IPTC-17990-MS

Evaluation and Comparison of Available Tracer Methods for Determining

Residual Oil Saturation and Developing an Innovative Single Well Tracer
Technique: Dual Salinity Tracer
Rasoul Khaledialidusti and Jon Kleppe, Norwegian University of Science and Technology; Saeid Enayatpour, the
University of Texas at Austin

Copyright 2014, International Petroleum Technology Conference

This paper was prepared for presentation at the International Petroleum Technology Conference held in Kuala Lumpur, Malaysia, 10 –12 December 2014.

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Abstract
It is generally recognized that the determination of residual oil saturation (Sor) plays a considerable role
in managing and selecting the EOR methods. There are a number of methods to determine Sor and each
method has advantages and disadvantages. Among these methods, tracers are the most efficient, largely
due to the measurement over large reservoir volume and non-dependency on porosity. The objective of
this study is the evaluation and comparison of available tracer methods in different reservoir conditions
since 1971 until the present time and proposing a new tracer technique to overcome limitations of previous
tracer methods.
The first tracer technique to measure Sor, is well-to-well method. The major limitation of this technique
is the long measuring time. To get over this barrier, single well tracer techniques (SWTTs) were
developed. Due to the reversible nature of tracers, it is impossible to use two or more non-reactive tracers
in SWTTs without any irreversibe step. Single well chemical tracer technique (SWCTT) is the first SWTT
which utilizes hydrolysis reaction as an irreversible step. While SWCTT overcomes the limitation of
well-to-well technique, other limitations are encountered such as difficulty in finding partially reactant
tracer and predicting reaction condition in different reservoir conditions (temperature, salinity, and pH),
depth of investigation, and drift during soak period. Some other SWTTs are developed to remove some
of these limitations, but as far as these techniques utilize hydrolysis reaction, they could not overcome all
the limitations of SWCTT.
Since many limitations of SWTTs are as a result of the hydrolysis reaction, the main objective of our
innovative technique is to remove hydrolysis reaction and cause an irreversible step by utilizing the
dependency of partitioning coefficient to salinity. The sensitivity of partitioning coefficient to changing
reservoir condition leads to a delay in arriving back of tracers to the well and Sor determination using the
principles of chromatography.
2 IPTC-17990-MS

Introduction
It is generally recognized that the determination of residual oil saturation (Sor) plays a considerable role
in managing and the selection of EOR methods. There are a number of methods to determine Sor. The
detailed of these methods and advantages and limitations of each method are compared (Kidwell et al.,
1980, Donaldson et al., 1981, Blackwell, 1985, Chang et al., 1988, and Teklu et al., 2013). The most
common method for acquiring Sor is coring which include direct sampling from the rock. This method has
some limitations which cause uncertainty. The one is related to sampling technique because the sample
taken cannot be considered as a whole reservoir. The other limitation is that coring method can only be
used in new drilled wells. Another method for obtaining this information is logging methods which can
investigate only a short distance beyond the wellbore. Material balance calculations based on production
history are another method. Determination Sor by means of material balance needs more variables than
other methods. For example, it is imperative to obtain initial fluid saturation of the reservoir by some other
method and information about the source of the recovered flow to utilize material balance. Among these
methods, tracers are more efficient largely due to the measurement of large reservoir volume and
nondependency on porosity.
Well-to-well is the first tracer technique to measure Sor. In this method, two or more non-reactive
tracers with different partitioning coefficient between oil and water phases are injected into the formation.
Different partitioning coefficient leads to difference in arrival times to the production well. The separation
that occurs as a result of chromatography is preserved because the tracers continue traveling in a path
through the pore space without reversing back to the injection well. This technique has an important
limitation, long measuring time from injection to production well. For removing this limitation, single
well tracer techniques (SWTTs) were developed. Producing back the two banks of un-reactant tracer in
a single well leads to return to the well as they were injected and causes their arrival back to the well show
the injection scheme and not reflect Sor; consequently, because of reversible nature of tracers, it is
impossible to use two or more un-reactant tracers in SWTTs without any irreversibly step. Single well
chemical tracer technique (SWCTT) is the first SWTT which utilize hydrolysis reaction as an irreversibly
step. While SWCTT overcomes the limitation of well-to-well technique, other limitations are encountered
such as difficulty in finding partially reactant tracer and predicting reaction condition in different reservoir
conditions (temperature, salinity, and pH), depth of investigation, and drift during soak period. Some other
SWTTs are developed to remove some of these limitations, but as far as these techniques utilize hydrolysis
reaction, they could not overcome all the limitations of SWCTT. In this paper, the advantages and
limitations of all developed tracer techniques are compared and an innovative tracer technique in order to
remove the limitations of previous techniques is proposed.
Since many limitations of SWTTs are because of the hydrolysis reaction, the main object of innovative
technique is to remove hydrolysis reaction and cause an irreversibly by utilizing the dependency of
partitioning coefficient to temperature, salinity, or pH. In this method, two or more un-reactant tracers are
injected in the formation at different temperature, salinity, or pH condition and allow reaching to the
equilibrium condition. The sensitivity of partitioning coefficient to changing reservoir condition leads to
a delay in arriving back of tracers to the well and Sor determined using the principles of chromatography.
The existence of one mobile phase flow is necessary for the tracer methods; however, it is not necessary
that the other fluids be immobile prior to tertiary enhanced oil recovery projects. Having more than one
immobile phase flow causes complexity in the result analysis. Knowing this notion can be useful that if
only minor quantities of other phases are produced (less than 10%), the principle of chromatography will
be accurate to a reasonable extent. This estimation can be further revised by adapting the average
velocities of the tracers to account for flow of the immobile phase. In this paper, all methods are described
based on the fact that reservoir formation containing one mobile fluid phase, brine, and one immobile fluid
phase, oil. The partition coefficients which are used in the chromatographic analysis are ratios which
IPTC-17990-MS 3

describe the equilibrium distribution of a tracer between phases. These ratios are also known as
distribution coefficients and equilibrium ratios and can be determined by simple experimental procedures.
Where only two phases exist in the reservoir, a two-phase partition coefficient is determined for each
tracer. Where oil, gas and water coexist in the reservoir, three phase partition coefficients must be
determined if the method of this application is used to ascertain the relative saturations of all three fluids.
Three-phase partition coefficients are determined in a manner similar to the two-phase partition coeffi-
cient except that a third fluid, the second immobile phase, is added to the system and the tracer
concentration in the carrier fluid and each of the immobile fluids is established. The tracers must have
different partition coefficients between the carrier fluid and immobile phase or phases. While any
difference in partition coefficients would be satisfactory in a theoretically point of view, one partition
coefficient practically should be at least twice as great as another to clearly distinguish the arrival of the
tracers (Cooke 1971). This approach is more important if tracers travel in short time and the difference
in partition coefficients should me more. The best results are obtained in such a case where one tracer is
substantially insoluble in the immobile liquid and the second tracer is more highly soluble in the immobile
liquid than in the carrier fluid. The partition coefficient for the first tracer would be infinite; for the second
tracer it would be less than one.
A minimum of two tracers are required in the practice of tracer methods. Two tracers can be used where
only two fluids, oil-water or gas-water, exist in the reservoir or where three fluids are present and the
saturation of one fluid is determined by independent means. However, even under these circumstances,
more than two tracers may be employed. A third tracer with a partition coefficient which differs from
those of the other tracers would give additional comparative information. A fourth would give even more
information. There are, of course, limitations on the number of tracers in the carrier liquid. One tracer may
have an effect on solubility of another. Also there are economic limitations on the number of tracers to
be employed. Where three fluids, oil, gas and water, are present in the formation and the saturation of each
fluid is to be determined by this method, at least three tracers are required.
It should also be noted that it is not essential that the tracers be simultaneously injected into the
reservoir. Simultaneous injection would be more convenient in most instances and, therefore, would be
preferred. However as long as the tracers traverse the same region of the formation, they can be injected
together or sequentially and the results analyzed accordingly.
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:
(1)

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 fwi. 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:
(2)

Where ␤i is mathematical ratio proportional to the difference in arrival time of tracers. K 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:
(3)

From Eq. 1 and 2, the velocity of a typical tracer molecule can be calculated:
(4)
4 IPTC-17990-MS

Tracers with different partition coefficients will

have different velocities thereby allowing separa-
tion when fluids are withdrawn from the formation.
This separation can be mathematically related to Figure 1—Comparison of investigation region between interwells and
residual oil saturation. It should be considered that single well methods
an elution profile having a sharp peak provides
maximum accuracy. While insufficient volume of tracers may lead to undetectable amount of tracers in
the target well, an excessive volume of tracers makes flat peaks in the elution profiles that cause some
difficulty to interpret accuracy. Therefore, optimum injection of tracer solutions should be employed.
The carrier fluid must be miscible with the mobile phase and must be capable of solubilizing the tracers
which it carries and should be in the same state as the mobile fluid. The tracers also must be soluble in
the carrier fluid. This solubility must be to the extent that the concentrations of the tracers can be detected
at the target well. This detection is very vital to determine Sor accurately and the effects of dispersion,
diffusion, the sensitivity of partitioning factor to changing reservoir conditions and the sensitivity of the
detection means should be considered. It should be noted that tracers which have tendency to absorb by
rock surface, should not be used. Where brine, for instance, is the mobile phase, produced formation water
is the best choice for the carrier liquid.
The details of all tracer methods to determine Sor are described in the following section:

Tracer Methods for Determining Sor

All available tracer methods to determine Sor are listed:
● Interwell Techniques:
X Well-to-Well
● Single Well Techniques:
X Single Well Chemical Tracer
X Dual Temperature Tracer
X Modified Single Well Chemical Tracer
X Single Well CO2 tracer

Interwell Methods

Well-to-Well (PITT)
This method is developed by Cooke in 1971 to measure interwell Sor. In Cook’s method, a slug of carrier
fluid which is miscible with the brine inject into the reservoir and this slug displace through the formation
toward production well. The carrier fluid contains two un-reactant tracers having different partitioning
coefficient between oil and brine. Different solubility of tracers in oil and brine result in the separation
of the tracers and the tracer with lower partitioning coefficient reaches faster to the production well than
the other tracer. As times goes on, the distance between the peak concentrations of tracers increases.
Breaking through at the producing well takes just over 100 days for non-partitioning tracer and 150 days
for partitioning tracer (Cooke 1971). The amount of Sor can be determined by chemically analyzing for
the presence of tracers and monitoring the degree of separation of tracers at the observation well.
This method has a great advantages and that is utilizing large measured volume between two well to
determine Sor; however, it has a disadvantage that cause a limitation, long measuring time. To overcome
this disadvantage, SWTTs are developed which just one well is employed to determine Sor.
IPTC-17990-MS 5

Figure 2—Stage 1: Water and ester is injected into watered out section (left), Stage 2: Some of the ester hydrolysis to alchohol (middle), Stage 3: The
ester partition to oil and is delayed, compared to the alcohol.

Single Well Methods

Producing back the two banks of non-reacting tracer
in a single well leads to return to the well as they
were injected because of reversible nature of non-
reacting tracers. It causes their arrival back to the
well show the injection scheme and not reflects Sor;
consequently, because of reversible nature of trac-
ers, it is impossible to use two or more non-reacting
tracers in SWTTs without any irreversibly step.
Therefore, it is imperative to utilize a technique as
an irreversibly step in SWTTs.
Single Well Chemical Tracer (SWCT) Figure 3—SWCT test production profile with simulations to determine
This method is the first SWTT which utilize hydro- Sor (solid line: simulation, dotos: field data).
lysis reaction as an irreversibly step and is invented
by Deans (1971) to measure saturation functions farther away from the borehole in watered out reservoirs.
This novel method includes the injection of a chemical reactive tracer (e.g., ethyl acetate) into the
formation. The well is then shut in just over 10 days to allow the injected tracer to hydrolyze with the
water to form a second tracer, ethanol. The product tracer does not partition into the oil phase, so that
when the well is produced back the tracers will return at different times because they travel at different
velocities. The product tracer travels faster than the injected tracer, and the lag between the injected and
product tracers is used to calculate the oil saturation (Figure 2).
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 3). 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 Sor.
SWCTT is unique in its large depth of investigation (10 to 40 ft [3 to 12 m]) and the ability to control
the depth of investigation (Teklu et al., 2013). This novel method utilizes a hydrolysis reaction to cause
irreversibility step which includes the injection of a chemical reactive tracer (e.g., ethyl acetate) into the
formation and post waterflood to move the tracer to the investigation point. The well is then shut in to
allow the injected tracer to hydrolyze with the water to form a second tracer (e.g., ethanol). The important
note which should be considered is that only some part of reactive tracer must hydrolyze and form second
un-reactant tracer to detectable extent. To provide this point, managing injection, shut-in, and production
6 IPTC-17990-MS

time in different reservoir condition is needed as well as proper amount of injection rate and amount of
tracer. As far as the product tracer has different partitioning coefficient in comparison with the reactant
tracer or in ideal case does not partition into the oil phase, so that when the well is produced back, the
tracers will return at different times because they travel at different velocities. The product tracer due to
lower partitioning coefficient travels faster than the injected tracer, and the lag between the injected and
product tracers is used to calculate the oil saturation. 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). 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 Sor. Since SWCT was developed by Exxon in 1971 (Deans, 1971) various field (Bragg et al.,
1976, Deans et al., 1980) tests and experiments (Carlisle et al., 1982) have been conducted and different
models for test interpretation have been developed. Fifty-nine single-well tracer tests in 30 reservoirs were
surveyed (Deans et al., 1980) to examine tracer design, injection profile, shut-in time, and accuracy limits.
Test case no.11 is simulated using UTCHEM to show the different arrival times of injected and product
tracers (Figure 3).
The hydrolysis reaction rate varies in different reservoir conditions. High temperature, salinity and pH
will increase the reaction rate. The consideration of these conditions is necessary to obtain measurable
un-reacted ester and alcohol. Another important note that should be considered is about hydrolysis
reaction during injection and production rate. If these periods are relatively short compared to the soak
time and the reaction rate is relatively slow during these times, ignoring hydrolysis reaction during
injection-production periods to a great extent is a reasonable assumption. If the reservoir be in harsh
condition (high temperature, salinity and pH), hydrolysis reaction rate is considerable and in this situations
the principal rules such as injection, shut-in, production times, and tracer concentrations of SWCTT
should be revised in order to have a detectable amount of tracers (Mechergui et al., 2012).
While SWCTT has been used extensively for measuring oil saturations, most of the tests have been
conducted in sandstone reservoirs (Deans et al., 1986). This is because of the fact that SWCT tests in
carbonate reservoirs are difficult to interpret and lead to considerable distortions in most carbonate SWCT
tests. This difficulty is because of a characteristic heterogeneity in carbonate reservoirs which cause
excessive early arrival of poorly defined peaks for tracers, excessive early dilution of tracers, and poor
material balance between injected and produced tracers. To resolve all of these difficulties in carbonate
reservoirs, Deans and Carlisle (1986) used a modified form of the “dead-end” pore model. The pore
diffusion model has been used to simulate SWCT test profiles from carbonate formation and the model
assumes that a fraction of the available pore volume can only accessed by diffusion of the tracers. Unlike
some methods to determine residual oil saturation such as core analysis, 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. Accuracy of ⫾2 to ⫾3%
PV by the tracer method is confirmed in the laboratory results from pressure-core and mathematical-
model methods (Tomich, 1973).
Assuming that the flow pattern is reversible, the hydrolysis rate of the reaction tracer remain unchanged
during the process, and the main part of the reaction occurs during the soak period, Sor can be determined
from the arrival time of the two tracers and Ki as follows:
(5)
IPTC-17990-MS 7

Where Voi and Vwi are arrival volumes of oil and water tracers. It is imperative the Voi/Vwi ratio to be
constant thorough tracer production in order to determine Sor uniquely. If this ratio not be constant, the
test is flawed.
While SWCTT overcomes the limitation of well-to-well technique, other limitations are encountered
which is listed as follows:
ï Difficulty in finding partially reactant tracer and predicting reaction condition in harsh reservoir
conditions (high temperature, high salinity): In this technique, it is necessary that the reactant tracer
partially reacted under the reservoir conditions so that both the reactant tracer and the product
present in detectable amounts in the recovered materials. It should be considered that at high
temperature (above 100 c) and high salinity (200 g/L), the partitioning coefficient and hydrolysis
reaction rate will be considerably high so that the probability of complete reaction of the
partitioning tracer increases. Therefore, it should be considered that in order to have a detectable
concentrations of both the reactant and the product materials, it is necessary to increase the
concentration of the reactant tracer in the injected carrier fluid which leads to increasing cost as
well as choose a suitable reactant tracer in harsh reservoir conditions and the principles of this
technique such as injection, shut-in and production time should be revised in order to have a
successful test.
ï Depth of investigation and partitioning coefficient: As far as the reactant tracer partitions between
the oil and the water, some parts of the reactant tracer remain in the saturated oil during injection
and production time. This partitioning causes retardation in displacing the ester in comparison with
the total volume of the carrier fluid. This effect is more considerable by using high partitioning
coefficient. While the optimum partitioning coefficient for reactant tracers is about 2, the parti-
tioning coefficient of the majority of reactant tracers are about 6. High amount of partitioning
coefficient causes a limitation for large depth of investigation because for overcoming the problem
of solubility of reactant tracer in the oil, the injection and production time should be optimum
which this optimum amount causes a limitation in order to reach large depth of investigation. This
is one of the main reasons that limit us to reach to the larger investigation depth. Another reason
is because of the fact that hydrolysis reaction occurs also during injection time and it increases the
probability of complete reaction of reacted tracer. Therefore, we cannot increase the injection time
in order to reach a larger investigation.
ï Drift during soak period: It should be noted that fluid injected into a well will drift with the overall
reservoir fluids during soak time, the pumps are shut down. The amount of drift depends on the
petrophysical formation properties and is about 0.3 (m/day). As far as for obtaining a detectable
amount of second tracer, a long soak period is required and it leads to making an error because of
the drift effect. To overcome this problem, it is necessary to utilize shorter soak period which in
this situation the probability of making detectable amount of second tracer becomes harder.
ï Dependency of hydrolysis rate on pH: It is accepted that hydrolysis rate of reactant tracers are
largely dependent on pH and this rate will vary by about a factor of 10 by changing 1 unit in pH.
Due to the generated acid during hydrolysis reaction during soak time, pH drops and it causes
hydrolysis rate decrease (Figure 4). This means that difficulties can occur in generating enough
amount of second tracer if soak time be short. While considering high soak time can solve the
problem of dependency of hydrolysis rate on pH, it encounters another problem regarding drift
problem. Therefore, the optimum time should be considered for soak time to smooth to an
acceptable extent the problems of drift and dependency of hydrolysis rate on pH. The significance
of pH changes is debated. According to CTI (Carlisle, 2008) pH changes during the well shut-in
period does not affect the outcome of SWTT as long as sufficient ester hydrolysis takes place, and
8 IPTC-17990-MS

that the small amounts of acid formed during

hydrolysis will be consumed by natural base
components in the reservoir.
In order to remove these limitations, a number of
other SWTTs are developed which some of those
are practical and others not. In continue, the advan-
tages and disadvantages of all proposed techniques
are investigated and the main reasons for being
impractical are explained.
Dual Temperature Tracer (DTT):
As far as some limitations of SWCTT are due to
hydrolysis reaction, in this method, the hydrolysis
reaction is removed and employed tracers which
Figure 4 —Effect of pH on hydrolysis rate of methyl formate (S. L.
partition differently in respect to temperature as an Wellington et. al., 1994).
irreversibly step (Keller at. al., 1974a). The varia-
tion of partitioning coefficient of many tracers toward temperate, salinity and pH is proved (Carlisle et al.,
1982, Mechergui et al., 2012). The foundation of this method is based on this variation. Indeed, the
temperature dependency of the petitioning coefficient of a partitioning tracer is utilized to determine Sor
by the single well method.
A carrier fluid containing at least one un-reactant tracer that soluble just in the mobile phase in the
reservoir that is insensitive to temperature (e.g. methyl alcohol) and at least one another tracer having a
partitioning coefficient that is sensitive to temperature is injected and displace through the formation to
reach a point at a temperature substantially different than the reservoir temperature. To make this
temperature difference, a heat exchanging fluid at a different temperature from the reservoir temperature
which is soluble in the mobile phase flow is injected thorough the formation is used to heat or cool the
portion of investigation depth. Next, the carrier fluid containing tracers is injected through the formation
at the same temperature as the heat exchange fluid, and then the well is shut in for a while until injected
fluids reach to temperature equilibrium with the reservoir. Due to the variation of the partitioning
coefficient of the temperature sensitive partitioning tracer, the velocity of the tracer through the formation
during injection step will be different than its velocity during production step. This irreversibly step leads
to different in arriving time at the well during production period and different in the elution peaks of the
partitioning tracer and the temperature insensitive tracer. This difference can be employed to determine
Sor based on chromatographic principles.
The relative saturations of oil and water in a reservoir which oil phase is immobile and water phase
is mobile without any free gas can be calculated as follows:
(6)

Where “S” is the fluid saturation, “V” is the volume of the mobile phase produced at tracer peak
arrival, “K” is the partitioning coefficient, “A” is related to non-partitioning tracer, “B” is related
partitioning tracer; “i” is related to injection temperature and “p” is related to equilibrium reservoir
temperature. It should be noted that the existence of free gas phase is not detrimental to this method and
gas saturation can also be determined.
This method has some advantages such as simplicity, inexpensively and the most important one is that
the partitioning tracer does not react in the formation in amount that reduces its concentration or adsorb
upon the reservoir surface. In this method the limitations of SWCTT which are related to hydrolysis
reaction during injection, soak and production periods are eliminated; however, with the temperature idea
some other limitations would be encountered. The one is that the temperature dependence of partitioning
IPTC-17990-MS 9

coefficient of many tracers is subtle and only small changes in partitioning coefficient may be occurred
for substantial changes in temperature. Therefore, the choice of suitable temperature sensitive tracer is
very vital to get accurate results. The second that seems more important is that it is difficult to keep
constant the temperature of injected fluid during injection period because of conductivity. Heat transfer
phenomenon leads to variation of the temperature of fluid injection as times goes on. By variation of
temperature, the partitioning factor of sensitive tracer will change and this variation some uncertainties to
determine Sor. As a result it is impossible to know temperature away from the well bore after injection
period; however, it can be simulated using numerical simulations to estimate the temperature of the fluid
injection during these processes.

Modified Single Well Chemical Tracer (MSWCTT):

As it is discussed, one of the important limitations of SWCTT is related to the amount of the reaction of
reactive tracer under the reservoir conditions. It is imperative that the reactive tracer only partially react
so that both the reactant and product materials are available in detectable quantities. As far as the
hydrolysis reaction rate varies in different reservoir conditions specially in harsh conditions (High
temperature, salinity and pH), finding a suitable reactive tracer which only partially react in these
conditions to form a second tracer having different partitioning coefficient can be difficult. Utilizing high
concentration of reactive tracer and revising and managing the injection, soak and production times may
be a solution for solving this difficulty in these conditions; however, this is difficult and lead to increasing
the cost because of the increased chemical usage, difficulty in predicting reaction conditions, difficulty in
finding suitable tracer, and because of careful control of times that is required. In addition, using high
concentration of tracers causes broad flat peaks in the elution profile that are difficult to determine Sor
accurately. Therefore, SWCTT is modified in order to overcoming this limitation by Keller at. al., 1974b.
In MSWCTT, a low concentration of the second nonreactive tracer is added to the carrier fluid as well
as the first reactive tracer which is used in SWCTT. Any conventional radioactive or chemical tracer
material that is soluble in the carrier fluid and does not react under reservoir conditions, and that is not
appreciably adsorbed by the reservoir rock, can be employed as the nonreactive or marker tracer. The
carrier fluid displaces through the formation away from the well and shut in for a sufficient period. During
shut in period, the reactive tracer reacts in the formation to form a third tracer material having partitioning
coefficient differently than the second un-reactant (maker) tracer, and then the fluids returned to the well.
The produced fluids are analyzed for the presence of second and third tracers to determine Sor by
employing the principles of chromatography. Indeed, the principle of MSWCTT is based on the presence
of second (un-reactant or maker) and third (produced material) tracers and inconsequence it leads to
overcoming the problem of reaction rate which is high in harsh reservoir conditions. This is because of
the fact that in MSWCTT, it does not need to worry about the presence of the unreacted first tracer
because there is no need to measure it.
While employing every reactive and un-reactant (maker) tracer with different partitioning coefficient
is practical in MSWCTT, it is better to utilize two tracers with the same partitioning coefficient. It leads
to both tracers moves through the formation at the same velocity and avoid inaccuracies caused by fluid
drift within the reservoir. The only necessity should be considered is that the partitioning coefficient of
nonreactive tracer must be different with the partitioning coefficient of product tracer.
The most advantages of MSWCTT are that it is not necessary to use high concentration reactive tracer
using MSWCTT in the harsh reservoir conditions. The smallest volume of carrier fluid containing the
reactive and marker tracer that provides a detectable peak in the elution profile is desirable. This smallest
volume depends upon the degree of dispersion in the formation and leads to an elution profile having a
sharp peak which provides maximum accuracy. While MSWCTT remove the limitation of SWCTT in
harsh reservoir conditions, it could not overcome the limitations regarding hydrolysis reaction and these
still are available.
10 IPTC-17990-MS

Single Well CO2 tracer:

Another technique in order to overcome some limitations of SWCTT, specially the limitation of
employing in higher temperature is proposed by Richardson, 1986, Wellington et al., 1994. In this
technique, in order to form tracers having different partitioning coefficients relative to oil and water
phases, salts of both a carbonic acid and a halocarboxylic acid is utilized. These salts react within the
reservoir to form CO2 as the tracer and a salt of a hydroxycarboxylic acid. Since CO2 is considerably
partitioned between oil and water phases and hydroxycarboxylic acid quite dissolved within the water
phase in the reservoir, this technique has the ability to determine Sor.
It should be noted that the second SWCTT identical in volume to the first test without any soak time
is necessary if nonideal tracer response is observed. This second test permits to measure independently
parameters such as generator transient reaction, flow reversibility, fluid loss out of zone, dispersion,
wellbore crossflow velocities between otherwise noncommunicating layers and drift. If transient reaction
happens for more than 20% of the total amount generated during the test, determined Sor is so uncertain
and a unique Sor value cannot be obtained. In this condition, a third test with a longer soak time or a switch
to a more appropriate generator is necessary.
This technique has some advantages which are listed as follows:
ï Temperature range: As it is mentioned, SWCTT is limited to reservoirs of less than 200 F. This
technique eliminates this limitation by using different tracers. A very large number of choices are
available for selecting of the halocarboxylic acid which can be served as a CO2 generator in
different reservoir temperature. This frequency let us to determine Sor in the reservoir temperature
above 300 F by utilizing this technique.
ï Deeper penetration: As it is mentioned, there are two main reasons which cause a limitation in
SWCTT to reach to the investigation depth larger than 50 ft. The one is that the reacted tracer is
an ester which is partitions between the oil and the water phases. This partitioning causes
retardation in displacing the ester in comparison with the total volume of the carrier fluid. The
second is because of the hydrolysis reaction during injection time which it increases the probability
of complete reaction of reacted tracer. Therefore, we cannot increase the injection time in order to
reach a larger investigation. This technique overcome this problem because CO2 which is
employed as an oil tracer is not present in the carrier fluid and this tracer forms after the carrier
fluid reach to the target point. Thus, the CO2 oil tracer will penetrate larger than 50 ft into the
formation and in consequence will employed larger volume of reservoir to determine Sor.
ï Partitioning coefficient: The partitioning coefficient, Ki, of esters is about 6 in most cases. Ki for
CO2 is about 2 and relatively is insensitive to salinity and temperature. The CO2 value for Ki is
much more optimum from a test sensitivity point of view in most cases, since more of it is present
in the water phase, which comprises the substantially all of the produced fluid.
ï Drift during soak time: While in SWCTT, long soak periods are required and this causes drift
which is a source of error and corrections must be made. Also, considerable accuracy and
sensitivity is lost in the process. In the present process, the wide choice of acid generators which
react at different rates at different temperatures coupled with more rapid backflow will greatly
diminish the effect of drift in many cases. This is because acid generators can be more optimally
selected to correspond to the actual reservoir temperature involved. Also, the water tracer and oil
tracer will stay much closer together in the reservoir and hence cancel much of the errors
introduced by the reservoir drift velocity.
ï Hydrolysis rate vs pH: As it is mentioned, one of the limitations of SWCTT is because of the
slowing down of hydrolysis rate during soak time as the pH drops due to the acid generated;
however, by the use of this technique, mentioned difficulty would be removed.
IPTC-17990-MS 11

Table 1—Comparison of Different Tracer Methods

Method Advatages Disadvantages

Well-to-well Well-to-well investigation depth Long measuring time

Single Well Get over well-to-well barrier ● finding partially reactant tracer in dif-
Chemical Tracer ferent reservoir condition
(SWCT) ● depth of investigation
● drift during soak period
● T ⬍ 200 F
Dual Temperatur Removing hydrolysis reaction and difficulty to keep constant the
Tracer (DTT) problems related to this reaction temperature of injected fluid during
injection period because of
conductivity
Modified Single Removing the problem related to Difficulties related to hydrolysis
Well Chemical finding partially reactant tracer reaction
Tracer in different reservoir condition
(MSWCT)
Single well Co2 ● Proper in T⬎ 200 F Existence of CO2 in the reservoir
Tracer ● Deeper Penetration
● Efficient Partitioning coefficient

This technique may have other advantages toward SWCTT which all of those are discussed by
Richardson, 1986. While Richardson’s technique overcomes many limitations of SWCTT, this technique
did not catch on because CO2 is usually present in the reservoir and it causes a significant uncertainty and
should avoid using tracers that have a presence in the test region. In addition, CO2 generators are more
expensive than esters.
Comparison of All Developed Tracer Methods
While there are some features which are quite common in all tracer methods, there are some specific
points which are due to the nature of these methods. Two important common features are listed as follows:
1. Required relatively homogeneous formation because in the heterogeneous reservoir the probability
of getting flat peaks increase.
2. Average Sor can be determined.
Other features which belonged to each method are compared in Table 1.
After reviewing all existence tracer methods in order to determine residual oil saturation, the innovative
method which is based on the minimizing of other methods uncertainties is explained. The purpose of
developing this method is removing the uncertainties of previous methods so that the hydrolysis reaction
is removed and the disadvantages regarding hydrolysis reaction disappear. In addition, this method is
suggested with the help of the fact that some tracers have different partitioning in different salinities as
follows:
Dual Salinity Tracer: Proposed Technique
Using the feature of different partitioning coefficient of tracers in different pH, salinity, and temperature
can be helpful in order to cause irreversibility in un-reactant tracers. Since the reservoir is always buffered
to the extent that it is difficult to change pH. The natural buffering in the reservoir and its unpredictability
will crush the pH idea. With the temperature idea, as it explained, the temperature dependence of K is
subtle. Only small changes in K for substantial changes in temperature. Equally, it is impossible to know
temperature away from the well bore. But, changing salinity is pretty easy and it just needs to inject the
desired salinity.
In this developed method, two un-reactant tracers with the same partitioning coefficient can be used.
One of the tracers should be sensitive and the other one should be insensitive to salinity changes. In
12 IPTC-17990-MS

contrast to dual temperature method which tracers are subtle to change partitioning coefficient in different
temperatures, finding suitable tracers with different partitioning coefficient in various salinity is more
convenient. The other advantage of this method is that changing salinity of the reservoir is much easier
than changing the temperature. In this method, by using two un-reactant tracers, all uncertainties regarding
hydrolysis reaction is removed.
The process of this method described as follows:
1. Injection a slug of high salinity
2. Injection of sensitive and insensitive tracers with the same salinity of previous slug
3. Pushing the tracers to the target point in the reservoir with the same salinity of previous steps
4. Shut-in period to allow the partitioning coefficient sensitive tracer change
5. Production time.
The idea of two different partitioning tracers introduced through a staggered injection to measure Sor
is novel; however, the problem here is dispersion. It is very difficult to know what the exact salinity radial
profile is away from the well bore. This unknown region is where the tracers are positioned. For this
reason this novel method is not still practical and needs more comprehensive investigations. Injection of
enough water to actually change the salinity were the second tracer slug is located independent of
dispersion (inject the first tracer in resident water then over displace with a different salinity bank then the
second tracer), it still has a problem. Recovering the deep tracer and maintaining the same salinity in the
pore space this tracer travels through is just not practical. The mixing of the two salinity waters (dependent
on dispersion) will make some kind of blend salinity that the deep tracer sees during recovery. If you
measure salinity during back production you stand a chance but that is the salinity that joined the tracer
at the well bore. Since the tracer is partitioning in the oil-water media, this is not the same water that the
tracer experienced during the return trip to the well.

Conclusions
In this paper, all available tracer techniques to determine Sor are evaluated and compared. Each of the
tracer methods has some advantages and disadvantages. By comparision of all features of all methods it
can be concluded that SWCTT is the most proficient method which can be practivacl in the industry.
While SWCTT overcomes the limitation of well-to-well technique, other limitations are encountered such
as difficulty in finding partially reactant tracer and predicting reaction condition in different reservoir
conditions (temperature, salinity, and pH), depth of investigation, and drift during soak period. Some other
SWTTs are developed to remove some of these limitations, but as far as these techniques utilize hydrolysis
reaction, they could not overcome all the limitations of SWCTT. Since many limitations of SWTTs are
as a result of the hydrolysis reaction, the main objective of our innovative technique is to remove
hydrolysis reaction and cause an irreversible step by utilizing the dependency of partitioning coefficient
to salinity. Indeed, this innovative method can be ideal apparently, however; the problem is that it is very
difficult to know what the exact salinity radial profile is away from the well bore. This unknown region
is where the tracers are positioned. For this reason this novel method is not still practical and needs more
comprehensive investigations

Acknowledgments
The authors would like to acknowledge financial support for this research from the Research Council of
Norway, Statoil, and Institute for Energy Technology (IFE) AS (http://www.ife.no). We also would like
to acknowledge the resources and staff of the Department of Petroleum Engineering and Applied
Geophysics at the Norwegian University of Science and Technology.
IPTC-17990-MS 13

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