SPE 164483

A Critical Literature Review of Laboratory and Field Scale Determination of

Residual Oil Saturation
Tadesse Weldu Teklu, Jeffrey S. Brown, Hossein Kazemi, Ramona M. Graves, Colorado School of Mines; Ali M.
AlSumaiti, The Petroleum Institute

Copyright 2013, Society of Petroleum Engineers

This paper was prepared for presentation at the SPE Production and Operations Symposium held in Oklahoma City, Oklahoma, USA, 23−26 March 2013.

This paper was selected for presentation by an SPE program committee following review of information contained in an abstract submitted by the author(s). Contents of the paper have not been
reviewed by the Society of Petroleum Engineers and are subject to correction by the author(s). The material does not necessarily reflect any position of the Society of Petroleum Engineers, its
officers, or members. Electronic reproduction, distribution, or storage of any part of this paper without the written consent of the Society of Petroleum Engineers is prohibited. Permission to
reproduce in print is restricted to an abstract of not more than 300 words; illustrations may not be copied. The abstract must contain conspicuous acknowledgment of SPE copyright.

Abstract
In petroleum reservoirs only a small fraction of the original oil-in-place is economically recovered by primary, secondary,
and tertiary recovery mechanisms. A considerable amount of hydrocarbon ends up unrecovered or trapped due to microscopic
phase trapping in porous media which results in an oil recovery factor typically less than 50%. Waterflooding is by far the
most widely used method to increase oil recovery. The oil that remains in the porous media after waterflooding is called
remaining oil saturation (ROS) which is larger than the relative permeability residual oil saturation ( or simply ). This
residual oil saturation varies depending on lithology, pore size distribution, permeability, wettability, fluid characteristics,
recovery method, and production scheme. Determination of the residual oil saturation of a reservoir is a key parameter for
reserve assessment and recovery estimates. Further, reliable data is important for investigation of possible incremental
recovery under Enhanced Oil Recovery (EOR) methods.

Various residual oil saturation measurment techniques are available both at laboratory and field scale. None of the techniques
can be regarded as a single best method of determining . Depending on the complexity of the reservoir under study,
combinations of methods are always advisable for appropriate determination.

This study is an up-to-date review of techniques used in determining in laboratory and field. The study further reports on
the advantages and limitations of each method and provides recommendations for best practices.

Introduction
It is well known that only part of the original oil-in-place is economically recovered by conventional methods. Due to
macroscopic and microscopic phenomena, considerable amount of hydrocarbon is unrecovered or trapped during multiphase
flow in porous media. Determination of residual oil saturation ( ) is a fundamental requirement for studying and
understanding the behavior of a field during waterflooding and beyond. Especially, before embarking on a tertiary recovery
scheme, it is imperative to know the of the reservoir in order to assess its technical feasibility and profitability.

Capillary Number and Bond Number:

In EOR, a quick way to assess the contiribution of gravity to the additional oil recovery is to use the Bond number (N )
correlation (Figure 1). Bond number is a dimensionless number representing the ratio of gravity forces to capillary forces as
described in Eq 1.1 (Du Prey, 1978). It is a measure of the relative contribution of gravity and capillary forces, where beyond
a “critical” level, the residual oil saturation decreases; hence, additional recovery is achieved. Figure 1 is a plot of
experimental recoveries of residual phases versus the Bond Number.

∆
N Bond number ………………………………… (1.1)
/
Where is porosity [ ],
N is Bond number [ ] is permeability [ ].
g is gravitational acceleration [ / ], ∆ρ is the difference between phase densities [ /cc],
L is length [cm], σ is interfacial tension [ / ].
2 SPE 164483

Figure 1: Effect of core wettability on capillary desaturation for oil-brine systems (Filoco & Sharma, 1998).

For situations when reduction in in influenced by viscous displacement and interfacial tension reduction, the capillary
number (N ) correlation can be used. Capillary number is a dimensionless number that measures the relative contribution of
viscous forces and capillary forces as described in Eq 1.2 (Stegemeier, 1977). Beyond a “critical” capillary number, the
residual oil saturation decreases; hence, additional recovery is achieved. Figure 2 is a plot of the capillary number versus
residual oil saturation of various porous media and fluids (Stegemeier, 1977).

N capillary number …………………………………… (1.2)

where
N is capillary number [ ]. μ is viscosity [ ].
u is Darcy velocity / . σ is interfacial tension [ / ].

Figure 2: Average experimental recoveries of residual phases (Stegemeier, 1977). is the critical residual oil saturation
and is residual oil saturation.
SPE 164483 3

Residual Oil Saturation Determination Techniques

There are several ways to determine or estimate the , these includes:
 Laboratory Methods:
o Core Analyses,
o Core Flooding,
o Centrifuge,
o Counter-Current Imbibition (CCI),
o Digital Rock Physics (DRP).
 Field Methods:
o Well log analyses,
o Well tracer tests,
o Reservoir performance study (material balance calculations, pressure transient test and reservoir simulation).

Laboratory Methods

Core Analyses: coring provide the best means of direct measurement of reservoir properties. Residual oil saturation
measured in the laboratory from core is dependent on how the core is recovered and handled (conventional coring, pressure
coring or sponge coring).

In conventional coring, if reasonably careful attention is given to controllable variables in coring, handling and analysis, then
the most severe changes in oil saturation occurs during lifting the core to the surface. Attempts have been made to correct for
the expulsion (blowdown) and associated shrinkage of oil as pressure decreases, though the corrections are unreliable
(Rathmell et al., 1973). Due to expulsion issue, residual oil saturation from conventional cores is generally less than real in
situ values. Hence, conventional core values can only be used as a qualitative indicator.

Although there is certainly a dependence upon oil type, in situ saturation, and pore space configuration, there is no reliable
correction to account for flushing and blowdown in conventional cores. Rathmell et al. (1973) proposed an equation for
estimating waterflood residual oil saturations from core saturations where the cores must be taken with water-base muds
having a filtrate loss in excess of 5 cc at bottom-hole conditions (Eq 2.1). The flushing action of the drilling fluid during a
coring operation is commonly considered to remove most of the mobile oil existing in the core.

( ) res = ( ) core Bo E ……………………………………….…………………..…… (2.1)

where ( ) res = average post-waterflood residual oil saturation in the flooded region of the reservoir;
( ) core = average oil saturation from cores;
Bo = oil formation volume factor at the time of coring;
E = 1.11, bleeding factor.

The above equation is then corrected for waterflood displacement efficiency through multiplication by the reciprocal of the
conformance factor by Kazemi (1977). The conformance factor may be obtained from a reservoir simulation study that
accounts for reservoir heterogeneity, capillary effects and mobilities of oil and water. In the absence of a reliable reservoir
simulation result, the conformance factor is estimated by , as reported by Craig (1971). Hence the modified equation is:

( ) res = ( ) core Bo E ………………………..………………………….…….. (2.2)

where M = mobility ratio (the ratio of the mobility of water at the average water saturation in the reservoir at breakthrough
to the mobility of oil in the oil bank ahead of the displacing front).
V = permeability variation calculated from reservoir core samples.

Routine saturation measurements are usually done from conventional cores; hence, are not sufficient to describe in situ
saturations and residual oil saturations. The most significant variables that influence the measured saturations of cores (and
residual oil saturation) in this and other methods are:
 Formation properties: rock type, permeability, stratification, reservoir fluid properties, fluid pressure and
temperature, wettability, etc.
 Coring: core barrel diameter, diameter, mud composition, mud weight, drilling rate and mud pressure, etc.
 Core lifting: solution gas, oil shrinkage.
 Core handling: core preservation and storage.
 Core analysis: oil gravity, coring calibration, compaction correction, etc.
4 SPE 164483

Pressure coring solves expulsion and shrinkage problems by maintaining the core specimen at bottomhole pressure (BHP).
Experience has shown excellent accuracy in remaining oil saturation (ROS) profile from pressure coring (Yell, 1978; Bilhartz
and Charlson, 1978; Hyland, 1983).

Sponge coring uses a sponge-sleeve modification to a conventional core barrel. The sponge sleeve is made of a porous, oil-
wet, polyurethane sponge. The oil bleeding from the core is collected in the sponge and reconstituted back into the core
porosity to correct oil saturation for bleeding. The sponge-coring technique has been reported to provide oil-saturation
measurements approximating those determined by the pressure coring but at a cost closer to that of conventional coring
(Park, 1983; Park, 1984).

Core Flooding Method: Laboratory waterflood measurement is one of the most common ways of measuring residual oil
saturation. This is done with preserved or unpreserved cores, reservoir or synthetic fluids, and under room or reservoir
conditions; however, for reliable it is advisable to attain the reservoir conditions as much as possible. Figure 3 shows the
residual oil saturation (end point of relative permeability) measurement obtained from laboratory waterflooding. is a
strong function of wettability of the rock (Figure 3 and Figure 4).

Figure 3: Typical oil/water relative permeability curves for determination of

residual oil saturation for oil-wet and water-wet cores (Jennings 1957).

The following is typical experimental procedure to determine relative permeability end points and using coreflooding by
aging the core to retain the wettability (van Poelgeest et al., 1991; Alamdari et al., 2011):
1. Clean the core (if the core is unpreserved).
2. Saturate the core completely with brine.
3. Flood with refined dead oil at reservoir pressure and temperature to establish connate water saturation.
4. The produced fluids are collected and measured.
5. Flood with live crude oil to miscibily displace with live crude oil. Live crude can be obtained by recombination of
separator oil and separator gas under reservoir conditions.
6. The relative permeability of oil at connate water saturation (k , ) is determined.
7. Age the core at reservoir conditions for four weeks or more to restore the wettability of the core.
8. Waterflood the core to establish and relative permeability of water at k , .
9. Dean-Stark extraction method can also be applied as a last check on the amount of oil produced ( ) and compare
with determined from step 8.

Typically, the of oil wet cores are higher than that of water wet rocks (Figure 3; Figure 4) and of neutrally wet rocks
are lower than strongly water or oil wet (Figure 4).
SPE 164483 5

Figure 4: dependence on wettability and pore volume (PV) injected;

(BT is PV corresponding to breakthrough time) (Jadhunandan and Morrow, 1995).

Centrifuge Method: The centrifuge can be used to measure residual oil of core samples. It is a relatively fast and
reproducible method of measuring in the plugs. Measuring under approximate reservoir conditions is important for
reliable values. For instance, different gravity forces, wettability, or fluid characteristics at a given temperature for a
given initial saturation will give different residual saturations. Unless special precautions are taken, capillary end effects may
lead to inaccurate results (Slobod et al., 1951).

The following steps are followed in determining in a centrifuge experiment (Slobod et al., 1951; Alamdari et al., 2011;
AlSumaiti and Kazemi, 2012):
1. Core plug preparation, cleaning and saturation with brine.
2. From the dry weight and saturated weight the porosity can be determined (it can also be crosschecked using other
method).
3. Centrifuge the brine saturated core with crude oil until the connate water saturation is left inside the core. By
material balance, connate water saturation can be determined at this stage.
4. Place the core plug containing connate water and oil in to the core holder seen in Figure 5.
5. With air as the only other component present in the tube (core holder), the system can be rotated at high speed for
one hour or more.
6. The displaced oil is collected in the bottom of the tube.
7. The then can be calculated from the weight of the core knowing the connate water saturation.
8. Dean-Stark extraction method can be applied as a last check on the amount of oil produced ( ) and compare with
determined from step 7.
9. Once the is determined in the lab it can be translated to field scale using appropriate mathematical equations.

Figure 5: Core holder with bottom well for displaced fluids

for use in normal speed centrifuge (Slobod et al., 1951).
6 SPE 164483

Counter-Current Imbibition (CCI) Method: the application of air-mercury and oil-air capillary pressure data are also
one of the ways to determine . The residual non-wetting phase saturations are function of both pore geometry and initial
saturation. With properly defined imbibition curves and a good estimate of initial saturations, residual non-wetting
saturations could be used to approximate waterflood residual oil saturation for water-wet rocks (Pickell et al., 1966).

Good comparisons between from oil-air imbibition data and waterflood techniques on water-wet rocks are reported by
Pickell et al., (1966). They also found that there was usually good agreement between residual saturations obtained by the
mercury-air and oil-air systems. However, in shaly sands the mercury saturations tend to be excessively high. The oil-air
system has definite advantages: a) it appears more reliable, b) it is more rapid, c) rock samples can be reused.

Digital Rock Physics (DRP) Method: according to studies by Shan and Chan (1993), Abraham et al. (2009), Grader et
al. (2010), and Sheng et al. (2011), digital rock physics approach can be used to determine in addition to other
petrophysical parameters such as relative permeability curves, capillary curves, porosity, permeability, etc. In DRP, pore
scale structure of the core can be constructed from X-Ray Computed Tomography (CT) of the core using advanced image
processing techniques. Fluid dynamics computation on a pore scale using Lattice Boltzmann method (LBM) can be applied
to generate petrophysical parameters such as .

Field Methods

Well Log Analyses:

Well log analyses are the most widely used methods to obtain reliable in situ remaining oil saturation profile and . There
are many types of well logging methods which can be used for determination. On the basis of wellbore condition,
measurements using well log methods can be grouped as open-hole and closed-hole logs. Logs such as Resistivity, NML,
EPT, and Dielectric Constant logs are only applicable for open-hole wells. On the other hand, logs such as PNC, C/O log,
gravity log, and gamma ray log, are particularly valuable for measuring through casing.

Resistivity and Induction Log: The resistivity log is widely used because of its low cost and relatively deep
investigation. The resistivity measurement that allows computation of oil saturation, 1 , is determined by Archie’s
equation (Archie, 1942).

/
…………..…………………………..………… (3)
∅
where
= water saturation ∅ = porosity
= formation-water resistivity = lithology exponent
= true resistivity (from resistivety logs) = saturation exponent

There are two kinds of formation resistivity measurement approaches applicable for determination of using Eq 3:
conventional well logs and inject-log-inject approaches. Despite of its low cost and availability, the formation parameters
(porosity, cementation factor, saturation exponent, shale content, and reservoir pressure and temperature) make the
uncertainty (+10%) of conventional resistivity logs unacceptable for determination for EOR purposes. One way to reduce
uncertainties in resistivity logs is by logging twice (log-inject-log, LIL) (Murphy et al., 1973; Murphy et al., 1976). After the
formation was logged ( ), the oil could be removed by injecting chemicals. A slug of formation brine is then injected and
the formation is logged for resistivity again ( ). With knowledge of the saturation exponent, , could be determined as
in Eq 4a. This procedure is called the LIL (log-inject-log) technique and can improve measurements of resistivity log to
an accuracy of +2 to +5% saturation units (s.u.). Similar to resistivity log in principle, the dual induction log (DIL) measures
formation conductivity instead of resistivity to determine .

/
1 ………………………………………….…………..……….. (4a)

where is resistivity of formation after flushed with water.

With advancement of resistivity logs, can be calculated using the flushed zone resistivity value as follows:

/
1 1 …………………………………………..……….. (4b)
where is flushed zone water saturation, is flushed zone resistivity. Flushed zone resistivity can be measured with good
accuracy using micro-spherical focused logs (MSFL) or similar tools. The MSFL tool provides a measurement of the flushed
zone resistivity ( ) with low mudcake correction.
SPE 164483 7

The main difficulty of determining using resistivity logs is its dependence of value on the wettability. According to
study by Anderson (1986), the Archie saturation exponent, , is almost independent of the wettability when the brine
saturation is sufficiently high that the brine is continuous. However, the wettability effects become very important when the
brine saturation is lowered. In general, the Archie saturation exponent has a value of about 2 in water-wet formations and
cleaned water-wet core and can reach values of 10 or more in uniformly oil-wet core with low brine saturations. If saturation
exponent ( ) measured from clean core is used in logging analysis of strongly oil-wet, the saturation and values will not
be reliable.

Nuclear Magnetism Log (NML): The NML has been reported to be potentially the most accurate filed technique for
measuring (Robinson et al., 1974; Neuman and Brown, 1982). This tool measures directly after the water signals are
eliminated with injection of paramagnetic ions (inject-log process). NML techniques detects hydrogen in the water and oil
and applicable as inject-log. Water containing paramagnetic ions is injected into the formation and the Free Flow Index (FFI)
of oil is directly or computationally obtained. The following equation can be applied to estimate the remaining oil saturation:

…………….………………………………………………………..….. (5)
∅

where ∅ is porosity, FFI = Free Flow Index is a measure of bulk volume of oil present in the flushed zone.

The accuracy of NML depends largely on the porosity estimate and the signal-to-noise ratio. Because NML measures oil
saturation directly, random errors can be minimized and systematic errors can be determined.

NML tools had many operational limitations and retired from service in the late 1980s. New technique has been developed to
determine residual oil saturation using pulsed nuclear magnetic resonance (NMR) logging (Horkowitz et al., 1997). The
pulsed NMR technique is as accurate as NML tools with reduced cost and operational problems. Unlike the inject-log NML
technique, the new generation of pulsed NMR logging tools eliminates the need for doping the drilling mud with magnetite
(paramagnet). Akkurt et al. (1998) used enhanced diffusion method (EDM) to exploit the diffusion contrast between oil and
water separating their respective NMR signals to determine . NMR tools measure the diffusion coefficient (D) of fluids.
The diffusion of gas and water molecules can be described by a single number. Crude oils, on the other hand have
distributions of molecular diffusion coefficient based on their density (viscosity). This contrast can be identified using EDM
to measure .

Electromagnetic Propagation Tool (EPT) and Dielectric-Constant Log: The EPT estimates by measuring the
phase shift and the attenuation rate of an electromagnetic wave propagated through the formation at a frequency of 1.1 GHz
(Wharton et al., 1980). The EPT log is less sensitive to salinity change than the resistivity log; hence it is valuable for use in a
formation with unknown or fresh salinity. The EPT log is reported to be efficient in evaluating where conventional
resistivity logs fail to provide consistent water-saturation calculations. In general, the EPT has a good thin-bed resolution and
a short investigation depth of about 2 in. (5 cm); thus, the invaded zone around the wellbore will affect the measurement
significantly.

Based on the same measurement principle as EPT, the dielectric constant log, determines by using electromagnetic wave
at frequency ranging from 16 to 60 MHz (Geng et al., 1997). The dielectric-constant log is also valuable for distinguishing oil
form water that is fresh or of unknown salinity. An accuracy of between +6 to +9% s.u. in the can be achieved in the field
by the dielectric-constant log. The depth of investigation of dielectric-constant log is 1.3 to 1.7 ft (0.39 to 0.5 m).

Pulsed Neutron Capture (PNC) Log: PNC log is convenient for measuring residual oil (or remaining oil) since it can be
used in cased-hole. Because of the nature of the measurements, most of the effects of the borehole, casing and cement can be
eliminated (Richardson et al., 1973). The PNC log is also called thermal decay time log (TDT) or neutron lifetime log
(NLL). The most significant use of PNC logging is to discriminate among gas-bearing, oil-bearing, and salt-water-bearing
formations in cased holes. Saturation can be determined from PNC log data when porosity, rock type, formation hydrocarbon
type, and formation water salinity are known or could be estimated using the following formula:

Σ Σ 1 ∅ Σ ∅ Σ 1 ∅………………………………………………..….. (6a)

where Σ is bulk macroscopic thermal neutron capture cross-section, s.u. (sigma unit = 10 / ), measured by PNC
logs; Σ is matrix macroscopic thermal neutron capture cross-section, s.u.; Σ is formation water macroscopic thermal
neutron capture cross-section, s.u.; Σ is formation-hydrocarbon macroscopic thermal neutron capture cross-section, s.u.;
is water saturation, and ∅ is porosity.
8 SPE 164483

In flushed zone, Eq 10a can be used to determine residual oil saturation if other parameters are known or estimated with
acceptable accuracy. However, in spite of its advantage of logging only once, the uncertainty in determining the cross section
of the rock matrix makes the conventional PNC log unreliable for measurements. The LIL waterflood technique enhances
measurement by injecting contrasting-salinity water (Σ Σ ) to eliminate the need of capture cross-section
measurements of the rock matrix and residual oil. By logging, change Σ , and relog, (i.e LIL), we can arrive at the following
simple and reliable equation for estimation:

1 ……………………………………………………………………..…..….. (6b)
∅
where Σ , Σ , Σ and Σ are the sigma value of the formation and water measured before and after 2 injection
respectively.

The main advantage of LIL PNC method is its good (+4% s.u.) to excellent (+2% s.u.) accuracy of determining behind
casing (Richardson et al., 1973). In case of low porosity and low displacement efficiency (DE) field cases, LIL PNC can be
further modified by LILIL (three times logging). This approach is called modified LIL PNC and for further clarification of
the method reader is referred to Pathak (2012).

Continuous Carbon/Oxygen (C/O) Log: is pulsed neutron log that utilizes a pulsed 14 MeV neutron source and a
gamma ray detector, similar to those employed in thermal neutron decay logs but at a higher neutron pulsing rate (20 kHz)
with different detector time gates and energy range. Gamma rays from neutron inelastic interactions with carbon, oxygen,
calcium, and silicon are developed into C/O and Ca/Si ratios which are employed to determine oil saturation and lithology,
both independent of formation water salinity and shaliness (Smith and Schultz, 1974). Because the C/O ratio (or Ca/Si ratio)
is insensitive to the chlorine content of wellbore formation water, C/O logs can be used in areas where PNC is not applicable.
The LIL technique has been used with the C/O log to measure in several fields with good accuracy (Lock and Hoyer,
1981; Fertl, 1984). The remaining oil saturation is estimated using the following equation:

/ / %
………………………………………………………………………… (7)
/ % / %
where C/O is inelastic gamma ray Carbon to Oxygen ratio measurement.

Gravimetric Log: The gravimetric logging method uses the logging tool traversed in the borehole to measure the formation
bulk density over a radius of 50 ft (15 m) at spaced locations. The is determined by use of the matrix density, water
density, oil density, fractional porosity of the formation, and bulk density. The gravity logging method is independent of the
bore-hole size, rugosity, shale content, lithology, acidization, and casing. The method has large radius of investigation but a
poor vertical resolution (Maute and Gournay, 1985). Bulk density of oil bearing formation can be described as follows:

ρ ρ 1 ∅ ρ ∅ ρ 1 ∅………………………………………………..….. (8a)

where ρ = bulk density (g/cc), ∅ = effective porosity, ρ = matrix density (g/cc), = water saturation, ρ = water density
in-situ (g/cc), ρ = oil density in-situ (g/cc).

In aquifer drive (log-produce-log method) or in waterflooding (log-inject-log), can be measured by investigating the
gravity difference in the two logs.

Assuming matrix density, oil densities, and porosity remain the same and water density changes between the first and the
second log, the following equations can be derived (where subscripts 1 and 2 refers to quantities in first log and second log
respectively):

ρ ρ 1 ∅ ρ ∅ ρ 1 ∅………………………………………………..….. (8b)

ρ ρ 1 ∅ ρ ∅ ρ 1 ∅………………………………………………..….. (8c)

Solving the two equations,

…………………………………..……….....….……………...….. (8d)
∅

If is at residual oil saturation condition (in the log-inject-log if enough water is injected to displace all the oil from the
wellbore or in the case of log-produce-log if enough time is given to move the oil-water contact to have 100% water
production from the depth of investigation in the second logging), with prior knowledge of other quantities, Eq 10d can be
used to determine residual oil saturation with very good accuracy (Maute and Gournay, 1985).
SPE 164483 9

Well Tracer Tests:

A novel method of looking at residual oil farther away (say about 10to 40 ft, or 3 to. 12 m) from the borehole was suggested
by Deans (1971). In this method a chemically reactive tracer is injected into the formation and allowed to hydrolize into two
components. One of these components is preferentially partitioned by the oil, so that when the well is produced back the
tracers will return at different times because they travel at different velocities. The formation with its residual oil in effect acts
as a chromatographic column causing separation of the tracers. The separation can be related to the residual-oil saturation.
Tomich et al. (1973) described the theory of the tracer method by considering the velocities of the component fluids.

The local velocity of a typical tracer molecule ( ) is:

………………………………….…………………………………….…..…. (9a)

When the formation water is flowing at a velocity ( ) and the residual oil is stationary. The fraction of time the tracer
molecule stays in water is . If the distribution of the tracer between oil and water is at equilibrium, as will occur when ( )
is very small, the following equation holds true:

…………………………………………..…………………….…. (9b)

Where is mathematical ratio proportional to the difference in arrival time of tracers. is the laboratory-measured
distribution of partition coefficient; this coefficient is defined as the equilibrium ratio of tracer concentration in the oil phase
to concentration in the water phase as:

………………………………………………………………………….. (9c)

From Eq 9a and 9b, the velocity of a typical tracer molecule can be calculated:
………………………………………………………………………..……. (9d)

Tracers with different partition coefficients will have different velocities thereby allowing separation when fluids are
withdrawn from the formation. This separation can be mathematically related to residual oil saturation.

Single Well Chemical Tracer (SWCT) is a backflow tracer test normally performed on watered out wells. The technique is
applicable in both sandstone and carbonate reservoirs for a wide range of conditions. Unlike core analysis, single well
chemical tracer (SWCT) method samples a much larger volume of reservoir around a single well. The residual oil saturation
measured represents an average over as much as several thousand barrels of pore space. Moreover, since chemical tracer
method is an in-situ measurement, additional limitations of other methods are also avoided.

In the single well tracer technique, a primary tracer bank consisting of ethyl acetate ( tracer dissolved in formation
water is injected into a formation that is at residual oil saturation. This bank is followed by a bank of tracer-free water. The
well is then shut in to permit a portion of the ethyl acetate to hydrolyze to form ethanol ( , the secondary tracer (see
the chemical equation below). Finally, the well is produced and the concentration profiles of the two tracers will be
monitored.

C4 H 8 O2  H 2O C2 H 5OH  C2 H 4 O2 ..........................(10)
 ethyl acetate   formation water   ethanol   Acetic acid 

Ethyl acetate is soluble in both the water and oil phases, but ethanol is, for all practical purposes, soluble only in the water
phase. As a result, the ethanol travels at a higher velocity and returns to the wellbore earlier than does the ethyl acetate. The
difference in arrival times can be used to determine the residual oil saturation through the use of computer programs that
simulate the tracer test (the greater the oil saturation, the greater the difference in arrival times) (see Figure 6). Field tests
have demonstrated the reliability and applicability of this technique (Deans, 1971; Tomich et al., 1973). This separation,
combined with the laboratory measurement of the ester oil/water partition coefficient (Ki) can be used to determine .
Figure 6 the procedures to determine residual oil saturation from SWCT technique. Figure 7 shows example of field
application and its value determined by measuring the separation of the primary and secondary tracers as mentioned
above.
10 SPE 164483

Figure 6: SWCT test production profile with simulations to determine .

Figure 7: value determined using SWCT for one zone in Means Field
(West Texas Carbonate Field) (Pathak et al., 2012).

Though single well tracer can be regarded as more reliable way of measuring residual oil saturation, it has its own limitations.
The following are some of the reported limitations:
 Unlike core and logging, we can’t have a saturation profile; rather we have a weighted average single value for the
measured zone.
 It is effective below a formation temperature of 200 oF.
 It needs a well shut-in for days or weeks, hence it is costly.
 The accuracy is dependent on the proper zonal isolation and effective squeezing of the zone under study. This is
sometimes difficult to achieve.
 Recovery of tracers is an issue.
SPE 164483 11

Cooke (1971) developed a well-to-well tracer test to measure the interwell . In Cooke’s method, two or more tracers
having different partition coefficients between oil and water phases are injected. As the tracer fluid moves through the
reservoir, one tracer is retarded more than the other. Then, the average inter-well can be determined by monitoring the
degree of separation of the tracers at the observation well.

In addition to determining , the application of interwell tracer tests is becoming increasingly important to the petroleum
industry for wider reservoir characterization purposes. Interwell tracer tests have been used to investigate reservoir flow
performance and reservoir properties that control gas and water displacement processes. Tracer data have been used to reduce
uncertainties attributed to well-to-well communications, vertical and horizontal flow, and residual oil saturation (Myne and
Pendleton, 1985; Wood et al., 1990; Allison et al., 1991; Tang 1991; Tang 1992; Tang 1995; Cheung et al., 1999; Du and
Guan, 2005).

Reservoir Performance Study Method:

All the following reservoir performance studies can only give remaining oil saturation (ROS). When the movable oil
saturation is zero after water flooding (or almost 100% water cut), the ROS will approach to the value.

Material Balance Method: Material-balance calculation is an average estimation of the remaining oil content in an entire
reservoir after produced-oil volume is subtracted from initial estimates of the reservoir. The volumetric or material-balance
equations are used to estimate initial oil in place. Material balance methods can lead to inaccuracies of ROS for the following
reasons (Babadagli, 2005):
 Errors in basic volumetric data of the reservoir compounded in the final calculated value of ROS, and
 Errors resulting from only a single ROS average value being computed for the entire reservoir.

In Material Balance method of determining the remaining oil saturation, calculations can be done using the following
equation if the total amount of oil in place (Noi) and the cumulative oil produced to the end of waterflooding (Np) is known:

…………………………………………………………..…..………… (11a)
∅
where
Noi = Initial oil in place S = Remaining oil saturation (ROS).
Np = Oil produced ∅ = porosity.
A = cross section area of the flooded region, ft2. BoWF = Formation volume factor of oil (after waterflooding).
h = height of the flooded interval, ft.

In equation 11a, prediction of Np is a critical task which should be done appropriately otherwise it will lead for erroneous
ROS calculation. One of the techniques used for this is the material balance equation shown below:

…..… (11b)

where
Bo = Formation volume factor of oil, rbbl/stb.
Bg = Formation volume factor of gas, rcuft/scf.
Bt = current two-phase formation volume factor, rbbl/stb.
Bti = Initial two-phase formation volume factor, rbbl/stb.
BW = Formation volume factor of water, rbbl/stb.
We = Cumulative water influx, rbbl.
Wi = Cumulative water injected, stb.
Gi = Cumulative gas injected, rcuft.
Wp = Cumulative water produced, stb.
Noi = Initial oil in place, bbl.
Np = Oil produced, bbl.
m = Ratio of initial gas cap size to initial oil zone size.
Rp = Cumulative produced gas-oil ratio, scf/stb.
Rs = Solution gas oil ratio, scf/stb.
= pressure drop, pis.
Swi = Initial water saturation.
c∅ = formation compressibility, 1/psi.
c = formation water compressibility, 1/psi.
12 SPE 164483

Production Data: production history plot is another reliable source to estimate the final production (Np). Graphical (Arps,
1945) and analytical (Fetkovich, 1987) techniques can be applied to forecast the production data.When multiphase
production occurs from a well, the saturations can be estimated using the production relative permeability data. The relative
permeability ratio can be obtained using:

…………………………………….………. (12)
where
K = relative permeability to water phase. μ = viscosity of produced water, cp
K = relative permeability to oil phase. μ = viscosity of produced oil, cp
qw = water production rate, bbl/day WOR = water oil ratio
qo = Oil production rate, bbl/day

If the flow rates are known, Oil saturation can be calculated by dividing the current reservoir volume of the oil (Vo) by the
current pore volume (Vp) as follows:

S ………………………………………… (13)
∅ /
where
S = current (remaining) oil saturation (ROS). c∅ = formation compressibility, 1/psi.
V = current (remaining) oil volume, bbl. = pressure drop, psi.
V = current reservoir pore volume, bbl. Noi = Initial oil in place, bbl.
Swi = Initial water saturation. Np = Oil produced, bbl.

In Eq 13, when oil production approaches economic limit (> 98% water cut), S approaches to residual oil saturation. The
advantage of estimating residual oil saturation by reservoir performance is that it is relatively easy to do once the input
parameters are obtained. However, the biggest limitation of this method is the difficulty of obtaining reliable input values for
the calculation. Each of the basic parameters can have a wide range of estimates which leads to a large uncertainty in
calculating remaining or residual oil saturation.

Well Testing: Well testing methods require the estimated effective permeability from well pressure-transient tests and a
relative permeability curve as measured on reservoir core in the laboratory. Because the oil/water relative permeability is a
function of water (or oil) saturation, the oil saturation can then be estimated from the effective permeabilities with the well
testing methods. In addition, saturation can be estimated through the following relationship if there is no free gas in the
system (Ramey, 1975).

∅
S …………………………………………………………… (14a)
where c∅ , c , and c are formation, oil, and water compressibilities, respectively; S = current (remaining) oil saturation
(ROS); the total compressibility, ct, can be obtained from pressure transient analysis using the following relationship
(Earlougher, 1977).

. /
c ………………………………………….…… (14b)
∅ /
where
c = total compressibility (1/psi); ∅ = porosity; r = reservoir radius, ft.
= total mobility and can be calculated by summation of each phase mobility . , ;
and / are the time and dimensionless time values obtained from the type curve analysis.

There are also analytical and numerical modeling techniques to estimate the waterflood performances but the accuracy of the
models strictly depend on the estimation of the Sor (or relative permeabilities), which is based on core analysis.

Numerical Reservoir Simulation: comparing with material balance and well testing, reservoirs simulation study gives a
better way to estimate remaining oil saturation and its distribution at any given time of the field. However, its accuracy is
dependent on having a realistic geologic model, reservoir initial condition and good history matching with enough production
data.
SPE 164483 13

Conclusions
This paper summarizes the existing methodology for determining residual oil saturation ( ) in laboratory and in field.

In the laboratory scale, can be determined from conventionally recovered cores. Improved reliability can be achieved
using pressure coreing or sponge coring.

In the field scale, there are several methods to measure and remaining oil saturation (ROS) with reasonable accuracy.
Depending on the type of reservoir, well completion and operating conditions, appropriate techniques should be applied to
determine and ROS. Field and ROS determination techniques can fall in the following categories: well logging,
backflow tracer, and multi well. Conventional logging is not reliable in determining ; hence, log-inject-log approach was
devised. Multi well and ROS determination includes interwell tracer and reservoir performance study using material
balance, numerical simulation, well transient analysis and production data.

Reliable remaining oil saturation (ROS) and residual oil saturation ( ) values are key parameters for reservoir management
and EOR decisions. Each determination technique has its advantages and limitations (Appendix 1). A more reliable
can be obtained by combining two or more methods.

Acknowledgments
The authors would like to thank Abu Dhabi National Oil Company (ADNOC), The Petroleum Institute (PI), Abu Dhabi;
Marathon Center of Excellence for Reservoir Studies (MCERS), and Center for Earth Materials, Mechanics, and
Characterization (CEMMC) at Colorado School of Mines for their support of this study.

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16 SPE 164483

Appendix 1: Advantage and Disadvantage of determination methods

Investigation depth Advantage Disadvantage
Coring
Conventional <10 in. (25 cm) Widely available Difficult to get in situ
Pressure <10 in. (25 cm) Excellent accuracy New well required
Poor to fair core recovery
Sponge <10 in. (25 cm) Good accuracy, not expensive Difficult to get gas saturation
Program required for good
Tracer Test 25 to 40 ft (7.5 to 12 m) Fair to excellent accuracy interpretation
Required relatively homogeneous
Large reservoir volume measured formation
Measured volume can be controlled Average only
Logging
Resistivity
Conventional 2 to 50 ft [0.6 to 15 m] widely available, large investigation radius Poor accuracy
LIL 2 to 50 ft [0.6 to 15 m] Excellent accuracy __
NML
Conventional 2 ft [0.6 m] __ For heavy oil only
Log‐Inject 2 ft [0.6 m] Direct measurement __
Dielectric constant
Conventional 1 to 2 ft [0.3 to 0.6 m] can be run under various formation Poor accuracy
EPT
Conventional 2 in. [5 cm] Can be run under various formation salinities Short investigation depth
Good Vertical resolution
PNC
Conventional 7 to 24 in. [17.5 to 60 cm] __ Poor accuracy
LIL, water 7 to 24 in. [17.5 to 60 cm] Excellent accuracy __
LIL, chemical 7 to 24 in. [17.5 to 60 cm] Porosity not required Three injections required
LIL, chlorinate oil 7 to 24 in. [17.5 to 60 cm] Movable oil saturation can be measured Four injections required
C/O
Questionable accuracy; unstable
Conventional 9 in. [23 cm] Can be run under various formation salinities performance
LIL, water 9 in. [23 cm] Can be run under various formation salinities; __
excellent accuracy
LIL, chemical 9 in. [23 cm] Can be run under various formation salinities; __
porosity not required
Gamma ray log
Questionable accuracy; hard to
LIL, water/chemical 2 to 4 in. [5 to 10 cm] Good vertical resolution; wide availability eliminate
wellbore radioactivity before
second log run
Gravity
(conventional and LIL) 50 ft [15 m] Good for all wellbore conditions, Poor vertical resolution;
large measured volume long injection/production time
Well Test Methods
Effective Permeability Well drainage area __ Poor accuracy
Interwell
Field test and improvement
Resistivity Well‐to‐well distance Interwell requirement
Well‐to‐well tracer Well‐to‐well distance Interwell Long measuring time
Oil displacement Well‐to‐well distance Interwell Long measuring time
Total Compressibility Well‐to‐well distance __ Poor accuracy
WOR Well drainage area Simple calculation Poor accuracy
Need accurate reservoir/
Material Balance Whole reservoir Simple calculation production data
Poor accuracy
Reservoir Simulation Whole reservoir Provide areal ROS Poor accuracy
Source: Chang et al. (1988), SPE Formation Evaluation, March 1988,