SPE-174653-MS

An Innovative Approach to Make HPAM an Effective Solution to Optimize

the Low Salinity ASP Application in Caracara Sur Field, Colombia - Field
Case
H. Cubillos, M. Stofferis, and J. Montes, CEPSA EP; R. Rodriguez, C. Prieto, P. Romero, N. Blin,
and A. Panadero, CEPSA Research Center.

Copyright 2015, Society of Petroleum Engineers

This paper was prepared for presentation at the SPE Enhanced Oil Recovery Conference held in Kuala Lumpur, Malaysia, 11–13 August 2015.

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Abstract
To ensure a technically and economically viable chemical Enhanced Oil Recovery (cEOR) project in the
Caracara Sur Field (Llanos Basin Colombia), several challenges were faced. One of the challenges
described in a previous work (Cubillos et al. 2013), is the design of an efficient chemical formulation
stable at reservoir conditions. Comprehensive laboratory work has been undertaken, resulting in an Alcali
Surfactant Polymer (ASP) formulation containing hydrolysed polyacrylamide (HPAM) as a mobility
control agent. HPAM is the most used polymer in the oil industry thanks to its low cost and availability
in high quantities. However, initially it was not clear that HPAM efficiently worked for Caracara Sur,
because HPAM properties limits its efficient application to low temperatures (⬍80 °C) and low-to-
moderate salinity reservoirs.
In this paper, we present the laboratory work that lead to find an innovative solution founded on the
synergy between the formation water properties (low salinity) and high temperature environment in the
Caracara Sur Field. The study focused on the polymer screening process, rheological properties of HPAM
with the low salinity brine of Caracara Sur, the HPAM performance in porous media and chemicals to
enhance its thermal stability. This work is only focused on the polymer selection and the synergy between
low salinity brine and polymer flooding.
The main results show that the developed formulation for the Caracara Sur reservoirs is a viable cEOR
alternative. By injecting low salinity brine and HPAM with the right mix of other chemical components,
it is possible to drastically reduce the cost of cEOR, whilst maintaining the same efficiency even at higher
reservoir temperature. As a final product, an optimal ASP formulation has been developed and success-
fully tested both at laboratory and field conditions.
Introduction
The Caracara Sur Field (Llanos Basin, Colombia) consists of multilayered compartmentalized sandstone
reservoirs (Cubillos et al. 2013). Reservoirs have Darcy-level permeability, contain medium-quality oil
(21° API) with an in-situ oil viscosity of 12 cP, and are subject to strong aquifer support. After eigth years
of development, oil production is starting to decline, encouraging the investigation of enhanced/inproved
2 SPE-174653-MS

oil recovery (EOR/IOR) methods. Careful screening of various methods has resulted in the selection of
surfactant-polymer flooding as the best EOR method for this field. This paper will only focus on the
polymer evaluation and the synergy between the low salinity brine and the polymer.
Caracara Sur (CCS) has some specific properties that will make polymer flooding a challenge but also
very promising. Firstly CCS has a reservoir temperature of 86 °C which in theory makes the utilization
of HPAM impractical due to thermal degradation. Secondly the produced CCS formation water is low
salinity and unique in the sense that is not a chloride brine but a bi-carbonate brine (Table 1). The vast
majority of connate brines in oil reservoirs are high in salinity (⬎ 10000 ppm TDS) and mainly composed
of NaCl with diverse concentrations of divalent cations. In the case of CCS the formation water is fresh
(ca. 2000 ppm TDS) and composed of 95% NaHCO3 and only 4% of NaCl, the rest being divalent cations.
This results in a very high pH, around 9.7 at reservoir conditions, and low divalent concentrations.

Table 1—Formation water composition

Composition Bicarbonate Sulfate Carbonate
Formation Na Ca Mg K ChlorideCl- (HCO3-) (S04 2-) (CO3 2-) Iron (Fe)
water ppm ppm ppm ppm ppm ppm ppm ppm ppm

646 6.5 1.5 16 181 850 3.5 10 1.0

Comprehensive laboratory work was undertaken to find the best polymer for mobility control in the
ASP application. The study was focused on evaluating the impact of high temperature, low salinity and
high pH formation water, whilst optimizing the polymer concentration as well as compatibility of the
polymer solution with the surfactant formulation. Different types of polymers were tested for filterability,
thermal-chemical degradation and mechanical degradation in porous media along with coreflooding to
define the Resistance Factor (RF), Residual Resistance Factor (RRF) and polymer adsorption (see
workflow Figure 1). Based on recent experiences in the industry with low salinity we expected promising
results of the low salinity polymer flooding, taking advantage of the synergistic effect of combining CCS
natural low salinity production water with polymer and surfactant and hence yielding a cost-effective
cEOR process (Mohammadi et al. 2012; Skauge et al. 2013).

Figure 1—Caracara Sur Polymer Evaluation Workflow

SPE-174653-MS 3

Experimental Procedure
A series of key performance parameters were defined to systematically screen the best performing and
cost-effective product for the Caracara conditions: Filterability to avoid injectivity issues, thermal
stability, mechanical degradation and mobility control performance in porous media (RF, RRF, Inaccess-
able Pore Volume - IPV and adsorption).
A comprehensive screening and qualification process was undertaken: seven commercial products
were thoroughly investigated. Only the main results and findings are published here.
In order to undertake this screening and qualification program, a state of the art laboratory was created
with the following main set-ups:
1. Filterability unit.
2. Thermal stability unit and Rheometer.
3. Core preparation units. Custom-designed to fulfil all operations prior to coreflooding: core
cleaning, saturation with water and oil, aging and core characterization (effective porosity,
dynamic porosity (using tracers), water/oil permeability).
4. Coreflooding units, custom-designed to fit specific needs (Figure 2).

Figure 2—Coreflooding Laboratory

The polymer solutions for all experiments were prepared using Caracara Sur produced water (Table 1).
Results and Discussions
Filterability test. During the preparation of polymer solutions care should be taken for low quality
polymers: Ineffective polymer hydration and debris in the polymer can lead to near well-bore plugging
(Seright, et al. 2009). Filtrability tests are addressing these quality issues. Considering the challenges of
the CCS field, the study focused on HPAM, co-polymer (ATBS/Acryl-Amide) and ter-polymer (Acryl-
amide/ATBS/Acrylic-Acid). Samples of HPAM of similar anionicity and molecular weight (ca. 20 MDa)
from five different manufacturers were evaluated.
A polymer solution (2000 ppm) was injected at constant rate (20 ml/h) with an ISCO pump through
a 3 microns, 47mm Millipore filter. The delta P was measured with a 15 mBar transducer and the effluent
was collected to check polymer degradation by viscosity measurement.
Examination of Figure 3 reveals that filterability varied considerable among the HPAM polymers.
HPAM #3, #4 & #5 have a poor filterability and were discarded, as they could potentially severely damage
4 SPE-174653-MS

the injectors. HPAM #2 was at the limit of what was deemed a good filterability, but finally only HPAM
#1, along with the the Co-polymer and Ter-polymer were selected for further rheological and mechanical
degradation studies.

Figure 3—Filterability Results of Five HPAM, Co-polymer and Ter-polymer

The filterability test, helps to select the best polymer for the further lab experiments, however this does
not guarantee that the future polymer dispatched to the field, will be of the same quality. One of the
learnings from this study was the need to verify the fabrication and QC process of the polymer vendor to
ensure the delivery of polymers within specifications.
Thermal stability test. The purpose of this laboratory process was to test the robustness of the polymer
solution at reservoir temperature with and without the presence of oxygen. The presence of dissolved
oxygen by itself may not be detrimental to the stability of HPAM polymers. However HPAM polymers
can experience severe degradation by free radical attack if oxygen combines with metals (specialy ferrous
iron), residual initiators (remaining from polymerization), or other free radical generating chemicals. For
this reason polymer manufacturers do not recommend using HPAM above 70 °C as thermal degradation
will occur at higher temperatures and instead recommend using co-polymer up to 95 °C and ter-polymer
above 100 °C. The degradation mechanisms at high temperature have been described thoroughly
elsewhere (Grollman, 1982; Sorbie, 1991; Levitt, 2008, Seright et al. 2010, Seright et al. 2014).
Several tests were performed, and for clarity they are grouped in three steps:
● Testing of polymers with oxygen presence: solutions of HPAM, co-polymer (ATBS/acrylamide)
and ter-polymer (acrylamide/ATBS/acrylic acid) were prepared using produced water with oxygen
presence (0.2 – 0.3 ppm).
● Testing of HPAM in produced water with alkali under the presence of oxygen.
● HPAM mixed with production water with very low oxygen concentration (⬍ 0.1 ppm).

The polymer solution was placed in ampoules and followed a de-oxygenation process, consisting of
five vacuum cycles of helium flushing. The ampoules were sealed and then placed in an oven at constant
reservoir temperature (86 °C).
1. Testing of polymers with oxygen presence
HPAM: The thermal stability tests with oxygen presence show as expected that HPAM is severely
SPE-174653-MS 5

degraded at 86 °C and lose 60% of its viscosity in 8 weeks even in the absence of divalent cations
(Fig. 4)

Figure 4 —Testing of HPAM (with and without alkali), co-polymer and ter-polymer, at 86 °C

Co-polymer and ter-polymer: Both co-polymer and ter-polymer with oxygen presence were stable
up to 25 weeks after which a slow degradation occurs (Fig. 4). The viscosity of the co-polymer
slowly increased up to 140% of its original viscosity due to the hydrolysis of the acrylamide
moieties. The Ter-polymer seemed to follow the same degradation trend as the co-polymer but it
tended to hydrolyse a lot more than the co-polymer. The increase in viscosity reached to 170% of
its original viscosity.
The absolute viscosity results show that on average co-polymers have 50% less viscosifying power
than HPAM and ter-polymer have 10% less. This implies that to reach the same mobility inside
the reservoir 50 to 10% more polymer needs to be added to the CCS production water.
2. Testing of HPAM with alkali under the presence of oxygen
To make HPAM more thermally stable under the presence of oxygen, it was decided to test adding
alkali such as sodium metaborate tetrahydrate (NaBO2. 4H2O). The results show that by adding
0.25% of NaBO2. 4H2O, the thermal degradation stopped completely for at least 36 weeks (Figure
4).
3. Testing of HPAM at very low oxygen concentration
The need to add alkali just to protect the polymer will mean an additional cost, which could be
avoided by creating an environment which has very low oxygen concentrations (ppb-scale). For
this reason another test of HPAM without alkali was performed under very low oxygen concen-
tration conditions.
Seright et al. 2009, showed that HPAM in the absence of divalent cations and oxygen was stable
at 120 °C. This observation is critical for CCS field as the level of divalent cations is extremely
low and it is possible that HPAM could be used instead of the more expensive co- and
ter-polymers.
As can be seen in the Figure 5, in a very low oxygen environment, HPAM was as stable as co-polymer
and ter-polymer. This means that maintaining dissolved oxygen at very low concentrations, HPAM is an
effective solution for Caracara Sur Field.
6 SPE-174653-MS

Figure 5—Testing of HPAM under very low oxygen concentration, co-polymer and ter-polymer, at 86°c

HPAM Performance
Polymer hydration. Another area where CCS brine and low salinity can have a beneficial impact is
during the polymer hydration in the surface facilities. Generally polymer comes in a powder form that
needs to be hydrated before being injected. To achieve proper hydration the polymer is stirred continu-
ously in a maturation tank for a couple of hours. As can be seen in Figure 6, HPAM will take 75 minutes
to fully hydrate at 50 °C using sea water. In the case of Caracara Sur brine the hydration time of HPAM
is greatly enhanced compared to sea water and would require only 30 minutes at 50 °C (temperature of
CCS production water prior to injection).

Figure 6 —Hydration Kinetic of HPAM at 50 °C

For comparison purposes the hydration time was also measured for polymer solutions based on sea
water. Calculations show that in CCS the polymer would take 45 minutes to reach the bottom of the well,
SPE-174653-MS 7

HPAM in low salinity brine would reach the formation fully hydrated but not HPAM in sea water. This
shorter hydration time of Caracara Sur injection water (low salinity and high pH), helped to optimize the
design of the mixing plant for the cEOR pilot (Figure 6).
Mechanical degradation in porous media. Mechanical degradation means that fluid stresses become
large enough to fragment polymer molecules, resulting in an irreversible loss of viscosity. The purpose of
the experiment is to evaluate the degradation rate (DR) induced near the wellbore. The assessment of the
DR near the wellbore remains a key parameter to establish a maximum flow rate, whilst maintaining the
polymer solution´s viscosity. Coreflooding experiments have been performed using Berea sandstone,
whilst monitoring the outlet viscosity and calculating the degradation rate using the following equation:
1

With ␮0 and ␮1 as inlet and outlet polymer viscosity respectively and ␮w for water viscosity.
From the experimental results presented in the Table 2, a degradation rate of 2.8 % is calculated for
a shear rate of 1680 s⫺1, reaching 30% at an injection shear rate of 13400 s⫺1.

Table 2—Results of Shear Degradation Rate in a Berea Plug at 86°C, 800ppm HPAM Solution, CCS brine
Confining DR immediately DR measured
Q Velocity Shear rate P inlet Pressure after sampling after ⴙ20h

mL/h ft/s sⴚ1 bar bar % %

100 0,0004 336 n/a 140 0,2 0,2

500 0,0018 1679 23,5 140 2,8 2,1
1000 0,0036 3358 56,8 140 4,1 4,0
2500 0,0089 8396 103,4 140 20,0 19,9
4000 0,0036 13434 132.4 140 30.2 30.3

Since the Berea core permeabilities were considerably lower than the permeabilities of the Caracara
reservoirs (between 1 and 2 D), the results of the coreflooding were upscaled by calculating the equivalent
shear rate for 1 D and 2 D permeability cases. The assumption is that the degradation rate is shear
dependent and using the results of the Berea core (k ⫽ 292 mD) as a reference at a given shear rate, the
Degradation Rate at the higher permeabilities was estimated. This calculation was done using a meth-
odology based on pore radius, which is calculated from permeability and porosity (Veerapen, et al. 1991).
Based on these results, well characteristics and estimated injection rates a low degradation (less than
5%) is expected for polymer injection at field application. Additionally, it should be considered that low
salinity waters such as Caracara brine, make polymer solutions less sensitive to shear degradation
(Maerker et al, 1975; Zaitoun et al, 2011).
RF, RRF and Adsorption - Coreflood Experiments. CCS core´s brine permeability was measured
at various injection rates. The effective pore volume was measured by the injection of a tracer (KI) before
and after polymer injection. Two core plugs were used: Core #1 was only water saturated, whilst Core #2
was initially conditioned until the end points (i.e. residual oil saturation, Sor, irreducible water saturation,
Swi) were reached, using the unsteady state method. Main core characteristics are described in Table 3.
8 SPE-174653-MS

Table 3—Caracara Sur Core Properties

Caracara Sur core plug Core #1 Core #2

PV at Sw⫽1 (by tracer), ml 14.25 13.2

PV at Sor (by tracer), ml -- 10.85
Porosity, % 29.5 at Sw⫽1 23 at Sor
Average pore radius, ␮m 6.3 at Sw⫽1 4.03 at Sor
Absolute permeability, mD 1500 2800

Two successive slugs of polymer solutions separated by brine slugs were injected at low polymer
concentration (300 ppm) and low velocity to evaluate dynamic polymer adsorption. Adsorption induces
a delay in the elution of the first polymer front.
The RF and RRF were measured by injecting polymer at a known concentration at different rates,
followed by water at the same rates. HPAM solutions were tested at four different concentrations (300,
400, 600 and 800 ppm) and at different flow rates. At each stage the relative viscosity to water (␮r), RF
and RRF were measured and then the RF was compared with the rheological data. Tables 4 and 5
summarise the results for both core plugs at a velocity close to the expected velocity in the reservoir (~1
ft/day). Note that for Core #2 the RRF was only determined at two polymer concentrations.

Table 4 —RF and RRF Measured in Core # 1 for HPAM at Sw ⴝ 1

Table 5—RF and RRF Measured in Core # 2 for HPAM at Sor ⴝ 0.28

● Adsorption: The adsorption level determined from material balance was very low (⬍10 ␮g/g) for
both polymer slugs. These low adsorption values can be attributed to the low salinity and high pH
SPE-174653-MS 9

of the water used for the preparation of the polymer solution as well as the relatively high reservoir
temperature of 86 °C (Figure 7).

Figure 7—HPAM Adsorption measurement on Core #2 at 300 ppm at Sorⴝ0.28, vⴝ1.2 ft/d

● Relative Viscosity: this has been determined apart from the coreflood experiments. The classic
non-Newtonian behavior of a polymer solution at increasing velocities/shear rates is observed.
● Residual Factor: RF data from the coreflood are in good agreement with the rheological data. All
values are close to the relative viscosity measured, established outside the coreflood experiments.
● Resistance Residual Factor: The RRF´s for core#1 (Sw⫽1) remain low (RRF ⬍ 2.5), indicating
a relatively low permeability reduction due to adsorption of a polymer layer. For core#2, which is
under conditions of residual oil saturation, the measured RRF level is more important, equal to 4.
● Inaccessible pore volume: At residual oil saturation (Core #2), it can be noticed that IPV is highly
reduced (~4%) compared with Core #1 (17%), which is fully water saturated. Oil trapped along
the core reduces the access to the polymer macro-molecule. This effect is even stronger in a low
salinity brine where the polymer coil is expanded so that the gyration radius (Rg) is bigger (4Li
Yiqiang, 2014). The IPV is moderately important due to the high molecular weight of the HPAM
polymer (ca. 20 MDa) but it should not be a major concern for CCS, due to the multi-Darcy
permeability.
Practical Implications/Recommendations
Laboratory: A decision was made early on in this study to run the polymer testing using CEPSA’s own
laboratory facility rather than outsource it to a 3rd party. This has had a number of tangible benefits:
● The ability to make the testing process continuous, allowing interruptions at any stage and seeing
immediate results.
● An enhanced interaction and discussion between the teams involved in the study.
● Only utilizing the processes that were required for this specific polymer study, resulting in a more
cost effective methodology.
● The ability to upscale the laboratory results quickly to field conditions.

Polymer filterability: This is a specific requirement to ensure that the Polymer is of the highest quality
for the laboratory testing and field application.
The level of quality of the original samples tested in the lab does not necessarily guarantee that future
polymer batches destined for the field have that same quality. From our experience, it is known that many
10 SPE-174653-MS

plants worldwide produce HPAM polymer but their QC process and consistency can differ dramatically.
To ensure that future polymer batches dispatched to the field will be consistently of high quality, specific
plants were visited to review their polymer manufacturing process and only those manufacturers were
pre-selected, who could subscribe to high QC standards and consistency.
Thermal/chemical stability: A basic requirement for any cEOR pilot is to provide a cost effective
solution. In other words to find a polymer that not only fits the technical requirements but is also not
excessively expensive.
For the Caracara Field it was initially assumed that conventional HPAM polymer would fail due to high
reservoir temperatures. Nevertheless it was decided to make some tests before rejecting this cheaper
polymer. It was found that, due to the low salinity of the field, the high temperature did not affect the
polymer as previously predicted.
Whatever the selection, two critical physical conditions are needed to prevent/reduce polymer degra-
dation over time:
a. Central processing facilities with a closed system to ensure very low oxygen concentration.
b. A mixing plant equipped with nitrogen blanketing to ensure an oxygen free polymer make up.
It was concluded that HPAM polymer is a fit for purpose solution for ASP application in the Caracara
Sur Field. The low salinity, high pH injection water in Caracara shows potential for overcoming
temperature concerns for cheap HPAM polymer solutions in other potential fields. If injection water can
be diluted to low salinities economically and if cheap alkali can be added to increase the pH, the cost of
polymer can be reduced significantly in higher temperature environments. In addition to the benefits of
a cheap mobility control by polymer flooding, low salinity flooding is known to mobilize additional oil.

Acknowledgements
The authors would like to thank CEPSA EP and ECOPETROL Management for their support and
permission to publish this paper.

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