply by replacing ATBS with acrylic acid. Stability of the
terpolymer containing NVP, acrylamide and acrylic acid were compared to the same terpolymers where AA was replaced by
the same number of moles of ATBS. Polymers containing more than 25 mol% NVP were aged at 105°C and 120°C whereas
polymers containing less than 25 mol% NVP were only aged at 105°C. Aging test results, in the presence of 200 ppb oxygen
and under anaerobic conditions using the brines given in Table 1, are shown in Fig. 3, 4 and 5.

Fig. 3- Thermal stability at 105° C of terpolymer NVP/ATBS/AM (2500 ppm in Middle-East brine – 2300 ppm in 30K+3) and NVP/AA/AM
(2400 ppm in Middle-East brine – 2200 ppm in 30K+3) in 2 different brines at 105°C. Doted curves = 0 ppb of O2, solid curves = 200
ppb of O2.
6 SPE-169108-MS

Fig. 4- Thermal stability at 105° C of terpolymer NVP/ATBS/AM (3000 ppm in Middle-East brine– 2900 ppm in 30K+3) and NVP/AA/AM
(2900 ppm in Middle-East brine– 2600 ppm in 30K+3) in 2 different brines at 105°C. Doted curves = 0 ppb of O2, solid curves = 200
ppb of O2.

Fig. 5- Thermal stability at 120° C of terpolymer NVP/ATBS/AM (3000 ppm in Middle-East – 2900 ppm in 30K+3) and NVP/AA/AM
(2900 ppm in Middle-East – 2600 ppm in 30K+3) in 2 different brines at 105°C. Doted curves = 0 ppb of O2, solid curves = 200 ppb of
O2 .

Discussion
The presence of 200 ppb of oxygen has low impact on the stability of the different polymers when compared to total
anaerobic conditions. This outlines the improved robustness of polymers containing NVP. The oxygen was present during the
first seven days of the experiment since the ampoules were prepared with a minimum head space to keep most of the oxygen
partitioned in the liquid phase. After aging for 7 days, samples were withdrawn from the oven and placed in total anaerobic
conditions. According to Henry’s law, with an atmosphere that only contains nitrogen, most of the oxygen is stripped from
the liquid phase. In field conditions, oxidative degradation occurs during the first few days only because oxygen is consumed
rapidly when it enters the geological formation (Seright et al. 2010). Thus, the experimental protocol mimics time exposure
to oxygen that could occur in the field. Long-term stability test results show that all the polymers containing AA have poor
stability at 105°C even when the NVP content is above 25 mol%. The presence of AA is detrimental because it can accelerate
the auto-catalytic hydrolysis of acrylamide and also impact the calcium stability of the polymer (Levitt et al. 2010).
Replacing AA by ATBS leads to improved stability. Polymers with ATBS and a lower amount of NVP (< 25 mol%)
maintain 80% of the initial viscosity over 60 days at 105°C. At 120°C, the level of NVP has to be increased to ensure a
residual viscosity plateauing at 50% of the initial viscosity (Fig. 3). Hence, a polymer containing more than 25 mol% of NVP
is fairly stable at 120°C with the residual viscosity remaining stable in both synthetic sea water and Middle-East brine over a
SPE-169108-MS 7

one year-aging period of time..

Thermal stability of commercial polymers

The previous results show that ATBS is superior to AA to enhance polymer stability at high temperature, with a minimum
level of 25 mol% NVP necessary to provide stability at 120°C. Thermal stability tests of commercial polymers containing 15-
25 mol% and 35-50 mol% of NVP (Table 2) have already been described in the literature (Gaillard et al. 2010, Vermolen et
al. 2011). Additional tests were conducted over one year at 105°C and 120°C in a Middle-East reservoir brine (Table 1) to
confirm earlier conclusions. Results are presented in Fig. 6.

Table 2- Industrial products evaluated for 1 year stability

Product Code name AM ATBS NVP

Superpusher SAV 522 SAV522 25-45% 20-25% 35-50%
Superpusher SAV 505 SAV505 50-65% 0% 35-50%
Superpusher SAV 225 SAV225 50-65% 20-25% 15-25%
Flopaam AN 125 SH AN125 75-80% 20-25%

Fig. 6- Thermal stability at 105°C and 120°C of copolymer AM/ATBS (AN125: concentration = 1850 ppm), copolymer NVP/AM
([SAV505] = 3000 ppm) and terpolymers NVP/ATBS/AM ([SAV225] = 2100 ppm, [SAV522] = 2900 ppm). Doted curves = 0 ppb of O2,
solid curves = 200 ppb of O2

As previously stated, the presence of 200 ppb of O2 has no impact on the stability of the different polymers. It is interesting to
note that the solution of AN125, which contains no NVP, precipitates after 40 days. This is a clear indication that this
polymer is not robust enough in hard brine and temperature of 105°C (Hsieh et al. 1992, Audibert et al. 1995). The presence
of 15-25 mol% NVP in the polymer (SAV225) maintains 50% of the initial viscosity under the same test conditions.
However for elevated temperature of 120°C, the level of NVP has to be increased up to 35-50 mol% to ensure stability. This
confirms the results obtained from Vermolen et al. (2011), showing that a high level of NVP is required to ensure stability
over 1 year in brine containing divalent cations. It is interesting to see here that the two products containing 35-50 mol%
NVP (SAV505 and SAV522) show a viscosity drop in the first few days before remaining stable over one year at 120°C.
This may be explained by a drift of composition in the polymer with chains containing a high level of NVP and chains with a
low level of NVP. Further analytical investigations are described in the next section to assess how ATBS, AM and NVP
monomers are incorporated into the polymer to tentatively explain this behavior.

Evaluation of polymer compositions during polymerization

Polymerization processes
Polymerizations were conducted using the gel process for producing EOR grade polymers in dry form. Polymers were all
obtained in powder form using either: 1) precipitation in alcohol mixtures for partial conversions, or 2) direct drying process
in the laboratory. Mini gels were obtained after polymerization in 100 mL glass reactors to assess partial conversions. The
reactor set up and initiator system were adapted to minimize heat transfer and wall inhibition effects. Monomers and water
were introduced into a 100 mL insulated reactor. The solution was cooled to Ti = 10°C and flushed with nitrogen for 15
8 SPE-169108-MS

minutes. The initiator system was added and temperature of polymerization was followed as a function of time. At targeted
times (at temperature: T), the polymer gels were poured in cold alcohol (either methanol or ethanol) in a warring blender to
stop polymerization. The gels were crushed, filtered, washed and dried. Each polymerization was left until achieving a stable
final temperature Tf corresponding to 100% conversion. Since fully adiabatic polymerizations were performed, partial
conversions were estimated through the heat of polymerization using the following equation:
𝑇 − 𝑇!
𝐶𝑜𝑛𝑣% = ×100 Equation 8
𝑇! − 𝑇!

The instantaneous incorporation rate was determined by calculating the difference of composition between two samples
collected at two different conversions. Compositions of the polymer at different conversions were analyzed using 1H NMR.

Polymer with high level of NVP: SAV522

SAV522 was synthesized using mini gel polymerization: the percentage of instantaneous incorporation compared to theory is
plotted for each conversion and shown in Fig. 7.

Fig. 7- Instantaneous incorporation rate (%) of each monomer during polymerization of SAV522.

For SAV522, a significant drift of composition is observed over the course of the polymerization. A high level of ATBS is
incorporated in the first formed polymer chains, while NVP is mainly incorporated at the end of the polymerization. Thus, in
the same product, some macromolecules contain a high level of ATBS and some others contain a high level of NVP. Final
product composition has been analyzed and is very close to theoretical one as shown in Fig. 8. ATBS is confirmed to be
slightly over incorporated. The follow-up of UL viscosity over the course of the polymerization outlines that the polymer
chains formed at the end of the polymerization have a very low Mw since in the last 15% of conversion, the UL viscosity is
lowered by 0.15 cps. A rough calculation gives a UL of 1,3 to 1.5 cps for those nonionic chains containing a high amount of
NVP. In conclusion, the composition of SAV522 is not appropriate since a significant part of the NVP is incorporated in low
Mw, low anionic polymer chains with little to no contribution to viscosity. Moreover, the vast majority of the ATBS is
consumed in the formation of higher Mw polymer chains that do not contain enough NVP to be stable at 105°C and above.

This drift of composition may explain the stability of SAV522. The viscosity drop observed during the first days of the aging
test at 120°C (Fig. 6) is linked to the degradation of the chains formed during the first part of the reaction with a low NVP
content. Medium and long term stability might be attributed to the polymers with high NVP content. These chains having a
low Mw, need high dosage to reach targeted viscosity.
SPE-169108-MS 9

Fig. 8- Final compositions of SAV522

Polymer with medium level of NVP: SAV225

SAV225 was synthesized using mini gel polymerization: the percentage of instantaneous incorporation compared to theory is
plotted for each conversion in Fig. 9.

Fig. 9- Instantaneous incorporation rate (%) of each monomer vs conversion during polymerization of SAV225

For SAV225, a slight and random drift of composition is observed over the course of the polymerization but overall all
monomers are homogeneously incorporated in all polymer chains. In this experiment, UL viscosity increases over the course
of the polymerization which is in favor of good incorporation of the monomers. Thus, the drift of composition is fairly low
for this product when compared to SAV522. Since ATBS is a sulphonic acid and NVP bears a basic tertiary amine, they may
have a concerted incorporation mechanism through acid base complexation, helping a one to one alternate propagation. This
mechanism would be in accordance with prior literature data (Guven et al. 2008, Kurenkov et al. 2006). In the case of
SAV522, the polymer composition is unbalanced, both the ATBS and NVP try to self-correct their incorporation, creating a
large drift in composition over the span of conversion. ATBS, being at half the molar amount of NVP, is over incorporated in
the early stages, leaving an excess of NVP available at the end of the polymerization when ATBS is no longer available in
the monomer form.
From these observations, we may assume that, in order to ensure a better incorporation of these two monomers and to avoid
any drift of composition, their relative ratio has to be balanced.
The lack of stability observed for SAV 225 at 120°C (Figure 6) may be explained by the relatively low amount of NVP.
Higher amounts of NVP in similar balanced compositions might be necessary to ensure better stabilities. This will be
addressed in the next section.
10 SPE-169108-MS

Development of industrial products

The lessons learned from these preliminary studies are that terpolymers containing NVP can be stable for up to 1 year at
120°C. ATBS is preferred to acrylic acid as monomer. A minimum level of NVP is required in the composition to ensure
stability. Using NMR and mini gel polymerizations suggested that the incorporation of each monomer during the
polymerization process may be driven by a concerted insertion of NVP with ATBS. Thus, an optimized ratio of monomers
has been defined in order to develop a full range of industrial NVP based polymers and ensure the best incorporation of each
monomer during polymerization while limited drifts of compositions (Table 3). The polymers contain very low to high
amounts of NVP. The mini gel method with NMR was used for all the products to assess the incorporation of each monomer
and results confirmed the assumption that a specific relative ratio of monomers was necessary to get homogeneous
compositions.
Table 3- Theoretical composition of polymer with optimized composition of ATBS and NVP

Concentration to achieve 10 cps RCE*

Commercial name Code name NVP
@25°C in Middle-East brine
Superpusher SAV118 SAV118 Low 2 000 ppm 3.4
Superpusher SAV226 SAV226 Low 2 000 ppm 4.4
Superpusher SAV225 SAV225 Medium 2 100 ppm 5.0
Superpusher SAV333 SAV333 High 2 600 ppm 7.0
Superpusher SAV442 SAV442 High 3 200 ppm 9.0
Superpusher SAV522 SAV522 Very High 2 900 ppm 9.0
Superpusher SAV505 SAV505 Very High 3 000 ppm 10.2
Low : 5-20 mol%, Medium 20-30 mol%: High : 30-45 mol%, Very High : >45 mol%
*RCE: Relative Cost Efficiency compared to standard HPAM (20 million Dalton, 30 mol% anionicity) as reference cost = 1

Thermal Stability
All SAV products given in Table 3 were dissolved in Middle-East brine. The concentration of each product was determined
to achieve 10 cps at 25°C and is reported in Table 3. It can be seen that increasing the level of NVP induces an increase of the
necessary concentration of polymer to reach the target viscosity. Lower Mw are obtained when the amount of NVP is too
high. The RCE of polymer is related to both the dosage necessary to reach a desired viscosity and to the cost per unit of the
polymer based on raw materials cost. Since the incorporation of NVP reduces the Mw, a higher polymer dosage is necessary
to achieve target viscosity, thereby increasing the RCE. RCE is considered in Table 3. The values correspond to the extra
operational expenditure (OPEX) cost factor that has to be applied compared to regular HPAM under Middle-East conditions.
For example, SAV505 is 10.2 times more expensive to use than regular HPAM. It can be also seen that SAV505 is 2 times
more expensive than SAV225 in Middle-East brine. It is then very important to assess the stability performance of each
polymer to optimize the cost for each field condition. The aim of this part is to determine the candidates giving the best
stability cost-wise for 105°C and 120 °C.

Stability of all the products (Table 3) in Middle-East brine was evaluated at 105°C and 120°C for 1 year. Initial viscosity and
viscosity after one year are given in Fig. 10 and 11.

Fig. 10 - Thermal stability of NVP containing polymers at 105°C in Middle-East brine. Polymer concentrations: 2000ppm (SAV118),
2000ppm (SAV226), 2100ppm (SAV225), 2600ppm (SAV333), 3200 ppm (SAV442), 2900ppm (SAV522), 3000ppm (SAV505)
SPE-169108-MS 11

The first conclusion is that if NVP content is below 20 mol%, the stability at 105°C is not achieved. A minimum of 20 mol%
is required to ensure better stability. SAV225 is the best compromise for fields at 105°C considering cost and stability. The
dosage to achieve 7 cps after one year is only 2100 ppm compared to products with a higher amount of NVP that require at
least 2600 ppm (7-8 cps after one year). Price is divided by 2 compared to polymers with a higher level of NVP such as
SAV505 as shown in Table 3.

Fig. 11- Thermal stability of NVP containing polymers at 120°C in Middle-East brine. Polymer concentrations: 2000ppm (SAV118),
2000ppm (SAV226), 2100ppm (SAV225), 2600ppm (SAV333), 3200 ppm (SAV442), 2900ppm (SAV522), 3000ppm (SAV505)

For a temperature of 120°C, SAV225 is not robust enough and only 2 cps of residual viscosity is obtained after one year. At
120°C, a minimum level of 30 mol% NVP is required. In this case SAV 333 is the best economical option since the
remaining viscosity is 7cps at a dosage of 2600 ppm while 2900-3000 ppm are needed for products with higher level of NVP.
Obviously, this evaluation only takes into account the stability in a specific brine and a systematic evaluation has to be
performed for each case study. Total dissolved salt, amount of divalent, presence of contaminants (iron, oxygen, H2S) and
temperature are the parameters to take into account to determine the most economical product for each case. However, the
results presented in this study give guideline for product selection.

SAV225 and SAV333 behavior in porous media

According to long-term stability tests, SAV225 and SAV333 were identified as the best candidates for polymer floods in
reservoirs having temperature of 105°C and 120°C respectively. These temperatures are representative of many carbonate
fields in the Middle-East. Therefore polymer injection in low-permeability carbonate cores were carried out. Two core flood
experiments are reported: 1) at 105°C using Superpusher SAV225, and 2) at 120°C using Superpusher SAV333. Cores
characteristics are given in Table 4.

Table 4- Cores characteristics

Core Absolute
Length Diameter Weight Saturation PV Porosity Polymer Concentrations
number Permeability
500, 1100, 1900 and
Core #1 6,44 cm 3,79 cm 141,5 g Sw = 1 71 mD 18,8 mL 25,8 SAV225
2500 ppm
750, 2000, 3000 and
Core #2 6,44 cm 3,80 cm 137,0 g Sw = 1 150 mD 21,6 mL 29,5 SAV333
4000 ppm

Superpusher SAV225 injection at 105°C in Core #1

Main results obtained during the injection of the Superpusher SAV225 in Core #1 at 105°C are summarized in Table 5:
12 SPE-169108-MS

Table 5: Injection ofSuperpusher SAV225 in Core #1 at Sw = 1

C (ppm) η r at 105°C Rm (1 ft/day) Rk (1 ft/day)

(extrapolation)
500 1,9 1,7 1,1
1100 2,5 2,0 1,1
1900 5,5 4,1 1,3
2500 9,5 8,8 1,6
Adsorption ≈ 84 µg/g
IPV ≈ 24%

- Adsorption and IPV measurements :

The adsorption and IPV measurements are shown in Fig. 12. A significant delay is observed between the two fronts of
polymer indicating high adsorption level (Γ ≈ 84 µg/g). In the case of sandstones, the rock surface is negatively charged thus
introducing anionic charges in the polymer reduces the affinity of the polymer to the rock surface thereby reducing the
amount of adsorbed polymer. In the case of the Estaillade material, the rock surface is positively charged, so the presence of
anionic charges along the polymer backbone increases the affinity of the polymer to the rock thus the amount of adsorbed
polymer. An IPV of 24% was measured. In sandstone rocks, this value is about 10 to 12% for regular HPAM with Mw of
about 20 million Daltons. A higher IPV value could have been expected here considering the low rock permeability (Kw =
71 mD, see Table 4) and its bi-modal porosity. However, the relatively low average molecular weight of SAV225 (about 5 to
7 million Da) provides good injectivity.

- Injectivity :
Injectivity curves of Superpusher SAV225 in Core #1 at Sw = 1 show similar trend at all concentration. Rm tends to stabilize
even if a slight drift is noticeable (Fig. 13). At the lowest injection rate (2 mL/h) the injectivity curve presents an unusual
trend decreasing after 0.2 PV before reaching stabilization after 1.2 PV. This behavior might indicate that some degradation
occurred at lower flow rate, where the residence time of the polymer is longer at 105°C, in the coreflood set-up.

Fig. 12- Adsorption and IPV measurement of SAV225 500 ppm in Core #1 (Sw = 1)
SPE-169108-MS 13

Fig. 13- Injectivity curves of SAV225 1900 ppm in Core #1 (Sw = 1)

- Mobility and permeability reduction curves :

The values of Rm and Rk reached during the injection of the Superpusher SAV225 solutions in Core #1 at 500, 1100, 1900
and 2500 ppm are reported in Table 5 for a propagation rate of 1 ft/day, together with the values of relative viscosity. Rm, Rk
and ηr curves obtained at 1900 ppm are also reported in Fig. 14. Similar trends were observed at 500, 1100 and 2500 ppm. As
shown in Table 5, the mobility reduction at 1 ft/day is slightly lower than the relative viscosity of the injected solution.
According to Fig. 14, the mobility reduction increases while increasing the injection rate. At the lowest injection rate, Rm is
below the relative viscosity which could be due to polymer degradation. At 5 mL/h, Rm is close to ηr. At higher injection
rates, Rm increases and becomes higher than ηr. The shear-thickening effect may be a combination of polymer stretching
under elongational flow and better stability conditions when residence time is short in the set-up.
Permeability reduction values were found to be low (1.1 to 1.3)
14 SPE-169108-MS

Fig. 14- Mobility and permeability reduction curves of SAV225 1900 ppm in Core #1 (Sw = 1)

Superpusher SAV333 injection at 120°C in Core #2

Table 6- Injection of Superpusher SAV333 in Core #2 at Sw = 1

C (ppm) η r at 120°C Rm (1 ft/day) Rk (1 ft/day)

(extrapolation)
750 1,5 3,3 1,3
2000 3,3 2,7 -
3000 5,1 3,9 -
4000 6,6 6,3 1,2
Adsorption ≈ 28 µg/g
IPV ≈ 16%

- Adsorption and IPV measurements :

The adsorption and IPV measurements determined by injection of 2 separate fronts of SAV333 at 750 ppm in Core #2 are
shown in Fig. 15. The adsorption level is lower than in the Corflood # 1 (20-30 µg/g). IPV is also lower (16%). The higher
permeability of Core #2 (Kw = 150 mD) regarding Core #1 (71 mD) probably contributes to this trend. SAV333 presents
both higher ATBS and higher NVP content than SAV225. Since SAV333 has more anionicity than SAV225, higher
adsorption may have been expected due to more electrostatic affinity for the cationic rock surface. However, the anionic
monomer is a sulfonate and is less sensitive to cationic charges than carboxylates. The other difference between both
polymers is the amount of NVP. Due to the steric hindrance of the NVP groups, more complex interactions between the
polymer and the rock surface may be induced. Thus increasing the NVP content could lead to a decrease in adsorption.
SPE-169108-MS 15

Fig. 15- Adsorption and IPV measurement of SAV333 750 ppm in Core #2 (Sw = 1)

- Injectivity :
Injectivity curves of Superpusher SAV333 in Core #2 at Sw = 1 obtained for each concentration indicate better injectivity
than SAV225 (Fig. 16). As for the IPV, this behavior is consistent with the higher permeability of Core #2 compared to
Core #1.
Also at the lowest flow rate (2 mL/h), Rm starts to stabilize before decreasing after 0.4 PV. This behavior indicates that
polymer degradation occurs at low flow rate most likely due to the longer exposure time of the polymer solution at the
temperature of 120°C. The protocol of de-oxygenation of the solutions injected during coreflood experiments at high
temperature has to be optimized in order to reach lower oxygen content and prevent polymer degradation. Addition of
stabilizing chemicals such as isopropanol/thiourea may help to tackle this experimental issue.

- Mobility and permeability reduction curves :

The values of Rm and Rk reached during the injection of the Superpusher SAV333 solution in core #2 at 750, 2000, 3000 and
4000 ppm are reported in Table 6. Rm, Rk and ηr curves obtained at a concentration of 3000 ppm are given in Figure 17. .
Similar trends are observed at 750, 2000 and 4000 ppm. The results obtained are in good agreement with the results obtained
for SAV225 at 105°C; Above 1 ft/day, Rm increases with the injection rate which is likely due to the contribution of
elongational effects and shorter residence time at 120°C. Lower oxygen exposure are needed to minimize polymer thermal
degradation in high-temperature core floods.
16 SPE-169108-MS

Fig. 16- Injectivity curves of SAV333 3000 ppm in Core #2 (Sw = 1)

Fig. 17- Mobility and permeability reduction curves of SAV333 3000 ppm in Core #2 (Sw = 1)
SPE-169108-MS 17

Conclusions

Solutions of acrylamide based terpolymers containing NVP were evaluated at 105°C and 120°C. The incorporation of acrylic
acid in NVP terpolymers led to poor stability in solution over time. When acrylic acid was replaced by ATBS stability was
strongly improved. The level of NVP has to reach 35 mol% to sustain temperature of 120°C for 1 year. Drifts in composition
were suspected based on the aging viscosity profile. A new method of synthesis was developed for this purpose. The
incorporation of each monomer ATBS, acrylamide and NVP had been followed by NMR during gel polymerization. NVP
and ATBS seem to follow a concerted mechanism and the ratio of both monomers has to be balanced in order to limit drift of
compositions. Thanks to these results, new industrial products with balanced ratio of ATBS and NVP were synthesized and
their stability in solution was evaluated at 105°C and 120°C. The optimization of composition in term of monomer ratio
enables the selection of the most appropriate chemistry for high temperatures. Optimized products SAV225 and SAV333
were defined as the most economical solutions for conditions of 105°C and 120°C respectively. Relative cost is 2 times lower
for SAV225 and 1.30 to 1.45 times lower for SAV333 compared to SAV with higher content of NVP.
These two polymers have been chosen for coreflood tests in carbonate rocks temperatures of 105 and 120°C in sea water.
They both show good overall injectivity and propagation. Although adsorption has been found to be higher than in sandstone
rocks with same permeability, it remains at quite acceptable level. At the lowest flow rate, polymer degradation was observed
during core-flood experiment probably because of the longer exposure time at high temperature. New deoxygenation and
coreflood protocols are under testing to reach lower oxygen exposure.

Acknowledgements
The authors would like to thank Total and particularly Danielle Morel, Philippe Cordelier, Stephane Jouenne and David
Levitt, Schlumberger and particularly Jean-Philippe Caritey and Véronique Barlet-Gouedard, for the financial and technical
support of the work performed and for their authorization to present this paper. The authors would like to thank the CITEPH
program from the GEP/AFTP and Bruno Grassl from the University of Pau for the supports all along the project.

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