Journal of Petroleum Exploration and Production Technology (2020) 10:283–296

[Link]

ORIGINAL PAPER - EXPLORATION ENGINEERING

Evaluation of new surfactants for enhanced oil recovery applications

in high‑temperature reservoirs
Nazliah Nazma Zulkifli1,2 · Syed M. Mahmood1 · Saeed Akbari1 · Arif Azhan A. Manap2 · Nor Idah Kechut2 ·
Khaled Abdalla Elrais1

Received: 2 November 2018 / Accepted: 10 June 2019 / Published online: 26 June 2019
© The Author(s) 2019

Abstract
Surfactants have been successfully used for enhanced or improved oil recovery in reservoirs having mild conditions (low
temperature, low salinity). Reservoirs having harsh conditions, however, offer unique challenges in that most surfactants
precipitate and chemically degrade due to a combined effect of high temperature and hardness salinity. Industry’s efforts are
continuing to develop or formulate surfactants for oil recovery applications to high temperature and salinity. The aim of this
study was to evaluate several modified anionic surfactants/formulations that were claimed to be able to overcome the unfa-
vorably high-salinity brine (sea water) and high temperature and to understand the impact of high temperature to surfactant
adsorption. A series of experiments were conducted to characterize and quantify the effects of aging time in high temperature
(106 °C) and seawater salinity (32,000 ppm with 1600 hardness) on surfactant performance. Results for both sulfate- and
sulfonate-based surfactants were deemed not to be satisfactory. Sulfate-based surfactants encountered hydrolysis problem at
high temperature, whereas sulfonate-based surfactants precipitated in the presence of divalent ions. This study then focused
on alkyl ether carboxylate (AEC) as the main surfactant, and blends of AEC with alkyl polyglucoside (APG). To find the
optimum conditions, phase behavior tests were performed with a fixed seawater salinity but with different blending ratios of
surfactant and co-surfactant, as well as overall surfactant concentrations, similar to the salinity scan. Type III microemul-
sion was observed for both surfactant solutions of AEC and AEC–APG blend with IFT of 1­ 0−3 mN/m (millinewton/meter).
Surfactant adsorption resulted in lower adsorption in the high-temperature region. The results of this project are urgently
needed by the industry for future screening in order to find suitable surfactants for applying to reservoirs with harsh condi-
tions. The study also intends to provide an understanding of adsorption relationship to high temperature, as a guideline in
addressing surfactant losses due to adsorption at high-temperature field application.

Keywords Chemical enhanced oil recovery · High temperature · High salinity · Surfactant adsorption

Introduction 2018). Surfactant is a surface acting agent, and they can

adsorb at a surface of the fluid–fluid interface to alter the
Surfactants are widely used and have a very large number surface properties significantly, thus reducing the surface
of applications, especially in the petroleum industry for tension and interfacial tension (Hocine et al. 2016). The
enhanced oil recovery (EOR) process because of their ability interfacial or surface tension is a measure of the difference
to influence the properties of the rock surface and oil–water in nature where the two phases are meeting at the interface
interface (Puerto et al. 2012; Lu et al. 2014; Hesham et al. or surface; the higher the dissimilarity in their natures, the
higher the interfacial tension or surface tension between
them (Rosen 2004; Hadian et al. 2018; Hematpur et al.
* Nazliah Nazma Zulkifli
[Link]@[Link] 2017). Surfactant has a molecular structure that consists
of a hydrophilic group which has a strong attraction to the
1
Petroleum Engineering Department, Universiti Teknologi solvent and the hydrophobic group, which has very little
PETRONAS, Persiaran UTP, 32610 Seri Iskandar, Perak, attraction to solvent. Surfactant is classified depending on
Malaysia
the nature of the hydrophilic part. These classes are anionic,
2
Kawasan Institusi Bangi, Petronas Research cationic, zwitterionic, and non-ionic (Sheng 2011).
Sdn. Bhd. (PRSB), 43000 Kajang, Selangor, Malaysia

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284 Journal of Petroleum Exploration and Production Technology (2020) 10:283–296

There are two surfactant mechanisms in EOR process surfactant, CMC determination has been commonly made
application, which are lowering the interfacial tension (IFT) by measuring the surface tension or interfacial tension as a
and emulsification of oil and water (Bevlere et al. 1988). function of surfactant concentration. Before reaching CMC,
Surfactants are used to reduce interfacial tension, which the surfactant is adsorbed at the oil–water interface; thus,
leads to an additional mobilization of oil trapped by capil- interfacial tension keeps reducing by surfactant concen-
lary forces in the rock matrix. In the reservoir, trapped oil tration. After reaching CMC, however, there is no further
droplets (residual oil) cannot be displaced due to the high reduction in interfacial tension by surfactant concentration.
energy required to overcome capillary pressure (Pc) under It is due to the fact that at CMC point, micelles start to form
normal oil–water IFT. The surfactant is used to overcome and aggregate in the liquid phase. By increasing the sur-
this problem since it is capable of reducing oil–water inter- factant concentration above CMC, surfactant molecules will
facial tension from 10–30mN/m to 0.001mN/m. By low- move to the liquid phase and form more micelles instead of
ering oil–water IFT, capillary number (Nc) will increase. moving to the surface and reduction in IFT (Schramm 2000).
Thus, oil droplet can be displaced easier and increase oil Addition of surfactant in injection brine will cause emul-
recovery. The capillary number for strongly water-wetting sification of oil in water. In EOR, the microemulsion is a
media can be calculated, as shown in Eq. (1) (Chatzis and stable translucent micellar solution of oil and water. Types
Morrow 1984): of microemulsion and salinity effect on phase behavior will
determine the potential surfactant formulation for EOR pro-
Nc = 𝜈𝜇∕ 𝜎, (1) cesses (Southwick et al. 2016). The purpose of the phase
where v is the Darcy velocity (m/s), µ is the dynamic vis- behavior test is to determine the chemical formulation for a
cosity of the liquid (mPa s), σ is the interfacial tension specific application. In practice, the range of salinity is stud-
between fluids (mN/m), and Nc is the capillary number ied to find the relative surfactant solubility in brine and oil.
(dimensionless). Optimum salinity is targeted for EOR formulation, where the
In EOR methods involving surfactant injection, critical surfactant is equally soluble in oil and brine, which results
micellar concentration (CMC) is important for IFT reduction in the lowest IFT between oil and brine.
and surfactant adsorption. IFT reduction will be increased However, a study on modified phase behavior test also
by surfactant concentration. However, the reduction will can be done for a fixed salinity application, and more hydro-
be stopped after reaching CMC, as schematically shown in philic and more hydrophobic surfactants are mixed in dif-
Fig. 1 and reported in the literature (Sheng 2011; Kamal ferent ratios to produce under optimum, optimum, and over
et al. 2017). Moreover, the surfactant adsorption will be optimum conditions similar to salinity scan (Southwick
increased by surfactant concentration to the CMC point, in et al. 2016). For a fixed water salinity application, such as
which maximum adsorption will occur. After CMC, adsorp- seawater application as the injection water, modified phase
tion will be stopped, and cumulative adsorption will reach behavior test can be done to determine optimum surfactant
the plateau region (Schramm 2000; Hamed et al. 2018). formulation for a typical field condition (i.e., fixed water
At low surfactant concentrations, most of the solution salinity). The present study focused on fixed salinity, where
properties are similar to the simple electrolyte, but at higher seawater is used as brine for surfactant mixture. The opti-
surfactant concentration, unusual changes are observed mum ratio of the main surfactant (AEC) and co-surfactant
which can be used for CMC determination. For EOR (APG) is identified based on modified phase behavior.
The high potential of surfactant-based flooding has been
demonstrated in favorable conditions, such as at low tem-
perature and soft brines. However, there are a very limited
number of surfactants available that can be applied under
harsh conditions of high temperature (> 100 °C) and high
salinity/hardness. Sulfates surfactant can improve surfactant
tolerance to high salinities. However, they are subjected to
hydrolysis at high temperature because it has sulfur-to-oxy-
gen bond. Sulfonate surfactants such as olefin sulfonates and
alkyl benzene sulfonates are stable at high temperature but
sensitive to divalent ions (Abbas et al. 2017). Sulfonates
are stable at high temperatures because they have sulfur-
to-carbon bond, which is not easily subjected to hydrolysis.
At high temperature, the performance of surfactant-based
Fig. 1  Schematic of the concentration dependence of surface tension flooding can be drastically decreased due to the instabil-
for the solution of a micelle-forming surfactant ity of the applied surfactant. Chemically and the thermally

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Journal of Petroleum Exploration and Production Technology (2020) 10:283–296 285

stable surfactant is required to be identified, and its per- surfactant concentration. To evaluate surfactant adsorption,
formance is mandatory to be evaluated for chemical EOR the difference in initial surfactant concentration to final con-
applications. Chemical stability is whether the surfactant centration during flooding is measured. This difference is
molecule degrades under specified targeted condition, converted to the gram of surfactant and divided by gram
whereas solubility is whether surfactant dissolved and does of rock to determine adsorption value (g/g). Reviewing
not precipitate in the solution (Jurgenson et al. 2015; Morel previous publications showed that most of the adsorption
et al. 2016; Adkins et al. 2012). The addition of co-solvent researches had been focused on a relatively low tempera-
or co-surfactant enables the surfactant solution to be pre- ture and adsorption at high temperature (> 100 °C) has been
pared with a concentrated brine solution, even at high diva- ignored. Therefore, this study intends to fill the gap and
lent cations concentration (Bevlere et al. 1988). The biggest systematically experiment the effect of high temperature on
impediment to the use of a thermally stable surfactant in adsorption and provides a guideline in addressing surfactant
chemical EOR is the very poor solubility and compatibility losses due to adsorption at high temperature.
of these surfactants in water containing high divalent cations
such as calcium and magnesium, especially at high tempera-
ture where the solubility and compatibility are drastically Materials and methods
reduced. Thus, this study is meant to identify workable sur-
factant formulation at harsh field conditions and also to find Materials
a co-surfactant and an optimum ratio for blending surfactant
system that can improve the selected surfactant’s compat- Surfactants that were used in this study are alkyl ether car-
ibility with brine, chemically and thermally stable. boxylate (AEC) and alkyl polyglucoside (APG). The general
The cost of the surfactant is one of the most expensive structure of each surfactant is shown in Fig. 2. The carboxy-
items in the total cost of chemical EOR project. One of the late surfactant functionality will promote temperature sta-
criteria for economic success is minimizing the surfactant bility, and there are established methods to introduce this
loss due to adsorption. Therefore, the knowledge of sur- hydrophilic headgroup in alkyl alkoxylates. It has outstand-
factant adsorption is critical and needs to be studied, espe- ing tolerance against high temperatures and high salinity
cially at high temperature. Adsorption refers to a collection while delivering high interfacial activity (Lu et al. 2014;
of molecules on the surfaces, either internal or external of Jun et al. 2014). Anionically modified APG was used as co-
liquids or solids (Dabrowski 2001). During transportation surfactant, because it has excellent tolerance against salinity
through porous media, surfactant molecules tend to aggre- hardness due to its hydrophilic glucose moiety, and improves
gate on the surface of the rock which lowers the initial AEC solubility (Jurgenson et al. 2015). Table 1 shows the

Fig. 2  General chemical struc-

ture of used surfactants: a alkyl
ether carboxylate (AEC), b
alkyl polyglucosides (APG)

Table 1  Properties of alkyl Surfactant Type Key properties Supplier

ether carboxylate and alkyl
polyglucoside surfactants Alkyl ether carboxylate (AEC) Anionic surfactant Appearance: yellowish, BASF
obtained from the supplier viscous, liquid
pH: 7.1
Density: 1.0241 g/cm3
at 23 °C
Active matter (%): 45
Alkyl polyglucoside (APG) Anionic surfactant Appearance: yellowish, BASF
liquid.
pH: 8.5
Density: 1.109 g/cm3 at
23 °C
Active matter (%): 51.5

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Table 2  Sea water composition the selected formulations were tested for their adsorption
No. Test description Unit Test methods Analysis
relationship with temperature.
Surfactant screening was started by close observation of
1 pH at 20 °C – APHA 4500 H 7.76 the surfactant solution solubility and compatibility at ele-
2 Conductivity uS/cm APHA 2510B 49,537 vated temperatures (80 °C and 106 °C) to simulate actual
3 Salinity mg/L APHA 2520B 32,390 challenging reservoir conditions. Optimum surfactant for-
4 Total dissolved solids mg/L APHA 2540C 35,200 mulation in surfactant flooding desires to be compatible with
6 Density @ 20 °C g/cm4 ASTM 4052 1.0237 the applied solvent (sea water in this study) and avoid pre-
8 Sulfate, ­SO42− mg/L HACH 8051 2000 cipitation problem and also to ensure the good performance
9 Chloride, ­Cl− mg/L APHA 4500Cl-B 18,520.85 of the whole process. In this study, only two variables of sur-
10 Bicarbonate, ­HCO3- mg/L APHA 2320 B 148.29 factant concentration and surfactant/co-surfactant ratio were
11 Carbonate, CO−2 3 mg/L APHA 2320 B 0 adjusted to find the best possible surfactant formulation. In
12 Hydroxide, ­OH− mg/L APHA 2320 B 0 addition, the proposed surfactant formulation requires to be
Total Anion 20,669.14 chemically stable for a period of time for high-temperature
13 Iron, Fe mg/L APHA 3120B 0 application (Zhou et al. 2013). The surfactant solubility and
14 Sodium, Na mg/L APHA 3120B 10,080 compatibility were assessed, and non-soluble composition
15 Calcium, Ca mg/L APHA 3120B 380 was identified if the surfactant solution showed cloudiness,
16 Magnesium, Mg mg/L APHA 3120B 1222 phase separation, and precipitation.
17 Potassium, K mg/L APHA 3120B 368.5
18 Strontium, Sr mg/L APHA 3120B 6.456 Oxygen control preparation
19 Barium, Ba mg/L APHA 3120B 0
Total cations 12,056.956 The surfactant screening test was done in the oxygen control
condition to avoid oxygen presence in the system. In fact,
the surfactant may quickly oxidize at high temperature and,
available information for the surfactants, which was pro- therefore, lose its property (Sheng 2011). Besides, it is a
vided by the supplier and has not independently verified. must to remove the oxygen from the system to have a similar
Table 2 shows the composition of injected water, which was condition to the reservoir since most of the oil reservoirs are
mixed with the above-mentioned surfactants. in anaerobic, reducing environment (Akbari et al. 2017).
Therefore, for laboratory testing, the chemical preparations
Experimental procedure were in the oxygen control condition where we removed
dissolved oxygen from the solution. To do so, a specific pro-
This study involved surfactant screening in monitoring cedure was followed. Firstly, the prepared surfactant solu-
the surfactant performance at high-temperature and high- tions were vacuumed and purged with nitrogen to remove
salinity/hardness conditions. Surfactant screening criteria the dissolved oxygen for at least 2 h, with the alternate cycle
involved solubility at high temperature, interfacial tension of nitrogen and vacuum flow (setup is shown in Fig. 3).
test, microemulsion phase behavior, and thermal stability. Then, the samples were transferred into an automated glove
After finding the optimum surfactant solution composition, box (MBRAUN) as shown in Fig. 4 to further reduce dis-
solved oxygen and to ensure the surfactant samples and the

Fig. 3  De-gas (vacuum) and

nitrogen purging setup

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Journal of Petroleum Exploration and Production Technology (2020) 10:283–296 287

Fig. 4  MBRAUN glove box

environment is in oxygen-free condition. Oxygen content Solubility and compatibility

was monitored using a dissolved oxygen probe (­ CHEMets®
Visual Kit) to assure that the oxygen content is less than Surfactant solutions stock was received from BASF chemi-
50 ppb (part per billion). cal supplier. Diluted surfactant solution was prepared by
For long-term thermal stability and adsorption test, sur- using dilution Eq. (2), and the active percent for each stock
factant solutions were stored in glass ampoules. Ampoules surfactant is considered.
containing surfactant solutions were sealed using fire to
avoid solution evaporation and dried out at high tempera-
Dilution equation = M1V1∕M2V2, (2)
ture. Figure 5 shows the vacuum and nitrogen purging setup where M1 is the concentration in molarity (moles/liters) of
for ampoules fire sealing. Alternate nitrogen purging and the concentrated solution, V1 is the volume of the concen-
vacuum flow were applied for the solution for 2 h. trated solution, M2 is the concentration in molarity of the
dilute solution (after more solvent has been added), and V2
is the volume of the dilute solution.
Surfactant and co-surfactant were mixed at predeter-
mined concentrations and various ratios of surfactant: co-
surfactant (80:20, 70:30, 60:40, and 50:50), to determine

Fig. 5  Vacuum and nitrogen

purging setup for fire sealing

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the most compatible and soluble surfactant solution for temperatures. The properties of the oil type, which were
further test. Surfactants were prepared in saline seawater used in this study, are provided in Table 3.
brines at elevated temperatures, to simulate challenging res- In this study, since it is a fixed water salinity applica-
ervoir conditions. Surfactant solution has a high tendency tion where the injection water is seawater, a modified phase
to precipitate in seawater brine with high divalent cations. behavior test was applied. In this test, a surfactant and co-
Therefore, in order to ensure good performance of the sur- surfactant solutions were mixed at different ratios. The total
factant, good solubility and compatibility of surfactant with surfactant solutions were added into crude oil to produce
injected brines are critical. The surfactant solutions were under optimum, optimum, and over optimum conditions
physically observed for its stability and compatibility up similar to traditional salinity scan to determine optimum
to 60 days. Surfactant solubility and compatibility were surfactant formulation (Southwick et al. 2016). For EOR
assessed, and non-soluble composition was identified if the purposes, the best phase type is Type III, followed by Type I
surfactant solution showed cloudiness, phase separation, and and Type II, according to Windsor (Sheng 2011). The transi-
precipitation. tion from Windsor type I to III is shown in Fig. 6, which can
occur due to several parameters such as salinity, surfactant
Phase behavior test concentration, and, so forth (Chan and Shah 1979).

Microemulsion phase behavior study was then tested to Interfacial tension (IFT)
identify optimum surfactant formulation. For this particular
study, tests were performed at high temperature using sea- Interfacial tension (IFT) test was then used for further
water injection brine as a solvent, which contains divalent screening of the selected potential surfactant formulations
ions (hardness). The test was conducted by adding the sur- which were previously selected based on their good compat-
factant solution in reservoir crude oil in the tubes, and then ibility with the sea water brine and having Type III and Type
mixed thoroughly and allowed to equilibrate. Equilibrium I from phase behavior test previously done. The surfactant
between the surfactant and crude oil had been quantified by solutions are compatible with brines when it is completely
visual inspection of phase behavior such as microemulsion soluble with no precipitations. The IFT measurement equip-
phase shift, phase volume, color transparency of aqueous ment used in this study was spinning drop tension meter
phase until it has no change for at least 2 weeks in elevated (SVT20 Data Physics) which can handle test temperatures
up till 120 °C. Targeted IFT value for surfactant solution in
EOR process is ultra-low IFT, at the range of ­10−3 mN/m
Table 3  Crude oil properties (millinewton/meter) and below, between oil and water so
No. Test description Unit Results that oil droplet can be displaced easily due to resulting high
capillary number (Wu et al. 2010).
1 Volatiles mass% 75
2 Asphaltene and inorganic (n-pen- mass% 0.06 Thermal stability
tane insoluble)
3 Saturates mass% 18
This study is designed for surfactant application in high-
4 Aromatics mass% 4.7
temperature conditions. Surfactant solution was prepared
5 Resins mass% 0.16
and stored in fire-sealed glass ampoule, to avoid evaporation
6 Wax content mass% 6.3
and solution dried up. Prepared surfactant solutions were
7 Kinematic viscosity @ 90 °C mm2/s 1.047
measured for their concentration, and their concentration

Fig. 6  Three types of microemulsions adapted from James Sheng (2011)

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Journal of Petroleum Exploration and Production Technology (2020) 10:283–296 289

will be taken as initial concentration, in which later will be have higher exposed surfaces area than consolidated cores
used as references in determining surfactant concentration and will give a worst-case value for surfactant adsorption.
loss over time. The surfactant solutions were tested for a The sand and clay samples were sieved prior to testing. For
long term up to 2 months for thermal stability where the this study, silica sand used is at the size of 250 nm to the
surfactant solutions were aged at high temperatures 106 °C 300 nm range, and for clays, the size range used was below
and then the concentration, pH, and oxygen content of sur- than 100 nm size. The ratio of 1:5 of crushed sand to the
factant solutions were measured throughout predetermined chemical solution was used. The silica sand was washed
sampling days. In this step, as previously discussed in the with brine, and the muddy-like solution formed at the top of
oxygen control procedure, aging the solution at anaerobic the solution was removed as many times as needed until a
condition is a must which was carefully provided in this clear solution observed, as shown in Fig. 7. Then, the sand
work. Each ampoule containing surfactant solution was was exposed to injection brines, for overnight. The sands
taken out from the oven to measure their concentration loss were dried and weighted according to predetermined weight
over time. Degraded surfactant concentration by thermal was and ratio.
measured by measuring remaining surfactant concentration, Samples were stored in glass ampoules, and the dissolved
using high-performance liquid chromatography (HPLC). oxygen in the samples was removed by vacuum and nitrogen
HPLC is a separation technique for components in the form purging of the solution for almost 2-h sequence flow. The
of column chromatography that pumps a sample in a mobile surfactant and sand samples were aged for 24 h and sampled
phase (solvent) at high pressure through a column with a out to determine the remaining surfactant concentration.
stationary phase. During aging, the samples are constantly agitated for every
1 h. At sampling time, surfactant solution samples were
Surfactant adsorption investigation at high temperature taken out from the top of the solution, and then centrifuged
the solution to separate sands and clays. The pH of the solu-
Static adsorption was carried out to quantify the loss of tion was recorded, and adsorption values were calculated by
surfactant by means of adsorption onto the rock. All static measuring the remaining surfactant concentration. The unit
adsorption tests were performed in anaerobic conditions at of chemical adsorption in the laboratory is reported as the
elevated temperature. Static adsorption experiment was per- mass of adsorbed chemical per unit mass of rock (mg/g rock)
formed using crushed sand samples. Crushed sand samples as given in Eq. (3). Surfactant concentration measurement
was done using HPLC.

[Initial Conc. − Final Conc.] (mg∕L) ∗ Vol. of Solution (L)

Adsorption, mg∕g = . (3)
Dry Weight of Rock (g)

Fig. 7  Crushed silica sand

washing process. a Sand with
muddy-like solution while b
cleaned sand after several rinses

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Fig. 8  Common surfactant

type’s compatibility and solubil-
ity, at 25 °C

screening. Figure 8 shows their solubility and compatibility.

It is clearly seen that sulfonate-type surfactants precipitate in
seawater brine, due to its sensitivity to divalent ions present
in the brines. On the other hand, sulfate surfactant shows
very good solubility. However, Shupe (Shupe 1978) in his
patent explained that sulfate linkage in the molecular struc-
ture of surfactant causes the molecules to be highly sensitive
to temperature. This results in hydrolysis or other perma-
nent degradation of the molecules to a non-reactive form.
Therefore, surfactants with sulfate units are not suitable for
formations with high temperatures. Thus, carboxylate-type
surfactant was proceeded for further evaluation at high tem-
perature (Fig. 9).
Alvares (Jurgenson et al. 2015) reported that using
AEC alone at harsh condition might not meet required sur-
factant performance criteria. Thus, co-surfactant is needed
to enhance surfactant performance, especially solubility.
Therefore, single-surfactant AEC and blend of AEC and
APG surfactant formulations at various concentrations and
Fig. 9  Solubility test a clear surfactant solution and b cloudy sur- ratio were tested for solubility and compatibility with sea
factant solution water at a baseline temperature of 80 °C and reservoir tem-
perature of 106 °C. All samples were prepared using sea
Results and discussion water as brine and aged at a predetermined temperature in
sealed glass ampoules containing no oxygen. Then, sur-
Solubility and compatibility at high temperature factant solubility and compatibility were assessed, and non-
soluble composition will be identified if the surfactant solu-
Three types of surfactant were tested for its solubility in tion showed cloudiness, phase separation, and precipitation.
seawater brine at ambient conditions for a preliminary

Table 4  Summary result for Surfactant blend composition Total surfactant concentration (wt%)
surfactant solubility at various
concentrations and blending 0.05 0.1 0.2 0.4 0.6 0.8 1
ratio after 60 days at 106 °C
AEC Clear Clear Cloudy Cloudy Cloudy Cloudy Cloudy
AEC + APG (ratio 80:20) NA Clear Cloudy Cloudy Cloudy Cloudy Cloudy
AEC + APG (ratio 70:30) NA Clear Cloudy Cloudy Cloudy Cloudy Clear
AEC + APG (ratio 60:40) NA Cloudy Clear Clear Clear Clear Cloudy
AEC + APG (ratio 50:50) NA Clear Clear Clear Clear Clear Clear

NA test did not perform at this condition

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Journal of Petroleum Exploration and Production Technology (2020) 10:283–296 291

Table 5  Summary result for Surfactant blend composition Total surfactant concentration (wt%)
surfactant solubility at various
overall concentrations and 0.05 0.1 0.2 0.4 0.6 0.8 1
blending ratio after day 60 days
at 80 °C AEC Clear Clear Cloudy Clear Cloudy Cloudy Cloudy
AEC + APG (ratio 80:20) NA Clear Clear Clear Clear Clear Clear
AEC + APG (ratio 70:30) NA Clear Clear Clear Clear Clear Clear
AEC + APG (ratio 60:40) NA Clear Clear Clear Clear Clear Clear
AEC + APG (ratio 50:50) NA Clear Clear Clear Clear Clear Clear

NA test did not perform at this condition

Fig. 10  APG surfactant compatibility and solubility at 0.3% and 1.0 Fig. 11  APG surfactant compatibility and solubility at 0.3% and 1.0
wt% concentration, at 80 °C after 30 days (left) and 60 days (right) wt% concentration, at 106 °C after 30 days (left) and 60 day (right)

Tables 4 and 5 show the summary results for surfactant solu- hardness conditions even with co-surfactant applica-
bility after 60 days at 106 °C and 80 °C, respectively In these tion, since several blend surfactant formulations showed
tables, a word of clear indicates that the surfactant solution incompatibility at high temperature. Table 4 also shows
appearance is clear and no precipitation or cloudiness was that changing the surfactant/co-surfactant ratio can help to
observed (Fig. 10a) and cloudy means that the surfactant find an optimum ratio, for this case (50:50 for AEC + APG,
solution became cloudy and was not compatible with the respectively), which can result in a compatible formulation
injection seawater brine (Fig. 10b). for high-temperature application.
Results show that surfactant solubility behavior differs APG alone was also tested to check APG stability as
at a high temperature of 106 °C as compared to the base- co-surfactant at high temperature. Figure 10 shows that the
line temperature of 80 °C. At 106 °C, most of the samples APG solution is stable at 80 °C even after 60 days for both
became cloudy and showed the sign of incompatibility concentrations of 0.3 to 1.0 weight %. However, APG sur-
with the sea water. This cloudiness is coming from the fact factant at a high temperature of 106 °C encounters color
that oxygen bond in the surfactant chemical structure can changing and phase separation, as evidenced by Fig. 10,
be affected, due to oxidation by increasing the tempera- which can be the main cause of instability observed in the
ture above 80 °C. Therefore, it makes surfactant molecules blending surfactant formulation in 106 °C. The color change
become less water soluble, thereby changing the partitioning of the APG solution to yellowish at 106 °C, which was
coefficient (Bevlere et al. 1988). At 80 °C, surfactant blend clearly observed at high concentration of APG, is possibly
is too hydrophilic and, therefore, showed good compatibility due to the degradation of APG at high temperature. There-
with brine, thereby producing only normal emulsion with fore, APG is only recommended to be used as co-surfactant
no tendency to form a microemulsion phase. On the one in the high-temperature application at optimum ratio and
hand, the cloudiness reported at 80 °C for AEC surfactant lower concentration to enhance the solubility of the main
alone (Table 5) shows that using a co-surfactant is a must surfactant in the sea water (Fig. 11).
when good compatibility with the sea water is desired. On
the other hand, it is still extremely difficult dealing with
the harsh condition of high-temperature and high-salinity/

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Fig. 12  Phase behavior of

formulations of a AEC sur-
factant only and b AEC with
APG at ratio 50:50 at 106 °C at
seawater brine. Total surfactant
concentration increases from
left to right from 0.2 wt% to
1.0 wt%

Phase behavior IFT measurement

Microemulsion phase behavior test of single-component Results of the IFT test are presented in Fig. 13. The figure
AEC and a blending formulation of AEC with APG at an shows that AEC surfactant alone at a concentration range of
optimum mixing ratio of 50:50 were also performed in this 0.4 wt% to 1 wt% is able to lower down the interfacial ten-
work. Different surfactant concentrations prepared with sion to approximately ­10−3 mN/m region at 106 °C. There-
seawater brine and tests were performed at an elevated tem- fore, it has good performance and high interfacial activity
perature of 106 °C, and the microemulsion produced was at high temperature. This low IFT result is expected since
monitored visually until the mixture system equilibrates. based on phase behavior microemulsion test, type III Wind-
Figure 8 shows the result of this test for a range of sur- sor was observed for the same surfactant solutions concen-
factant concentration from 0.2% to 1.0 wt%. On the one tration range. However, the range of surfactant concentration
hand, Windsor type III was produced for all concentrations that results in optimum condition from the two tests of phase
of single AEC, although cloudiness can be observed in the behavior and IFT cannot be directly compared because oil-
brine phase, as shown in Fig. 12a. It also shows that AEC is to-water ratio in phase behavior test is 100 times higher than
a robust surfactant, as it is able to reduce interfacial tension the IFT test. Therefore, a shift of optimum concentration is
and produce microemulsion phase at low concentration of expected between these two tests.
0.2 to 1.0 wt%. However, only two low concentrations of Based on the solubility test, using AEC alone will be
0.2 wt% and 0.4 wt% showed Windsor type III behavior risky as the solution may face cloudiness and, in some
for blending of AEC and APG at optimum ratio, as shown cases, even may encounter surfactant precipitation prob-
in Fig. 12b. At a concentration of 0.6 wt% to 1.0 wt% for lem. Therefore, the addition of co-surfactant to enhance
blend formulation, surfactant becomes more hydrophilic and solubility might become a necessity. Figure 13 also shows
shows Windsor type I. the IFT behavior of the blend formulation of surfactant and
co-surfactant as a function of total surfactant concentra-
tion at 106 °C and expressed that ultra-low IFT (at region
­10−3 mN/m) is achieved at a low surfactant concentration

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Journal of Petroleum Exploration and Production Technology (2020) 10:283–296 293

Fig. 13  Interfacial tension, IFT Measurement

mN/m of AEC and AEC/APG
surfactant at different concen- 1.0000
trations at 106 °C in seawater
salinity brine
0.1000

IFT, mN/m
0.0100

0.0010

0.0001
0.05 0.1 0.2 0.4 0.6 0.8 1
Surfactant Concentraon, weight%

AEC at 106C 50:50 AEC:APG at 106C

of blend formulation (0.1% to 0.2 wt%). 2000 ppm is the not a problem since injection fluids are degassed. All blend-
concentration where the lowest IFT is observed for blending ing AEC/APG solutions were observed yellowish (due to
surfactant formulation. APG color) but clear in solutions, while AEC surfactant was
observed slightly cloudy when prepared. Initial concentra-
Effect of thermal on surfactant performance tion prepared for both surfactant solutions (AEC and AEC/
APG) is at 1.0 wt%. Figure 14 shows the results for the ther-
The remaining concentration in the targeted environment mal stability of the surfactant solution in seawater brines at
represents a criterion for any chemicals to be used. Continu- 106 °C. From the graph, it is clearly seen that after 60 days,
ous aging of the displacing fluid is detrimental to EOR. For both surfactant solutions maintained their concentrations at
this reason, prolonged thermal stability tests were conducted 1.0 wt%. The experimental accuracy of the HPLC method is
for selected surfactant in the injection brines. The surfactant around 2%, which in this case equals to 0.02 wt%. Surfactant
solutions were evaluated for their stability to maintain their peak was qualitatively the same as the original samples,
concentrations throughout the aging time. Dissolved oxygen thus showing that no degradation was observed. For AEC
is also measured for all samples, to ensure that the surfactant surfactant, even though the surfactant concentration main-
solutions were kept in anaerobic condition. This step is cru- tained, it is clearly seen that the surfactant solution turns
cial since surfactant must be in free oxygen condition, as cloud over the aging time. Blending AEC/APG surfactant
oxygen is such a concern. Organic molecules can be sensi- was observed to have no degradation, and clear solution was
tive to oxygen at high temperatures. In reservoir, oxygen is observed but with a higher intensity of yellowish solution,

Fig. 14  Surfactant thermal deg- Surfactant thermal degrada on in seawater brines at

radation at 106 °C in seawater
salinity brine 106°C
2.00
Surfactant Concentra on, %

1.80
1.60
1.40
1.20
1.00
0.80 AEC
0.60 AEC:APG
0.40
0.20
0.00
0 10 20 30 40 50 60 70
Elapsed days

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294 Journal of Petroleum Exploration and Production Technology (2020) 10:283–296

Fig. 15  Adsorption relation- Adsorp on due to temperature effect

ships due to the temperature
effect 5.00 9.000

Adsorp on, mg/g rock

4.00 8.000

7.000
3.00
6.000

pH
2.00
5.000
1.00 4.000

0.00 3.000
80 90 100 106 120
Temperature, C
Total ads, mg/g rock pH

reduction in solubility, and compatibility up to 60 days of adsorption due to the temperature effect. The ionic sur-
observation. This is believed due to the initial concentration factant efficiency decreases when temperature increases,
of the solution that is too high, 1.0 wt%. because at high temperature, physical bonding to the
surface is weaker; thus, it is anticipated that surfactant
Temperature effects on surfactant adsorption adsorption decreases when temperature increases and this
study proved the relationship. Solubility means surfactant
The high-temperature condition with more than 100 °C has stronger bonding in water, and it has been observed
is the primary focus of this study. Therefore, adsorp- that at high temperature, the solubility decreases, which
tion behavior in the high-temperature region was stud- indicates that the bonding to water is weaker, thus sup-
ied, and the adsorption trend was observed. For adsorp- porting lower adsorption at high temperature.
tion, temperature region was investigated at a range of Surfactants used are an anionic surfactant, which is the
80 to 120 °C. Based on the previous study, most of the preferred surfactant type used for EOR process to mini-
adsorption test was done at room temperature (mostly mize surfactant adsorptions at sandstone reservoir. pH is
25 °C). Thus, this study was done to confirm the adsorp- the prominent factor that contributes to the charge on the
tion behavior in the high-temperature region. Figure 15 mineral colloids (Paria and Khilar 2004). In sandstone,
shows surfactant adsorption trends due to the temperature the surface charge is typically positive at lower pH and
effect. For this investigation, clay content and mineral- decreases to a negative value at higher pH. The pH value
ogy, salinity and surfactant concentration were fixed, by at which the net charge on the surface is zero is termed a
using reservoir conditions. For this specific experiment, point of zero charges. In this experiment, the pH of the
it is very important to clearly distinguish between thermal aqueous solution was measured after adsorption test, and
and adsorption effect. Thus, all samples were measured there is not much change in pH for surfactant solution at
in relation to controlled samples, to exclude the thermal different temperatures.
degradation effect. Adsorption loss measured is purely
due to surfactant adsorption to solid surface. Surfactant adsorption: surfactant separation
Surfactant adsorption trends were observed in the
high-temperature region, up to a tested temperature of Carboxylate surfactant is used as the main surfactant in this
120 °C. Surfactant adsorption slightly decreases as the study, and at high temperature, head of the surfactant mol-
temperature increases from 80 to 120 °C. Temperature ecule dissociates more, which turns the solution into car-
increase generally causes a decrease in the efficiency and boxylic acids. Figure 16 shows that carboxylate surfactant
effectiveness of ionic surfactant. However, the change is adsorption is relatively higher than APG surfactant. This
relatively small compared to that caused by pH change observation can be related to the chemical structure for car-
(Rosen 2004). That is why most of the time, changing the boxylate and APG surfactant. APG surfactant chain is sus-
solution pH to higher than surface point zero of charge is pected to be shorter than carboxylate surfactant. Longer sur-
favorable to reduce surfactant adsorption. However, there factant tail prefers to adsorb on the solid surface. That is why
is still an interest to identify and understand surfactant AEC surfactant adsorbs more compared to APG surfactant.

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Journal of Petroleum Exploration and Production Technology (2020) 10:283–296 295

Fig. 16  Surfactant separation Adsorpon due to temperature effects : Surfactant

for adsorption due to tempera-
ture effects separaon (based on mg/g adsorpon)
5.000
4.500

Adsorpons, mg/g rock

4.000
3.500
3.000
2.500
2.000
1.500
1.000
0.500
0.000
80 90 100 106 120

Temperature, C
total adsorpon AEC adsorpon APG Adsorpon

This assumption is supported by the properties and obser- EOR application by achieving type III microemulsion,
vations of the APG that the solution density is water like; and able to reach ultra-low IFT and stable for long term.
thus, shorter tail is expected. In addition, AEC is a viscous • Surfactant loss due to adsorption decreases at increasing
surfactant solution; therefore, longer tail is expected. temperature. This phenomenon is mainly due to weaker
physical bonding to surface at high temperature; thus,
decrease in surfactant adsorption was observed when
temperature increases.
Conclusion • This finding provides guidelines for surfactant adsorp-
tion study for high-temperature application, where the
The aim of this study was to find a specific surfactant for- temperature impact for surfactant adsorption is not sig-
mulation to be stable at a temperature as high as 106 °C and nificant. And maximum surfactant adsorption occurred
using sea water as a solvent (fixed salinity/hardness condi- at low temperatures.
tion). The selected surfactant formulation was then evaluated
for the surfactant adsorption behavior at high-temperature
and high-salinity/hardness conditions. Based on the present Open Access This article is distributed under the terms of the Crea-
tive Commons Attribution 4.0 International License ([Link]
study, the following conclusion can be made: mmons​.org/licen​ses/by/4.0/), which permits unrestricted use, distribu-
tion, and reproduction in any medium, provided you give appropriate
• Single-surfactant system such as modified alkyl ether credit to the original author(s) and the source, provide a link to the
carboxylate (AEC) was not capable of meeting perfor- Creative Commons license, and indicate if changes were made.
mance criteria required for harsh environment (high-tem-
perature/salinity/hardness conditions). Therefore, a blend
formulation (surfactant and co-surfactant) is required for
such extreme conditions. References
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