Accepted Manuscript

Status of Surfactant EOR Technology

Dr. James Sheng

PII:

S2405-6561(15)00033-4

DOI:

10.1016/j.petlm.2015.07.003

Reference:

PETLM 24

To appear in:

Petroleum

Received Date: 2 May 2015

Revised Date:

7 July 2015

Accepted Date: 8 July 2015

Please cite this article as: J. Sheng, Status of Surfactant EOR Technology, Petroleum (2015), doi:
10.1016/j.petlm.2015.07.003.
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Status of Surfactant EOR Technology

Abstract

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Surfactant EOR mechanisms

Factors affecting interfacial tension
Trapping number
Screening criteria
Laboratory work
Numerical simulation work
Summary of pilot and large-scale applications
Surfactants used
Salinity gradient
Surfactant EOR in carbonate reservoirs
Surfactant EOR in shale reservoirs

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Surfactant enhanced oil recovery (EOR) includes surfactant flooding and surfactant stimulation.
The main functions of surfactants are to reduce interfacial tension and wettability alteration
(Sheng, 2013a). This paper is to review the EOR technology related to surfactant injection. The
reviewed topics include the following:

[1]Introduction

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Most of oil fields are under waterflooding. It is well known that some oil called residual oil will
remain unproduced after waterflooding. The literature information is not consistent regarding
whether polymer flooding can lower residual oil saturation over waterflooding. Even though
polymer flooding may reduce residual oil saturation (Wang et al., 2001; Niu et al., 2006), a
significant portion of oil will remain in the reservoirs. To produce the residual oil, surfactants
have to be injected. Therefore, surfactant EOR is a fundamental method. This paper will provide
a status of this EOR technology.
[2]Surfactant EOR Mechanisms

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The main functions of surfactants are to reduce interfacial tension and wettability alteration
(Sheng, 2013a). Surfactant EOR mechanisms are discussed separately according to these two
functions.
[2.1]Reduction in interfacial tension
To explain the function of interfacial tension reduction, we need to first introduce the
relationship between capillary number versus residual oil saturation. The capillary number, NC,
is defined as
NC =

u
,
(cos )

(1)

where is the displacing fluid, u is the displacing Darcy velocity, is the contact angle, and is
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the interfacial tension (IFT) between the displacing fluid and the displaced fluid (oil). Several
forms of the capillary number defined by Eq. 1 have appeared in the literature and summarized
by Sheng (2011). Many experimental data show that as the capillary number is increased, the
residual saturations are decreased (Lake, 1989). The relationship between a residual saturation
and the capillary number is called the capillary desaturation curve. Stegemeier (1977)
summarized some published data between the capillary number and residual oil saturation. His
summarized data show that to reduce waterflooding residual oil saturation by half, the capillary
number must be increased by 1000 times from a typical number of 10-7 for waterflooding
(Sheng, 2011). From the definition of capillary number (Eq. 1) with cos omitted for simplicity,
there are three ways: (1) increasing injection fluid velocity u, (2) increasing displacing fluid
viscosity and (3) reducing the IFT . It is easy to understand that the capillary number cannot
be practically increased 1000 times by the first two ways. It is known that the interfacial tension
between a surfactant solution and oil can be reduced from 20-30 to the order of 10-3 mN/m. In
other words, by adding surfactants, the capillary number can be practically increased by more
than 1000 times. Due to the low IFT, oil droplets can flow more easily through pore throats
because of reduced capillary trapping. The oil droplets move forward and merge with the oil
down the stream to form an oil bank.
Another mechanism is related to swelling. In the type I microemulsion, oil drops are solubilized
in the large water phase. In the type II microemulsion, water is solubilized in the residual oil so
that oil volume becomes larger. In the type III microemulsion, water and oil solubilize in each
other forming a middle phase. Because of solubilization, oil is swollen so that oil phase
saturation becomes larger, and the resulting oil relative permeability is increased. Thus it is
easier for the oil to be produced.

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Surfactant injection reduces residual saturations so that each relative permeability is increased.
Sheng (2011) analyzed the permeability ratio of aqueous phase to oleic phase from published
relative permeability data and found that the relative permeability ratio is decreased in the high
aqueous phase saturation range, when IFT becomes lower. Thus, the oil sweep efficiency is
improved because of surfactant injection.
[2.2]Wettability Alteration

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Wettability alteration mechanism targets more on carbonate reservoirs. Carbonates are more
likely oil-wet (Sheng, 2013b & c). As the rock becomes more water-wet, water imbibition is
enhanced and the residual oil saturation is reduced. In natural fractured carbonate reservoirs,
surfactant injection changes the matrix to more water-wet. Then water can imbibe from fractures
into matrix blocks to displace oil out. The relative permeability models and capillary pressure
models resulting from wettability alteration were proposed by Adibhatla et al. (2005) and
Delsahd et al. (2009). Sheng (2013b) compared the effects of different mechanisms in oil
recovery related to surfactant EOR. Particularly, the effects of wettability alteration and IFT
reduction were compared. His numerical simulation results show that wettability alteration plays
important roles when IFT is high, and it is effective in the early time. IFT plays very important
roles with or without wettability alteration and is effective during the EOR entire process.

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[3]Factors Affecting Interfacial Tension

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As discussed in the proceeding section, one of the fundamental mechanisms of surfactant-related

EOR is reduced IFTs, which are closely related to water and oil solubilization. The relationship
between IFT and solubilizaton is described commonly by the Healy and Reed (1977a & b)
correlations equations and the Huh (1979) equation. Huh equation is more conveniently used.

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Many parameters can affect IFT, such as surfactant and its concentration, solvent and its
concentration, salinity and divalents, oil composition (alkane carbon number), water-oil ratio
(WOR), and system parameters (temperature and pressure). Generally, experiments are needed to
quantify their effects. For some parameters, it is even difficult to qualitatively theorize their
effects. Particularly for surfactant concentration, it may be believed that a higher surfactant
concentration should lead to a lower IFT. For some surfactants, IFT could decrease as the
surfactant concentration is increased, as reviewed by Sheng (2010). One relevant parameter is
the optimum salinity. If the pseudocomponents represent the system well, and the system has
only sodium (no divalent), the optimum salinity should be independent of overall surfactant
concentration and WOR (Hirasaki, 1982). For a more complex system, the optimum salinity may
be dependent on overall surfactant concentration (Nelson, 1982). When an alcohol is added,
because alcohol has different partition coefficients in oil and water phases, the optimum salinity
will be affected by WOR (Baviere et al., 1981).
[4]Trapping number

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When the Darcy equation is used in Eq. 1 and the cos is dropped, the capillary number becomes
v
k p / L k p
NC =
=
,
(2)

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In the equation, p is the potential of displacing fluid and p/L is the potential gradient.
Before discussing the trapping number, the Bond number is defined as
NB =

kg( )
,

(3)

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Where is the density difference between the displacing fluid and the displaced fluid.
To include the gravity or buoyancy, the trapping number is derived for a one dimensional flow
along a formation with a dipping angle (Pennell et al. 1996; Sheng, 2011):
N T = N C + N B sin .

(4)

For a two-dimensional flow, the trapping number is (Jin, 1995)

NT =

N C2 + 2 N C N B sin( + ) + N 2B .

(5)

Here is the angle between the actual flow direction and the dipping reservoir with the dip angle
(count-clockwise). can be calculated from the following relationship:

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tan( + ) =

p
z

+ g

(6)

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Jin (1995) also gave the derivation of trapping number for three-dimensional heterogeneous,
anisotropic porous media. Note that the capillary number defined in Eq. 2 partly includes the
gravity effect in the potential term. The trapping number includes the full gravity effect by
adding the Bond number. Unfortunately, Eqs. 4 and 5 are not validated by some available
experimental data (Sheng, 2011).

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[5]Technical Screening Criteria

Technical screening criteria for surfactant flooding are summarized in Table 1. Criteria are
empirical, mainly based on field project data and technical knowledge about surfactant flooding.

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Many parameters can affect the surfactant flooding process, but the most critical are reservoir
temperature, oil composition, formation water salinity and divalent contents, and clay content.
Oil viscosity and formation permeability may be less important. Table 1 lists the median values
of the important parameters from real surfactant flooding projects based on our survey. The
values of each parameter are analyzed using the rank and percentile method, and values are taken
at the 50th percentile. Some of important parameters are discussed next.

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[5.1]Formation, formation water salinity and divalents

Most of surfactant flooding projects were carried out in sandstone reservoirs. Fewer applications
were carried out in carbonate reservoirs. One reason for fewer applications in carbonate
reservoirs is that anionic surfactants have high adsorption in carbonates and cationic surfactants
are expensive. Clays cause high surfactant adsorption. Therefore, clay contents must be low for a
surfactant EOR application.

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Generally, technical screening criteria provide a guide on formation water salinity and divalents.
In practice, reservoirs have been under waterflooding for some years. The reservoir water
salinity may be close to that of the injected water before surfactant injection. Because limited
salinity data before surfactant flooding are available from real projects, the initial formation
water salinity is shown in Table 1. The injection water salinity for surfactants should be close to
the optimum salinity at which the lowest interfacial tension between oil and water can be
reached. The optimum salinity depends on the crude oil, surfactants used, etc. For most of
surfactants, the optimum salinity is not very high. Divalents may be associated with surfactants,
thus detreating surfactant performance. In this paper, a 50,000 ppm of TDS and 100 ppm
divalents are proposed based on the earlier published values and the data from real projects.
[5.2]Reservoir temperature and depth
Surfactants are quite different. Some surfactants like sulfonate groups can be stable above
200C (Isaacs et al., 1994). The temperature used in steam-foam flooding can be very high (e.g.,
250 oC) (Sheng, 2013d). In other words, surfactants are available which can be applied to hightemperature reservoirs. However, Table 1 shows that most of researchers have proposed 93.3 C
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as a limit for reservoir temperature. The median temperature for the surveyed surfactant projects
is only 25.3 C. Without a detailed study, 93.3 C is used for the temperature criterion in this
paper. More research may raise this limit. Puerto et al. (2012) screened alkoxyglycidylether
sulfonates (AGES) with n-octane/NaCl-brine systems. They found that the systems could be
stable up to 120 oC with optimal salinities up to 20% NaCl with suitable combinations of
hydrophone and alkoxy chain type (ethylene oxide (EO) or propylene oxide (PO) and chain
length). Barnes et al. (2008) presented internal olefin sulfonates which could be stable even up to
150 oC. However, these results are from laboratory and not applied in field projects yet. The
application conditions of a furfactant mean that not only is the surfactant stable at these
conditions, but it also must be able to satisfy other conditions which can lead to a high oil
recovery at a low cost, such as low adsorption and higher solubilization ratios.

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The reservoir depth should not a limiting factor for surfactant flooding as long as the reservoir
temperature limit is not violated.

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[5.3]Formation permeability
As surfactants can reduce residual saturations, relative permeabilities are increased. Thus
effective permeabilities are increased. As a result, surfactants can be injected in low-permeability
reservoirs compared with polymers. Sometimes, surfactants are injected in a low-permeability
reservoir to increase well injectivity. For example, an alkaline-surfactant solution was injected to
improve well injectivity in the Big Sinking field in the Appalachian Basin of East Kentucky
(Miller et al., 2004). Rilian et al. (2010) reported that surfactant stimulation increased the
formation permeability and decreased skin damage in the Segoma field. Because actual
surfactant projects had much higher permeabilities (152 mD from the survey presented in Table
1), the criterion for permeability is set 10 mD, following Taber et al.s (1997a & b).

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[5.4]Oil composition, viscosity and API gravity

Oil composition is very important to surfactants, as it affects the range of salinity within which
the interfacial tension is low. Interestingly, no criterion has been proposed regarding oil
composition in the literature. The surveyed field projects had average oil viscosities of 5.8 cP
(see Table 1). A new criterion cannot be justified without a detailed study. Thus Taber et al.s
(1997a & b) <35 cP is used as a criterion. Most authors include API gravity as a screening
criterion, but during surfactant flooding API gravity is less significant than the effect of
viscosity. Therefore, API gravity is not listed as a necessary criterion in this paper.
[5.5]Oil saturation
Surfactant flooding can reduce residual oil saturation. Even for a watered-out field, surfactant
flooding can be implemented to recovery the residual oil from waterflooding. But a higher
remaining oil saturation may justify the investment for surfactant injection, as more oil will be
recovered from surfactant injection. Considering that the real projects showed the oil saturation
before surfactant flooding is 0.4, the criterion So > 0.3 is proposed.
[5.6]Storage capacity
Some criteria were proposed in the literature regarding porosity (Carcoana, 1982; Goodlett et
al., 1986; Al Adasani and Bai 2011), thickness h (Carcoana, 1982; Goodlett et al 1986; Taber et
al., 1997a & b), the product h, the product So (Brashear and Kuuskraa, 1978), or the product
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hSo. The porosity is related to permeability. If the permeability is high enough, the porosity
should be high enough. Therefore, it is not necessary to impose a criterion for porosity. A higher
h does provide a higher volume to sweep, but proportionally more surfactant volume is injected.
Thus h is not an important criterion.

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[5.7]Aquifer and gas cap

Pressure maintenance in surfactant flooding is an important mechanism. If there is a strong
aquifer or gas cap, less pressure maintenance is needed. Thus, a strong aquifer or gas cap will
make surfactant flooding less beneficial.
[6]Laboratory Work

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There are so many kinds of laboratory tests which need to be done, but we could not afford to do
every laboratory test in practice. However, minimum three laboratory tests are needed: aqueous
stability test, salinity scan test and coreflood test. The aqueous stability test is to check if the
surfactants are compatible with the formation water and other chemicals. The salinity scan test is
a phase behavior test using pipettes (therefore, sometimes called puppet test), as schematically
described in Figure 1. Hands (1939) equations are used to describe the component distribution
among different phases and between the microemulsion phase and anther phase. The core
coreflood test to check oil recovery.

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Refer to Figure 1, when a surfactant solution with some salinity is mixed with oil, three types of
microemulsions will form in order as the salinity is increased: Winsor type I oil-in-water
microemulsion, Winsor type II water-in-oil microemulsion, and Winsor type III bicontinuous middle-phase microemulsion. Winsor type is also called type II(-) or lower-phase
microemulsion; Winsor type II is called type II(+) or upper-phase microemulsion; Winsor tpe III
is also called middle-phase microemulsion (Sheng, 2011). Important objective from the salinity
scan test are to select a surfactant or surfactants that can have high solubilization ratios of oil and
water volumes to the surfactant volume, and to determine the optimal salinity for the selected
surfactants. The optimal salinty corresponds to the maximum middle-phase volume in Figure 1.
According to Huhs (1979) equations, high solubilization ratios will generate very low interfacial
tensions (IFT), preferably in the order of 10-3 mN/m; and correspondingly a high oil recovery
factor (RF) may be obtained. Selection of surfactants based on the solubilization ratios may be an
alternative to the IFT measurement because we may use Huhs (1979) equations to calculate IFT
from the solubilization ratios. However, measuring IFT directly in the laboratory is preferred in
the Chinese literature.
Figure 1 Types of microemulsions (surfactant systems)

The core flood test is needed to see whether a significant oil recovery could be recovered. For
those three types of tests, the salinity scan test data are most important, as they are used to
calculate interfacial tension, to quantify phase behavior, microemulsion properties like viscosity,
and so on.
Generally, the salinity scan tests are conducted using dead oils because of the difficulty to do
such tests using live oils. Few papers reported the experimental work using live oils. When we
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say that a surfactant is more soluble in oil, it is equivalent to say that the optimum salinity is
lower. Nelson (1983) observed little difference in phase behavior as a function of equilibrated
dissolved methane, and the effects of methane on the optimum salinity of crude oils and
synthetic oils were opposite. Bourrel et al. (1987) observed the optimum salinity was increased
when methane was added in n-decane and n-hexane, but decreased in dodecyl o-xylene (C12OX).
Cottin et al. (2012) reported a slight increase in the optimum salinity of their live oil compared
with their dead oil. Puerto and Reed (1983), Roshanfekr et al. (2012), and Southwick et al.
(2012) observed that the optimum salinity decreased when methane was added in oils. Sagi et al.
(2013) also observed a decrease in the optimum salinity when either methane, ethane or CO2
was added in a dead oil. Jang et al. (2014) found that the optimum salinity of a live oil was closer
to that of the dead oil than expected and higher than that of surrogate oils made based on the
equivalent alkane carbon number approach. Apparently, more papers reported that the optimum
salinity of a live oil was lower than that of the respective dead oil. Kahlweit et al. (1988), Skauge
and Fotland (1990), Sassen et al. (1991), Austad and Strand (1996), and Roshanfekr et al. (2012)
all observed that the increased pressure reduced surfactant solubility in crude oils and the
optimum salinity increased. The effect of pressure was opposite to that of added methane (live
oil). And dissolution of methane dominated the pressure effect. Jang et al. (2014) found that the
solubilization ratios were higher thus the interfacial tensions were lower for live oils than their
respective dead oils.

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The above phase behavior tests with live oils can be conducted using high-pressure and hightemperature sapphire tubes (Jang et al., 2014; Oukhemanou et al., 2014). Live oils can be dead
oils dissolved with light components like methane at the reservoir pressure, or dead oils diluted
with solvents based on the concept of equivalent alkane carbon number at the atmospheric
pressure. Using the latter type of oils in corefloods is much easier (Oukhemanou et al., 2014).
[7]Numerical Simulation Work

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For simulation software, UTCHEM developed by University of Texas at Austin is the best
software so far to capture the mechanisms, but it is difficult to simulate a large field-scale case
because of slow computation algorithm (sometimes solutions are not convergent) and lack of
functions to include real geological features. Another weakness of UTCHEM is that it has not
been equipped with visualization package for post-processing analysis. Fortunately, this
weakness can be overcome by using commercial visualization packages, such as S3GRAF
(http://www.sciencesoft.com/products/s3graf/) and Krakem (https://www.esss.com.br/kraken/).
A fundamental mechanism of surfactant-related EOR methods is low IFT which leads to a high
capillary number and thus a low residual oil saturation. IFT is mainly a function of the amount of
oil solubilized in the microemulsion phase (Huh, 1979). However, ECLIPSE models a two-phase
system with the IFT as a function of surfactant in the water phase. In other words, different types
of microemulsion are not simulated. The interfacial tension is a function of surfactant
concentration. The capillary desaturation curve which describes the relationship between a
residual oil saturation and capillary number depends on rock type not phase. These concepts are
not correct. Computer Modeling Groups STARS-ME is a commercial adaption of UTCHEM. It
models the three types of microemulsions (Goudarzi et al., 2013). Surfactant injection is to
reduce residual oil saturation and the corresponding relative permeabilities are increased.
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Sometimes, a surfactant process is simulated by modifying flow parameters like relative

permeabilities, when a commercial simulator is used where surfactant mechanisms were not
included in the simulator.

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From the theoretical point of view, three types of microemulsion should be formulated in a
simulator. However, the type III microemulsion may not form at a low surfactant concentration
(Salager et al., 1979; Chan and Shah, 1981; Kang, 2001). Or the type III microemulsion volume
is so small that it cannot be seen or can be negligible. The amount of surfactant in the excess
phases would become a more significant fraction of the total (Nelson, 1981). In practical
surfactant flooding projects, the injected surfactant concentration is very low. Therefore, a
simple two-phase approximation of microemulsion may be justified to avoid a struggle to
formulate the complex type III microemulsion in a commercial reservoir simulator. Adibhatla et
al. (2005), and Liu et al. (2008) made efforts in this direction. Apparently, no new research
results have been published. Whether the two-phase approximation is sufficiently accurate to
describe practical cases needs to be investigated.

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As mentioned in the section of laboratory work, a fundamental laboratory test is the phase
behavior test. Using a simulator like UTCHEM to history match the experimental solubilization
ratios, phase behavior parameters are obtained. The essential approach for such simulation work
is to use coreflood blocks to represent a test tube at a specific salinity by setting the porosity
equal to 1 and the permeability to a very large value; the oil and water rates honor the water-oil
ratio for the test tubes; many pore volumes are flushed until the solubilization ratios in
coreflood blocks are almost equal to those in the test tube. Such coreflood simulation is repeated
for all the test tubes at different salinities. An example of such simulation is provided in Sheng
(2011).

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Similarly, laboratory core flood tests can be history matched to calibrate flow parameters which
may be used in a pilot-scale, field-scale or sector model to optimize the injection schemes and to
predict surfactant EOR performance, and using both the coreflood scale model and the up-scaled
model to do sensitivity studies and perform engineering analysis.

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Generally, chemical flooding simulators do not include gas phase. Such practice is justified
because the pressure is usually above the bubble point and a free gas phase does not exist. If the
reservoir is depleted, a gas phase needs to be included. Patacchini et al. (2014) used a four-phase
chemical simulator to include gas phase. By doing so, the effect of dissolved gas content on
phase behavior was modelled (Trouillaud et al., 2014).
[8]Summary of Pilots and Large-Scale Applications
It is impossible to present detailed project description and results in this paper. Here we only
summarize the main results of pilots and large-scale field applications.

[8.1]Single well tracer test before a pilot

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Eighty seven field projects worldwide have been surveyed:

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Indonesia
Romania
Russia
USA

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United Kingdom
France
Germany

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[8.2]Summary of surfactant projects

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Before carrying out a field pilot, generally a single well (chemical) tracer test (SWTT or SWCT)
is conducted. The SWTT is sometimes called chemical huff and puff (Chai et al., 2011). During
a SWTT, a slug of surfactant solution is injected in a well and the oil saturation before and after
the surfactant injection is measured. The main objective is to see how much oil saturation can be
reduced. Such test is less expensive, but there is an uncertainty in estimating oil saturation, and
limited information regarding interwell connectivity, sweep efficiency and injectivity can be
obtained. Surfactant may flow out of the well drainage area. The phenomenon is called drift
(Tomich et al., 1973). When a field pilot is conducted, more expensive observation wells may be
drilled.

All were onshore cases. A few cases were in carbonate reservoirs and the rest were in sandstone
reservoirs. Most of the projects were conducted in either five-spot patterns or inverted five-spot
patterns.

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For surfactant EOR in carbonate reservoirs, there are three surfactant stimulation projects
reported from 1990s 2000s (Sheng, 2013b). These projects are the Cottonwood Creek in the
Bighom Basin of Wyoming (Xie et al. 2005; Weiss et al. 2006), the Yates field in Texas (Yang
and Wadleigh 2000; Chen et al. 2001), and the Baturaja formation in the Semoga field in
Indonesia (Rilian et al., 2010).

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[8.3]Injection scheme and amount of chemicals injected

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A complete injection scheme may include a preflush, a main slug and a postflush. But a preflush
is not very common in surfactant flooding. In several of the surveyed surfactant projects, alkaline
preflush was carried out to soften the formation water (remove divalents) to avoid association of
divalents with the subsequently injected surfactants. Here are several examples. A slug of
sodium hydroxide and sodium silicate solution was preflushed in the Bell Creek
surfactant/polymer project (surfactant injection followed by a polymer drive) to soften the
formation water (Johnson et al., 1988); sodium carbonate was injected to preflush the Salem field
to reduce divalents through precipitation (Whiteley and Ware, 1977); sodium tripolyphosphate
preflushed the Cushing field to reduce barium ion (Gall et al., 1997). In the Glenn Pool
surfactant flood expansion project, lignosulfonate was tested as a sacrificial adsorbate (Hong and
Bae, 1990).
From the available data of the surveyed projects, the median amount of surfactant used in the
main surfactant slug was 52 in terms of the product of injection pore volume and concentration,
both units in %. This amount is much higher than that used in the ASP projects which is 9.44
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(Sheng, 2014a). The median injection pore volume was 0.1 PV, and the median surfactant
concentration was 5.2%. In the mobility control postflush slug, the amount of polymer injected
(product of pore volume and concentration, both units in %) was 5.65. The median postflush
pore volume was 0.7 PV, and the median polymer concentration was 0.08% (800 ppm). Biocide
concentrations injected were typically a few hundred ppm. However, in the Glenn Pool project,
3000 ppm was used (Hong and Bae, 1990).
[8.4]Chemicals used

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The alkalis used in the preflush were sodium hydroxide, sodium carbonate, sodium silicate and
sodium triphosphate. Both biopolymer and synthetic polymers were used in the postflush.
Typical types of surfactants used in EOR are petroleum sulfonate, alkyl benzene sulfonate,
carboxylate, and chrome lignin (lignite). The relatively new developed types of surfactants are
biosurfactant and Gemini (Wang et al., 2006). The surfactants used in field projects include
these: different petroleum sulfonates, ethyl sulphate, ethoxyalkylphenol sulfonate, alkane
sulfonate, fatty-acid alkanolamide double polyethenoxy ether, alkyl aromatic sulfonate, ether
sulfate, ammonium lignosulfonate (Petrolig ERA-27), nonioninc PLURONIC L64 (BASF),
nonionic POA, CAC, Petrostep surfactants, Butyl Cellosolve (Dow), SO3NH4, SPS (CS-2000),
Lignin II, TRS 10-410 Sulfonate, Witcos TRS 10-410, TRS-40, TRS-18, Peronate TRS 10-80,
Texaco LN60-COS, Conoco Alfonic 610-50, S13D, S2.

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Zhang et al. (2013) synthesized a novel hydroxyl propyl sulfobetaine surfactant that can be used
in high-temperature (3090 oC) and high-salinity (20,000120,000 ppm) reservoirs. The betaine
sulfactant is synthesized with cheap raw material of fatty acid, and its functional group of
hydroxylpropyl sulfo hydrophilic group can improve the surfactants heat resistant and salt
tolerant abilities. Many new surfactants are developed in laboratories in China which are
presented in our database. For surfactants used in hard brines, use of adsorption inhibitors was
proposed by Tabary et al. (2012).

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Surfactant is more effective (higher solubilization) without an added cosolvent such as alcohol.
In practice, cosolvents are almost always added to surfactant formulations to minimize the
occurrence of gels, liquid crystals, emulsions or polymer-rich phase separating from the
surfactant solution, to lower the equilibration time, and/or to reduce microemulsion viscosity.
Some cosolvents and alcohols used were Exxon Corexit 9439 (ethoxylated alcohol), isopentanol,
isopropanol (IPA), N-butanol, isobutyl alcohol, isopropyl alcohol, nonylphenol, hexanol,
primary amyl alcohol and normal butyl alcohol.
In terms of surfactants for wettability alteration in carbonates, cationics, anionics and nonionics
were used in research for chemical EOR in carbonate reservoirs. Many cationics were used in
laboratory studies, as reviewed by Sheng (2014b). Some of anionic surfactants used by
Seethepalli et al. (2004) were alkyl aryl ethoxylated sulphonates and propoxylated sulfate.
Hirasaki and Zhang (2004) used ethoxylated and propoxylated sulfates. Nonionic surfactants
were used by Chen et al. (2001) and Xie et al. (2005). For more details, see Sheng (2013b).
[9]Salinity Gradient
In surfactant flooding, it was believed that a negative salinity gradient was needed. The negative
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salinity gradient means the salinities of pre-flush water slug, surfactant slug, and post-flush slug
(polymer solution and/or water drive) are in descending order. The negative salinity gradient was
proposed based on the relationship that the optimum salinity decreases as the surfactant
concentration is decreased (Nelson, 1982). Because of surfactant adsorption and retention, the
surfactant concentration will be decreased as the surfactant solution moves forwards. If the
optimum salinity decreases with surfactant concentration, the optimum salinity also decreases as
the surfactant solution move forwards. Thus, the decreasing salinity will be consistent with the
decreasing optimum salinity so that the optimum salinity is maintained as the surfactant solution
move forwards. As Sheng (2010) discussed, some surfactants exhibit higher optimum salinity as
the surfactant solution is diluted. In other words, the surfactant optimum salinity could increase
as the surfactant solution moves forwards. If the same reasoning was followed, a salinity gradient
opposite to the negative salinity gradient (positive salinity gradient) would be needed. Simulation
results show that positive salinity gradient does not lead to a higher oil recovery (Sheng, 2010).
Therefore, this reasoning is questionable.

M
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One benefit of the negative salinity gradient is that a higher-salinity slug forms an oil external
microemulsion in the front. The oil external microemulsion has a higher viscosity so that it
would mitigate surfactant fingering ahead (Hirasaki, 1981). One problem to form a high-salinity
slug ahead of the surfactant slug is that a pre-flush water slug of a high salt concentration needs
to be injected in an originally low salinity reservoir. This will result in an additional cost for the
project.
Sheng (2010) did simulation study to investigate this issue. His simulation results show that the
negative salinity gradient may not be necessary. He proposed an optimum salinity profile
which has the following characteristics:

EP

3.

The optimum salinity must be used in the surfactant slug.

Two guard slugs with the same optimum salinity are placed immediately before and
after the surfactant slug. The optimum salinity in the guard slug before the surfactant
slug is preferred but not mandatory.
The salinity in the post-flush must be below the lower salinity bound of Type III.

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1.
2.

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His simulation results show that such optimum salinity profile leads to the highest oil recovery
compared with different salinity schemes, especially higher than that from the corresponding
negative salinity gradient. However, the simulation results have not been verified by
experimental data or field data. The validity of the results also depends on the robustness of the
simulation software used which is UTCHEM in this case.
[10]Surfactant EOR in Carbonate Reservoirs
As the survey results presented earlier in this paper show that almost all surfactant EOR were
conducted in sandstone reservoirs except a few surfactant stimulation projects in carbonate
reservoirs. The main mechanism is to change wettability. Many laboratory studies focused on
using cationic surfactants to change wettability from oil-wet to water-wet. Typical work was
done by Austad and his co-workers (Austad and Standnes, 2003; Standnes and Austad, 2002).
Hirasaki and Zhang (2004) explained how adding Na2CO3 change wettability of carbonate rock
surfaces. This is because of the dissociation of the naphthenic acids in the crude oil with
11

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increasing pH. Some even proposed that low-salinity water can change carbonate wettability
(Sheng, 2014b). For more details about surfactant EOR in carbonate reservoirs, see Sheng
(2013b).
[11]Surfactant EOR in Shale Reservoirs

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As unconventional shale oil and gas resources are becoming increasingly important hydrocarbon
supplies, improving hydrocarbon recovery using surfactants is one of the obvious choices,
because surfactants can reduce interfacial tension to reduce capillary phase trapping, and change
wettability to enhance water imbibition. The literature on shale oil rocks indicates that they are
most likely oil-wet (Phillips et al., 2007; Wang et al., 2011; Mirchi et al., 2014). Shuler et al.
(2011) did some surfactant spontaneous imbibition tests. The core slices they used were 1.5
inches in diameter and inches in thickness. Wang et al. (2011) also investigated brine
imbibition into the outcrop Pierre shale core slices. The core sample thicknesses were 0.655
mm. Both of these groups used very thin slices because it is well known that the spontaneous
imbibition process is very slow (Sheng, 2013b). Takahashi and Kovscek (2010) studied the
wettability of a low-permeability siliceous shale at different pH values and found that the shale
samples became more water-wet at very low or very high pH. Mirchi et al. (2014) observed that
adding surfactants in brine reduced the interfacial tension between brine and oil and increased
the dynamic contact angle of oil drops (became more water-wet).
[12]Acknowledgements

[13]References

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This work, especially field data collection part, was financially supported by the joint industry
project (JIP), Chemical EOR Knowledge Database. The financial support from the member
companies in this JIP are gratefully appreciated.

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Table 1 - Summary of screening criteria for surfactant flooding

Dickson et
al. 2010*
Surfactant
projects
Proposed in
this paper

<93.3

50,000

1,000

Sandstone

>50

<80

Low

Low

Sandstone

>40

<93.3

<100,000

>20

<93.3

100,000

>10

<93.3

>50

< 70

Low

< 200,000 if
Tr<60 oC,
< 50,000 if
Tr>60 oC,

>100

<93.3

152

25.3

39,078

>10

<93.3

<50,000

So
(frac.)

30

0.2

<20

>0.25

>0.3

Sandstone
&
carbonate
Sandstone
preferred

1000

Sandstone

<100

Aquifer

Gas cap

API
gravity

Depth,
ft

25

None to
week

None to
week

Weak

Week

>25

NC

<6561

<40

Sandstone
preferred
50,000

o
(cP)

RI
PT

>20

Clay

SC

121.1

Lithology

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Goodlett et
al. 1986
Taber et al.
(1997a,b)
Al-Bahar et
al. 2004

20

Divalent
(ppm)

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NPC 1984

Tr (C)

EP

NPC 1976
Brashear &
Kuuskraa
1978
Carcoana
1982

k (mD)

AC
C

Proposed by

Formation
water
salinity,
(TDS, ppm)
200,000

Low

Majority
sandstone

Low

Sandstone

Low

100

0.3

>25

<9000

<35

>0.35

>20

<9000

< 150

0.35

<35

>0.45

>20

5009000

5.8
<35

None

None

0.4

Generally
none

Generally
none

36.5

1808

>0.3

Weak

Weak

NC

NC

In the table, o is the oil viscosity, So is the oil saturation before ASP, Tr is the reservoir temperature, NC means not critical.
*For ASP

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