SPE-182811-MS

Single-Well Chemical Tracer Test for Residual Oil Measurement: Field Trial
and Case Study
Mohammed AlAbbad, Senthilmurugan Balasubramanian, Modiu Sanni, Sunil Kokal, Ibrahim Zefzafy,
Frederick Adam, and Adnan AlHajji, Saudi Aramco

Copyright 2016, Society of Petroleum Engineers

This paper was prepared for presentation at the SPE Kingdom of Saudi Arabia Annual Technical Symposium and Exhibition held in Dammam, Saudi Arabia, 25–28
April 2016.

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
Tracers are increasingly being deployed as an effective reservoir monitoring and surveillance (M&S) tool
in the oil and gas industry. In particular, the single-well chemical tracer test (SWCTT) is being widely
used to estimate remaining oil saturation (ROS) or residual oil saturation (Sor), especially in improved oil
recovery (IOR) and enhanced oil recovery (EOR) operations. The test provides a direct measure of ROS
in a wider reservoir volume compared to the measurements made by near wellbore logs or cores.
A SWCTT was designed and implemented in a carbonate field to determine fluid saturations. The
reservoir is heterogeneous with layers of high to low permeability limestone, porosity in the range of
20 –30%, and interspersed with patchy layers of dolomites and a very competent anhydrite seal. The
SWCTT was conducted in a very mature part of the field near the peripheral water injectors, to determine
the residual oil saturation before a planned IOR pilot test.
This paper presents the complete design and implementation of the test, operational challenges, and the
analyses and interpretation of the results. The depth of investigation was 13–14 feet from the wellbore.
Laboratory results of determining the partitioning coefficient of the chemical tracer are described and
presented. The design of the tracer test taking into consideration the reservoir properties are shared.
Considerable operational challenges in the field and appropriate solutions to overcome them provide a
very interesting case study. The returns and analyses of the samples provided a unique set of data that were
interpreted using a simple analytical tracer model which was comparable to the reservoir simulations
predictions. The Sor was obtained after fitting the tracer return data to a model of the classical
convection-dispersion equation. The results indicate that there was no displacement or drift that occurred
during the shut-in period. The mass balance of the tracers suggests that more than 98% of the tracers were
recovered with negligible tracer adsorption during the test duration. The results are in close agreement
with a similar test benchmarked independently by a commercial vendor using a different injection design
scheme.
2 SPE-182811-MS

Introduction
The single-well chemical tracer test (SWCTT) has been a reliable remaining/residual oil saturation
measurement technique over the past three decades (Deans, 1971 and Deans et al., 1980). Its concept is
based on the difference in the arrival times to the wellhead between two tracers originating from the same
point in the wellbore (chromatographic shift). Basically, a partitioning tracer is injected in the reservoir
where part of it partitions in the remaining oil phase and the other part undergoes a hydrolysis reaction
to produce a nonpartitioning tracer. This hydrolysis process takes place over a period of few days while
the well is shut-in. The well is then produced and wellhead samples are analyzed for tracer returns. The
analysis of the flowed-back samples are generally plotted as in Figure-1, where concentration vs. produced
volume is generated. From the difference in arrival times (maximum of the peaks) and the partitioning
coefficient value, one can obtain the remaining or residual oil saturation (ROS or Sor). The partitioning
coefficient is a physical property that relates tracer concentrations in oil and water phases at equilibrium
as shown in Equation-1.

Figure 1—Typical Tracer production profile curves used for interpretation from a SWCTT

The partitioning coefficient definition is:

(Equation 1)

where Co and Cw are tracer concentrations in oil and water phase respectively.
From chromatographic theory, the retardation factor (1⫹␤) which is equivalent to the peaks ratio
(see Figure 1) is defined as follows:
(Equation 2)
SPE-182811-MS 3

Rearranging Equation-2 gives,

(Equation 3)

The lab experiments are classified into two main parts: one is to examine the equilibrium criteria for
the tracers in both phases using the partitioning coefficient and use it in the analysis of the flowed back
samples, and the other is for the detection of tracers.
The partitioning coefficient (Kd) is the concentrations ratio of a component between two phases at
equilibrium. In our practice the component is a tracer (e.g., ethyl acetate) and the two phases are oil and
water. The Kd value will vary slightly depending on temperature and typically follows Equation 4:
(Equation 4)

Background
The main objective of the test was to measure the remaining oil saturation in a slightly matured part of
a carbonate reservoir before a planned IOR pilot test. One of the key requisites to assess the efficacy of
any IOR pilot test is a good understanding of the residual oil saturation (Sor) and its distribution in the
reservoir before and after the IOR pilot test.
Generally the fields in this area are developed via peripheral water injection, providing necessary
pressure support and voidage replacement to maximize hydrocarbon recovery. The test was conducted in
a down flank area of the field proximal to the peripheral injectors. The candidate reservoir is heteroge-
neous with layers of high to low permeability limestone, porosity in the range of 20 –30%, and
interspersed with patchy dolomitic layers and a very competent anhydrite seal.

Pre-Job Planning
Prior to the field operation, several pre-job activities were carried out and a host of tests were conducted
to ensure a successful field trial. These include the following:

Candidate Selection
The selected well is a vertical producer with about 38 feet of perforation across the topmost most
productive layers. The reservoir description indicates that the interval in question is probably a single flow
unit, or at most two flow units. The cement bond data showed that there is a good cement bond across the
interval to prevent cross-flow behind the casing during injection and flow-back periods. The reservoir
pressure is considered high enough to allow natural flow-back without any need for assisted flow.
Furthermore, the candidate well has had a previous SWCTT job which served as a benchmark for this
study.

Chemical Screening
Several chemicals were screened for the job. Ethyl acetate (EtAc) was selected as the main reacting tracer
for this test. Iso-propanol (IPA) and methanol (MeOH) were selected as the material balance and the cover
tracers, respectively. In addition, the quality of the chemicals were checked before being used via in-house
QA/QC protocols with NMR and GC-MS analyses (Figure-2).
4 SPE-182811-MS

Figure 2—QC of samples via GC-MS and NMR analyses.

Partitioning Coefficient Determination

A few partition coefficient (K) measurements for EtAc was conducted at different temperatures and
different water salinities. Here, actual oil and sea water samples were used to mimic reservoir conditions.
The EtAc was introduced first to the oil phase and in the second run into the water phase. A (K) value
of 4.6 ⫾ 0.1 was obtained. This is similar to the K values (4.5 - 4.7) obtained earlier from two other
independent measurements. Table-1 below is a summary of K determination at 60°C when the tracer is
introduced to the water phase.

Table 1—Partitioning coefficient of Ethyl Acetate at 60 °C, tracer added to the water phase.

Analytical Method Development for Tracer Analyses

The determination of ethyl acetate, methanol, isopropanol and ethanol was conducted using a gas
chromatograph (GC) equipped with a flame ionization detector (FID). The GC oven was fitted with a
SPE-182811-MS 5

polar chromatographic column (DB-Wax, 25 m ⫻ 0.25 mm ⫻ 0.25 ␮m) and was ramped from 50 ºC to
58 ºC at 1.5 ºC / min and from 58 ºC to 230 ºC at 50 ºC / min, with a final plateau of 10 minutes for column
flushing. The identification of the compounds was achieved in produced water, based on their retention
times. The retention times have been determined during the method development while injecting pure
compounds. A typical chromatogram obtained for a standard sample containing ethyl acetate, methanol,
isopropanol and ethanol is shown in Figure-3. The four tracers are well separated from each other. In
addition, no matrix interference with the tracers could be evidenced from the analysis of a blank sample
(sea water), suggesting that the four tracers can be quantified using this method. The composition of the
sample including the impurities was further confirmed with a GC hyphenated to a mass spectrometer
(MS), operated in scanning mode using the above separation conditions.

Figure 3—Typical chromatogram obtained for a standard sample.

The quantification of the four target compounds was achieved with an external calibration. The method
was developed to determine the concentration of the compounds in the 15 ppm – 6000 ppm wt. range. To
account for potential matrix effects, the standards were prepared with sea water. The calibration curves
are presented in Figures 4–7. The method showed excellent linearity in the working range with a
correlation factor(r2) greater than 0.999 for all tracers (Figures 4 – 7).

Figure 4 —Ethyl acetate calibration (EtAc)

6 SPE-182811-MS

Figure 5—Methanol calibration (MeOH)

Figure 6 —Isopropanol calibration (IPA)

Figure 7—Ethanol calibration (EtOH)

The performances of the method were evaluated based on repeatability and accuracy. The method
repeatability was measured using the relative standard deviation. The relative standard deviation was
calculated by analyzing a sample containing respectively 531, 506, 497 and 515 ppm wt. of ethyl acetate,
methanol, isopropanol, and ethanol, repeated ten times. The relative standard deviation was found to be
lower than 1.8, indicating an excellent method repeatability.
The accuracy of the method was evaluated by analyzing three quality control samples, having
concentrations scattered across the concentration range. The comparison between the measured and
theoretical concentrations, along with the corresponding relative error, are presented in Table-2 below.
SPE-182811-MS 7

Table 2—Quality control samples analysis.

The relative error between the measured concentration and the theoretical concentration for the four
tracers within each QC sample was found to be below 7.6 %, indicating an excellent method accuracy.
The composition of the four tracers in the collected samples during the field testing were determined
using the same GC-FID method.

Water Analyses
The injection water and produced water samples were also analyzed to determine their properties and how
these may affect the job design and interpretation of results. The compositions, trace elements, and tickler
diagram for sea water and produced water, are shown in Tables 3 and 4 respectively.

Table 3—Geochemical Water Analysis, Trace Element & Tickler Diagram for sea water injection
8 SPE-182811-MS

Table 4 —Geochemical Water Analysis, Trace Element & Tickler Diagram for Test well (U-07)

Job Design and Field Operations

The successful implementation of the field test could be attributed to; a) effective team work, (b)
interdepartmental collaboration, and (c) adherence to high safety standards. Given the volatility of the
chemicals involved and the delicate nature of the trial test, all necessary precautions were taken to ensure
an incident free operation.
A temporary secured water transfer line was installed to provide injection water from a nearby injector
well (I-7) to the site. This eliminated the need to have water tankers shuttling between the filling station
and test producer well P-7 (Figure-8) resulting in major cost savings.

Figure 8 —Temporary water transfer line setup.

A schematic of the major surface facilities (temporary transfer line, pumping equipment, storage
facility, test separator, dual stage filtration unit, lab cabinets, generator, etc.) layout deployed for the test
is illustrated in Figure-9.
SPE-182811-MS 9

Figure 9 —Schematic of the surface facilities layout.

The test was started by shutting in the candidate well and the surrounding injectors three days before
the commencement of the test to allow for stabilization and minimize drift. The test started by pumping
10,000 barrels of water at a rate of 1.65 BPM, followed by the tracer bank as shown in the Table-5.

Table 5—The injection design used for Well P-7 SWCTT.

The short flow back of about 150 bbl. was to ascertain that the well was still alive to flow back naturally
and also to remove any debris and particles that might have been inadvertently introduced by the injection
operation. After completing the injection of the 10,000 bbls and hence establishing the Sor status, the
tracers were injected and the well was shut-in for three days to allow hydrolysis of ethyl acetate to produce
ethanol. After finishing 72 hours of shut-in period, the well was put back on production at a rate of 1000
BPD, with 15 minute sampling frequency to analyze the return fluid.

Results and Interpretation

The test was aimed to obtain the residual oil saturation (Sor) by investigating an area of 13–14 ft away
from the wellbore with a partitioning tracer filling a donut-like shape of about 4 ft thickness (Figure-10).
10 SPE-182811-MS

Figure 10 —Area of investigation for the designed SWCTT.

The tracers hydrolysis soaking time was set to circa 72 hours based on the reaction rate at the reservoir
temperature. This soaking period yields approximately 8% conversion of EtAc to EtOH, which was
enough for the test objectives and also fits the available analytical capacity limits. The resemblance of the
(EtAc) curve and the cover tracer curve (MeOH), and the data from the mass balance tracer (Iso-
propanol), indicated a radial and uniform displacement flow without downhole drift, while conducting the
test. Table-6 summarizes the recovery of all tracers used.

Table 6 —Tracers main function and recovery from P-7 SWCTT

Tracer Tracer Symbol Tracer function Recovery, %

Iso-propanol IPA Mass balance 98.31

Methanol MeOH Cover/backup 89.11
Ethanol EtOH Produced tracer --
Ethyl Acetate EtAc Partitioning tracer 92.97

The test results can best be presented using the tracers return curves. The following plots highlight main
test target. In Figure-11, production data for the reactive tracer (EtAc) and product tracer (EtOH) are
shown; the retention or difference between the two peaks is then used to determine Sor.

Figure 11—EtOH (Product) and EtAc (Reactive) Tracers from P-7, SWCT Test Field-Measured Data.
SPE-182811-MS 11

From Figure-12, the material balance tracer (IPA) was used in all tracer injection stages (main and push
stage) to determine if any losses occurred during the test. Material balance for this test was 98.31%.

Figure 12—IPA (Material Balance) Tracer, P-7, SWCT Test Field-Measured Data.

Production data for the cover tracer (MeOH) are shown in Figure-13. The cover tracer is a backup to
the EtAc and to confirm the shape and peak position when there is a drift or excessive hydrolysis.
Figure-14 shows that the MeOH can serve as an accurate substitute for the EtAc. The EtAc data were well
resolved, so the EtAc data were used for the Sor measurement.

Figure 13—MeOH (Cover) Tracer, P-7, SWCT Test Field-Measured Data.

12 SPE-182811-MS

Figure 14 —EtAc (Reactive) and MeOH (Cover) Tracers, P-7, SWCT Test Field-Measured Data.

Figures 15, 16 and 17 reproduce the same plots with one homogenous layer model assumption ⬙curve
fitted.⬙ The equations used to match the field data were derived from the general convection/dispersion
equation (Deans et al, 1986 and Huseby et al 2012).

Figure 15—EtOH (Product) and EtAc (Reactive) Tracers, P-7, SWCT Test Best-Fit Single Layer Homogenous Model.
SPE-182811-MS 13

Figure 16 —IPA (Material Balance) Tracer, P-7, SWCT Test Best-Fit Single Layer Homogenous Model.

Figure 17—MeOH (Cover) Tracer, P-7, SWCT Test Best-Fit Single Layer Homogenous Model.

The single well chemical tracer test was interpreted using an analytical approach (Jerauld et al, 2010),
where analytical solutions to the convection/dispersion equations were fitted to the measured data from
the P-7 SWCTT data. The single layer assumption yielded a satisfactory estimate for the peaks in the
tracer curves. The obtained results showed that the residual oil saturation is Sor⫽0.217 ⫾ 0.005. This
estimate comes by employing the EtOH and EtAc curves. The residual saturation value was also verified
14 SPE-182811-MS

using (MeOH) curve as a quality check. The oil saturation of Sor⫽0.211 ⫾ 0.005 was obtained using the
(MEOH) curve. Table-7 summarizes MeOH and EtAc Sor values.

Table 7—Saturation estimated using MeOH and EtAc and a K-value of 4.5.
Curve used Sor value

Reactive tracer Ethyl Acetate (EtAc) So⫽0.217 ⫾ 0.005

Cover tracer Methanol (MeOH) So⫽0.211 ⫾ 0.005

Figure-18 below shows the overall tracer response curves combined in a single plot. It is worth
highlighting the lack of drift or displacement during the shut-in period.

Figure 18 —SWCTT overall tracer response curves from well P-7

Lessons Learned
The first in-house trial test of the SWCTT was successful. Nevertheless, A few key lessons were learned
before and during the field operations.
● When using ⬙frac. tanks⬙ for tracer mixing and subsequent injection, it is highly recommended to
have a dedicated mixing (⬙frac⬙) tank for each tracer to prevent contamination.
● Each ⬙frac tank⬙ should be equipped with two independent transfer pumps for circulation and
isolated regardless of any other operation going on (e.g., pumping, circulating).
● The piping design for the frac tanks should take into consideration flushing of dead volumes to
avoid contamination.
● Inspection of the piping network and equipment for tracer mixing, and injection should be done
during the water pre-flush water injection stage, and before the commencement of tracer mixing/
injection.
SPE-182811-MS 15

● Need to have enough spares (N⫹1) for each type of pump (diaphragm, transfer, chemical) for
quick recovery in case of any trip during SWCT mixing and pumping operations.
● On-the-fly chemical injection has the potential to reduce the number of ⬙frac tanks⬙ needed for
SWCTT operations, thereby reducing foot-print and cost.
Conclusions
The following are the key conclusions from the pilot test:
● The result of the field trial is very encouraging; the Sor measured by the test was 21.7%⫾0.5%.
It is very similar to the test conducted earlier by a commercial vendor with a value of 22%.
● The Sor measurement was obtained after fitting the tracer return data to a model of the classical
convection-dispersion equation. The results indicate that there was no displacement or drift during
the shut-in period. The mass balance of the tracers indicated that more than 98% of the tracers were
recovered with negligible tracer adsorption, and without any drift during the test reaction period.
● Quality control, effective communication and field coordination are the key recipes for any
successful field trial test.
● The job design, protocols deployed, and the field execution went quite well without any safety
incident. Special safety measures adopted proved adequate given the high flammability of some
of the chemicals deployed, and the hot weather condition during the period of the test.
● The test show-cased a great inter-departmental collaboration and teamwork.

References
1. Deans, H.A.: ⬙Method of Determining Fluid Saturations in Reservoirs,⬙ U.S. Patent 3623842 (1971).
2. Deans, H.A. and Majoros, S. ⬙The Single-Well Chemical Tracer Method for Measuring Residual Oil Saturation.⬙
DOE/BC-20006-18 U.S. DOE. October 1980.
3. Deans, H. A., and Carlisle, C. T., ⬙Single Well Trace Test in Complex Pore Systems,⬙ SPE Paper 14886, SPE/DOE
Fifth Symposium on Enhanced Oil Recovery. April 1986.
4. Huseby, O., Sagen J. and Dugstad Ø., ⬙Single Well Chemical Tracer Tests - Fast and Correct Simulations,⬙
SPE-155608-MS, SPE EOR Conference at Oil and Gas West Asia. 16 –18 April 2012, Muscat.
5. Jerauld, G., Mohammadi, H. and Webb, K. ⬙Interpreting Single Well Chemical Tracer Tests,⬙ SPE paper 129724. SPE
Improved Oil Recovery Symposium, 24 –28 April, Tulsa, Oklahoma, USA, 2010