SPE-179545-MS

Residual Oil Zone: Paleo Oil Characterization and Fundamental Analysis

Ahmed Aleidan, Hyung Kwak, Hendrik Muller, and Xianmin Zhou, Saudi Aramco

Copyright 2016, Society of Petroleum Engineers

This paper was prepared for presentation at the SPE Improved Oil Recovery Conference held in Tulsa, Oklahoma, USA, 11–13 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
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Abstract
In most reservoirs around the world, paleo oil exists below the free water level and is considered residual
oil to natural/geological waterflood. This non-trivial resource of residual oil will not flow by primary or
secondary recovery means but requires carefully designed enhance oil recovery (EOR) methods to
mobilize it. To date, there is no detailed analysis of paleo oil in the literature simply because it is difficult
to obtain a reservoir sample.
This study provides a comprehensive paleo oil analysis for samples obtained from reservoir sponge
cores. The oil in the sponge core was extracted, analyzed, and compared to main pay zone oil (MPZ).
Critical data have been unveiled on paleo oil characterization through fundamental studies on oil quality,
fingerprint, filling history, available hydrocarbon components and compounds, and molecular level
characterization. It was found that the global composition and overall quality of paleo oil is very similar
to the MPZ oil. However, the differences between the two oils were only apparent when the study was
further extended to include molecular level analysis and available hydrocarbon components and com-
pounds. These differences may define the appropriate the EOR methods to mobilize this oil and explain
trapping mechanisms caused by fluid properties.
Gas chromatography studies revealed that paleo oil extracts have the same Pristane/Phytane ratio as the
MPZ oil suggesting that they are of the same origins and share the same source rock. Further analysis
showed a good match of the Terpane biomarkers between paleo oil extracts and MPZ oil but with slightly
less maturity levels. Paleo oil quality was compared to MPZ oil using Pyrolytic Oil Productivity Index
(POPI) analysis which indicated same API range as the MPZ oil and same light volatile, thermally
distilled and cracked components. Paleo and MPZ oils were also analyzed using nuclear magnetic
resonance (NMR) to qualitatively test the similarity of the oil components and measure their apparent
viscosities. Both oils have shown very comparable viscosity measurements and NMR signatures. The
simulated distillation analysis showed that lighter components in paleo oil are less abundant than MPZ oil
while medium to heavy components are relatively similar. Fourier Transform Ion Cyclotron Resonance
(FT-ICR) study, which zoomed into the heavier components, revealed that paleo oil has less aromaticity
than MPZ oil and lacks aromatic sulfur and di-sulfur compounds, negligible amount of nitrogen
compounds, and no resin type components.
This study provides in depth information about oil extracted from the residual oil zone, which doesn’t
flow by primary or secondary recovery means. Up to our knowledge, there is no available information in
2 SPE-179545-MS

the literature that explains the components, compounds, quality and behavior of this oil because it is hard
to obtain reservoir samples. This data shed light on possible trapping mechanism caused by fluids in place.
The study also employed several methods and tools to confirm the conclusions and ensure repeatability
of results.
Introduction
Considerable amounts of paleo oil are widely assumed to be located in the naturally waterflooded zone
or residual oil zone (ROZ), below free water level (FWL), for both sandstone and carbonate reservoirs
around the world. Unfortunately, the investigation of ROZs, paleo oil characterization and fundamental
analysis are limited. Research on oils from the transition zone (TZ) or ROZ focuses mostly on: remaining
oil reserves studies (Christiansen et al. 2000, Fanchi et al. 2000, Koperna et al. 2006; Melzer et al. 2006),
the distribution of fluid saturations and production characteristic as it varies with reservoir depth (Reed
et al. 1984; Parker et al. 2000; Masalmeh et al. 2000; Koperna et al. 2006;), wettability variation within
an oil/water transition zone (Jackson et al 2005), production modes (Skauge et al. 2000, EfniK et al. 2006,
Carnegie 2007, Aleidan et al. 2014), rock-fluid characterization for miscible CO2 injection (Honarpour et
al. 2010), transition zone characterization (Builting 2010, Christiansen et al. 1999).
Christiansen et al. 2000 and Fanchi et al. 2000 proposed an improved method to estimate oil reserves
in oil/water transition zone using a numerical simulator and found that there exists a relationship between
oil saturation and depth. The results show that the amount of recoverable oil in an oil-water transition zone
depends on the distribution of oil saturation, and an experimental corroboration of the trapped oil
relationship. Melzer et al. 2006 and Koperna et al. 2006 have reported significant paleo oil reserves in the
ROZ found in five carbonate formations in the Permian Basin. Three geological mechanisms were
proposed to create this large ROZ in west Texas fields: reservoir tilting that caused oil to leak from the
eastern end, water invasion from the Rio Grande rift, and/or seal breaches that caused oil to leak out of
structure.
Koperna et al. 2006 reported updates on four pilot projects to recover residual oil from TZ/ROZ, two
in the Wasson oil field, one in the Seminole San Andres Unit and a in the Salt Creek. Two CO2-EOR
practices were discussed and the performance of residual oil production for these practices was simulated
using CO2-PROPHET with a full-Scale Reservoir Simulator. They show that 12 billion barrels can be
recovered out of the 30.7 billion barrels of TZ/ROZ resources in these five Permian Basin oil plays based
on reservoir modeling of injecting CO2-EOR to the TZ/ROZ. Dry oil produced from Wedge Zone instead
of transition zone was investigated by Efnik et al. 2006. A large amount of dry oil has been producing
from four wells drilled in flank of the field, in which reposition these new wells according to the concept
of Wedge Zone. The water saturation profiles for four wells illustrate a gradual increase in water
saturation towards the free water level indicating that it is mainly due to the variety of the rock quality
related the diagenesis with the entrapment history of reservoir. Skauge et al. 2000 used a simulation model
built using geological description characteristic to predict oil recovery by liquid CO2 immiscible injection
into the transition paleo zone. The results showed that high oil recovery factors could be achieved. The
mechanisms of displacing oil by liquid CO2 immiscible injection were vaporization and swelling of oil.
Recently, Aleidan et al. 2014 have investigated experimentally the potential of CO2 to mobilize paleo oil
by monitoring the produced oil versus remaining oil of the original oil in carbonate core. Experimental
study includes core flooding tests by CO2 injection, HPHT PVT Cell visualization of paleo oil and NMR
analysis. The results of these experiments are compared to NMR analysis to confirm the amounts of oil
mobilized oil after the CO2 flood and qualitatively determine the type of oil mobilized.
A study on the characterization of the transition zone was conducted by Christiansen et al. 1999,
Jackson et al 2005, and Builting 2010. Christiansen et al. 1999 utilized the unconsolidated pack samples,
spherical glass beads (70-100 mesh, strongly water-wet), proppant sand (20-40 mesh, strongly water-wet)
and plastic beans (20-40 mesh, Strongly oil-wet) to study experimentally the variety of oil saturation with
SPE-179545-MS 3

height, and trapping oil relationship as a function of initial oil saturation in transition zone. The results
from two experiments were reported for unconsolidated pack samples, spherical glass beads with strongly
water-wet and proppant sand with strongly oil-wet and show experimentally that oil saturation is a
function of depth of transition zone, trapped oil relationship for both glass beads and proppant beads
samples. Jackson et al 2005 used 3D network model, a pore-scale network model in conjunction with
conventional reservoir-scale simulation to predict the variety of wettability within an oil/water transition
zone and its impact on production. This model involves the variety of wettability with varying degree of
advancing contact angles for water-wet and mixed-wet Berea sandstone. The result from numerical
simulation showed that the initial production can be the same regardless of wettability change if the initial
water saturation in TZ is dominated by the primary drainage process, in which oil is filed into the reservoir
first. However, the initial water saturation and initial production are different depending on the wettability
of sample if the initial water saturation in TZ has been modified by means of movement of the free water
level following reservoir filling and wettability alteration. They emphasized that the oil in TZ cannot be
moved below free water level if the TZ remained uniformly water-wet, and then the paleo oil saturation
will be approximately constant that equals to water flood residual oil saturation until close to paleo-OWC,
and if wettability of reservoir varies with depth in TZ, a significant interval of mobile oil may exist below
free water level from which dry oil is produced. Builting 2010 proposed an upscaling saturation-height
technology to improve the transition zone characterization for Arab carbonates. Based on the different and
very specific study of upscaling the capillary pressure data (a large amount of mercury-injection data)
limestone and statistical analysis for Arab-D limestone, a closed-form analytic expression was derived for
upscaling capillary pressure function. This expression shows a significant improvement of estimating
hydrocarbon-volume for the TZ.
This study provides a comprehensive investigation of paleo oil revealing critical data on oil quality,
fingerprint, filling history, available hydrocarbon components and compounds, and molecular level
characterization. It was found that the global composition and overall quality of paleo oil is very similar
to the MPZ oil. However, the differences between the two oils were only apparent when the study was
further extended to include molecular level analysis and available hydrocarbon components and com-
pounds. These differences may define the appropriate the EOR methods to mobilize this oil and explain
trapping mechanisms caused by fluid properties.
Experimental Work
Coreflood material, equipment and procedures
Core plugs: the core plugs used in this study were drilled from sponge cores taken from the residual
oil zone of a producing reservoir. The cores are used in their native state targeting the available paleo oil
as shown on the logs. The dimensions of core plugs are 3.8 cm (1.5 in) diameter and up to 7.5 cm (3 in)
length. Average porosity and permeability of core plugs were 14 % and 20 mD, respectively. The
composite core plug was wrapped by a layer of Teflon tape, one layer of aluminum foil and then was
capped with a layer of Teflon shrink tube. The aluminum foil functioned as a diffusion barrier between
the core plugs and the overburden sleeve. The diffusion of supercritical CO2 from core plug into
overburden is minimized. The NMR measurements were conducted before and after core flood experi-
ments to determine the distribution of paleo oil.
Fluids: Three types of fluids, surfactant solution, 0.1 wt%-S887 in seawater, toluene and supercritical
CO2 (sc-CO2) were used for the laboratory corefloods in this study. The sc-CO2 is 99.6 mol% pure and
injected above the supercritical conditions (experimental temperature and pressure were above its critical
point-88°F and 1074 psi). The density and viscosity of sc-CO2 at test conditions of 3200 psi and 102°C
are 0.5337 g/cc and 0.042 cP, respectively. The density and viscosity of surfactant solution are 1.009 g/cc
and 0.367 cP at test condition, respectively. The toluene has 0.867 g/cc for density and 0.583 cP for
viscosity at a temperature of 20°C and pressure of 14.75 psi.
4 SPE-179545-MS

Coreflood apparatus and experimental procedure: For this study, coreflooding apparatus, RPS-
855-Z, from Coretest Systems Inc. (USA) was used for all tests described by Aleidan et al. 2014. The core
plugs for all ROZ coreflood experiments were plugged from the reservoir sponge core and had the original
oil in core (OOIC), paleo oil. No foreign fluids introduced to the core except surfactant solution, toluene
and sc-CO2 to displace paleo oil in the core plug. The experimental procedure for these experiments is
as follows:
1. All core plugs are scanned by NMR to establish baseline conditions
2. Core plugs were wrapped by a layer of Teflon tape, one layer of aluminum foil and then were
capped with a layer of Teflon shrink tube.
3. The Core plugs with the paleo oil (ROZ) are placed into a Hassler-Type core holder at a confining
pressure of 1300 psi and connected flow lines to core holder.
4. The temperature of oven is set to 102°C and allowed to stabilize overnight to reach temperature
equilibrium.
5. Pore and confining pressures are increased in 500 psi steps using first injection fluid at a flow rate
of 1.0 cc/min until pore pressure of 3200 psi (test pressure) is achieved and a confining pressure
of 4500 psi is set up using Auto-confining system. The bypass valve of the core plug is opened
during pore and confining pressure set up process.
6. After establishing the pore pressure of 3200 psi and confining pressure of 4500 psi, the fluid
injection starts as follows: For first core plug, toluene injection is 0.5 cc/min at pore pressure of
3200 psi and 20°C about 200 cc toluene is injected, it is allowed to soak for 18 hours. After
soaking, toluene injection restarts again at same injection rate until colorless effluents appear at the
outlet. The effluents are collected by fraction collector with time. For 2nd core plug, surfactant
solution is first injected at 0.2 cc/min about 65 cc and allowed to soak for about 18 hrs. After
soaking, surfactant solution is reinjected at 0.2 cc/min for about 20 cc and 0.5cc/min for about 20
cc/min until colorless of effluents. After surfactant solution was injected, sc-CO2 injection was
followed at 0.2 cc/min until no oil is produced. During surfactant solution and sc-CO2 injection,
the effluents are collected for fundamental studies on oil quality, fingerprint, filling history,
available HC components and compounds, and molecular level characterization.
7. At the end of core flooding experiment, core plugs are depressurized by decreasing pore pressure
to 0 psi in steps. During decreasing pore pressure, the bypass valves are opened.
8. Any oil production during the blowdown process is collected.
9. NMR scans is done on all cores after the coreflood experiments.

Nuclear Magnetic Resonance (NMR)

Instrument and Experimental Parameters: The conventional 1D Carr-Purcell-Meiboom-Gill (CPMG)
NMR method with low magnetic field has been used for the current study. The NMR system used for the
current study is a 5MHz Oxford Geospec for 1D CPMG NMR. The T2 decay raw data is processed with
GIT software for 5MHz is based on BDR inversion scheme. The important experimental parameters for
CPMG sequence with 5MHz, kept identical throughout the current study, are:
[CPMG]
Recycling Delay (RD): 15 sec
Echo Delay (Tau): 110␮sec
Total Number of Echo Train (NECH): 45456
Number of Scan (NS): 16
SPE-179545-MS 5

Mass spectrometry
Mass spectrometry: High resolution, high accuracy mass spectra of the crude oils were acquired on an
Apex Qe FT-ICR MS (Bruker Daltonics, Bremen, Germany) with atmospheric pressure photo ionization
(APPI). Data were acquired on ApexControl software (v3.0, Bruker Daltonics, Bremen, Germany).
Sample preparation: Samples were homogenized for 20s on the Vortexer at 2000 rpm, and then
approximately 50 mg of a sample were dissolved in 5 mL toluene (Fischer Scientific Certified ACS
grade). This stock solution was further diluted in toluene to a final dilution of 1:5,000 (wt/v).
FT-ICR MS: The diluted samples were delivered by a syringe pump at a flow rate of 20 ␮L/min. Gas
flow rates (nebulizer and dry gas) were set at 3 L/min. APPI furnace temperature was set at 400°C and
the drying temperature was set to 200 °C. Ion source potentials were set as follows: Capillary: 1.5 kV,
spray shield: 1.0 kV, capillary exit: 270 V. Ions were collected for 0.3 s in the source hexapole (h1) sent
to the icr cell with an ion transfer time of 1.6 ms. 128 transients were averaged before fast Fourier
transformation. Mass spectral slices were obtained using a quadrupole mass filter (Q1) for transmitting
only ions from m/z 550 to m/z 650.
Mass calibration: External mass calibration was achieved using sodium formate solution (5 mMolar
in water/methanol 1:1) in positive mode ESI. Internal calibration for each sample measurement was based
on the homolog series of benzothiophenes and alkylated benzenes present in the samples.
Data Processing: FT-ICR MS raw data files were processed using Data Analysis (v4.0, Bruker
Daltonics, Bremen) for peak picking with signal to noise ratio (S/N) of 6. The mass calibration of selected
signals was confirmed manually to be accurate within 1 ppm across the mass range.
Elemental Composition Assignment: The mass lists were processed using Composer software
(v1.0.6, SierraAnalytics, Modesto, CA, USA) for fine calibration of the mass scale and assignment of
elemental compositions based on the accurate mass of the molecular ions. Elemental composition
assignments were confirmed using the 34sulfur isotopic fine structure for sulfur series signals. Addition-
ally, assignments were carefully checked using different processing parameters and found stable within
reason. The elemental compositions were then classified according to the number and type of heteroatoms,
e.g. hydrocarbons (HC), mono-sulfur (S1), di-sulfur (S2), tri-sulfur (S3) or nitrogen-sulfur (N1S1) species
for molecules with no hetero atom, one, two, or three sulfur atoms, or one nitrogen- and one sulfur atom,
respectively.

Results and Discussion

Pyrolic Oil-Productivity Index (POPI)

Paleo oil quality as inferred by the API and density was measured using pyrolic analysis using POPI,
Jones and Tobey, 1999. The grinded rock samples containing paleo oil are used to characterize the quality
and condition of paleo oil and compared to the known quality of MPZ oil. Fig. 1 shows the output of POPI
analysis of paleo oil indicating same quality as the MPZ as evident by the calculated API, abundant light
volatile components and lack of thermally distilled and cracked components. This means that the samples
contain enough light component to show on the detector response at lower temperatures and it doesn’t
require higher temperatures to distil or crack the components.
6 SPE-179545-MS

Figure 1—results for paleo oil crushed samples POPI analysis.

Gas Chromatography (GC) and Bio-markers

GC coupled with flame ionization detector (GC-FID) and a temperature program up to 375°C were used
to determine paleo oil samples source rock and filling history. The Pristane/phytane ratio was used as the
main indicator and compared to known MPZ oil samples. A Pristane/phytane ratio of 0.58 compared to
0.63 for MPZ oil indicate that both samples came from the same source rock, a Jurassic oil from a
carbonate source. Fig. 2 shows the comparison of the GC-FID signature of both samples, paleo oil at the
top and MPZ at the bottom.

Figure 2—GC-FID signature for paleo oil (top) compared to MPZ oil (bottom).

Though the signatures look different but the ratio is in the same range confirming the same source rock.
To further confirm the source rock and similarity between the two oils, bio-marker analysis tests were run.
Fig. 3 compares the terpane distribution pattern (m/z 191) of paleo oil and MPZ oil. The results indicate
minor variations between these two samples. The pattern of tricyclic and tetracyclic compounds is
particularly similar and frequently used to assess the source rock organic facies and depositional
SPE-179545-MS 7

environment. These results confirm the similarity of paleo oil to MPZ oil from the same field. It also
agrees well to the carbonate source as already shown by the GC analysis. Minor variations may result from
the treatments during the extraction process. One striking difference is that paleo oil is less mature
compared to MPZ oil. This maturity sequence is also confirmed by other maturity sensitive parameters in
the aromatic hydrocarbon fraction.

Figure 3—Bio-markers signature for paleo oil (top) compared to MPZ oil (bottom).

Simulated distillation
The two samples, paleo oil and MPZ, were analyzed using simulated distillation to see the availability of
light components. Fig. 4 shows a comparison of the results for the two samples. It clearly shows that paleo
oil samples (right) lacks the components from C5 to C11 and heavier components from C24 and beyond.
However, the components between C12 and C23 are abundant. These results have serious implications on
the type of EOR method to mobilize paleo oil and how it reacts with the injectant. Our previous study,
aleidan et. al. 2014, showed that when CO2 is injected to mobilize paleo oil, it required a soaking period
to realize any production. The lack of components from C5 to C11, which are mostly desired to react with
CO2, explains the need for the soaking period for the CO2 to react with relatively heavier components.

Figure 4 —simulated distillation for paleo oil (right) compared to MPZ oil (left).
8 SPE-179545-MS

NMR
The NMR T2 distributions of paleo oil produced by CO2 injection from two different reservoirs have been
acquired and compared to MPZ oil from the same reservoir Fig. 5. The paleo and MPZ oil from each
reservoir show a similarity in T2 distributions. In other words, from both reservoirs, the distribution and
the relative proportion of hydrocarbon components from paleo oil and MPZ oil are quite similar. Some
differences between them, however, are also observed. The paleo oil from reservoir (a) on Fig. 5 is
missing hydrocarbon components with intermediate viscosity which corresponds to the missing C5 to C11
components from the simulated distillation study above. On the other hands, the paleo oil from researvoir
(b) on Fig. 5 shows the missing light hydrocarbon components and retention of relatively large portion of
heavy hydrocarbon components compare to MPZ oil.

Figure 5—NMR T2 distributiond of bulk Paleo oil (red) and MPZ dead oil (blue) from two different researvoirs. The NMR porosities are
normalized to 1 for all data to enhance the comparison between Paleo and MPZ oil.

The differences observed from the T2 distributions have become clearer from the comparison of NMR
driven viscosity, which is calculated from T2 logarithmic mean value by Eq. 1 (Table 1).
Eq. 1

Where Tk is temperature in °K and T2LM is the T2 logarithmic mean value in sec, Vinegar 1995.
The viscosity of paleo oil from reservoir (a) is lower than that of MPZ oil due to missing hydrocarbon
components with intermediate viscosity in the range of T2 between 20 msec and 1sec. In the case of
paleo oil from reservoir (b), the viscosity is more than three times of that of MPZ oil due to the lack
of lighter hydrocarbon component and relatively large proportion of heavy hydrocarbon component.

Table 1—NMR T2 distributiond of bulk Paleo oil (red) and MPZ

dead oil (blue) from two different researvoirs. The
NMR porosities are normalized to 1 for all data to enhance the
comparison between Paleo and MPZ oil.
Sample T2LM (msec) NMR Driven Visocisty (cP)

MPZ (a) 172 7.23

Paleo (a) 330 3.78
MPZ (b) 295 4.22
Paleo (b) 80 14.88
SPE-179545-MS 9

Mass spectrometry
High resolution mass spectrometry in combination with a soft (i.e., non-fragmenting) ionization measures
molecular ions with sufficient mass spectral resolution and accuracy to separate the signals and identify
the corresponding elemental compositions, namely the number of carbon-, hydrogen, and hetero atoms
present in the ion species. This is illustrated in Fig. 6, showing the full spectrum and a zoomed mass
spectral detail where the mass signals have been labeled with the identifications. Although an elemental
compositions can represent many isomers, information regarding the number of rings and double bonds
in the corresponding molecule (double bond equivalent, DBE) can be obtained. For petroleum samples,
the DBE can be used to estimate the ‘aromaticity’ of its components, i.e., how many aromatic rings each
molecule may contain.

Figure 6 —Mass spectrum (top) and mass spectral detail (bottom) of the paleo oil sample showing individual sulfur, disulfur and pure
hydrocarbon species.

The full-range mass spectra of the samples were very similar (not shown) in terms of detected
heteroatom classes, carbon numbers, and DBE distributions, because the less abundant ion species
were suppressed due to a high compositional complexity. To extend the dynamic range of the method
and overcome the sample complexity, mass spectral slices between m/z 550 and m/z 650 were
isolated, which reduced the overall number of ions in the ICR trap (reducing ion suppression) and
allowed observing less abundant species. The summed mass spectral abundances of the detected
hetero atom classes are shown in Fig. 7. It must be emphasized here that the method is not
quantitative and that only aromatic species, i.e., molecules with at least one aromatic ring are
detected. Hydrocarbon (HC), mono and di sulfur (S1 and S2) species were identified in the paleo oil
(grey bars) and in the produced oil (black bars). However, the produced oil additionally contained tri
10 SPE-179545-MS

sulfur (S3), nitrogen (N1), and nitrogen-sulfur (N1S1) species that were not detected in the paleo
oil.

Figure 7—Relative summed abundance of the identified component classes in the paleo oil (light bars) and produced oil (dark bars).
Only major component classes (above 1% summed relative abundance) between m/z 550 to m/z 650 are accounted.

The common classes were further characterized by their aromaticity distributions as shown in Fig.
8. Fig. 8 top shows that the mono aromatic species (alkyl benzenes) are most abundant in the paleo
oil, whereas tri- and tetra aromatic HCs (molecules with 3 or 4 aromatic rings and large alkyl groups)
are most abundant in the produced oil. A similar trend is found for the sulfur compounds (Fig. 8
middle), where di aromatic sulfur species, namely alkyl-benzothiophenes, are most abundant in the
paleo oil sample, whereas 3 ringed aromatic sulfur species, namely alkyl-dibenzothiophenes, dom-
inate the produced oil sample. S2 species are found more abundant in the produced oil sample, albeit
with similar distribution of aromatic rings than the paleo oil, with a maximum around 5 aromatic
rings per molecule (Fig. 8 bottom). S3 species are exclusively detected in the produced oil sample
with 5 or more aromatic rings.
SPE-179545-MS 11

Figure 8 —Double bond equivalent (DBE) distribution plots of aromatic hydrocarbon (HC) species (top), mono-sulfur (S1) species
(middle), and di-and tri-sulfur (S2 and S3) species (bottom). DBE represents the number of rings and double bonds in each molecule
and is an indicator of how ‘aromatic’ the molecule is; the tentative number of aromatic rings per molecule is indicated in each plot.

Overall, the produced oil sample contains a significantly higher portion of molecules with more
aromatic rings, and more hetero atom containing molecules, which are both associated with asphaltenic
material. It might be concluded that asphaltenes have been excluded from the investigated paleo oil
sample, possibly due to the lower solubility / stability of kerogen based asphaltenes in the associated
petroleum fluids, as opposed to a better solubility of the produced asphaltenes which are possibly better
stabilized in solution.

Conclusion
The initial analysis of paleo oil (oil from the residual oil zone) showed no significant differences compared
to the main pay zone (MPZ) oil. However, when a more fundamental approach was taken to look at the
details of the oil, differences were more apparent. These differences revealed some of the reasons why this
oil won’t flow which is very helpful to select the right EOR method for recovery. The main conclusions
on paleo oil properties and characterizations are summarized below:
12 SPE-179545-MS

– Paleo oil extracts have the same Pristane/Phytane ratio as the MPZ oil suggesting that they are of
the same origins and share the same source rock. Further analysis showed a good match of the
Terpane biomarkers between paleo oil extracts and MPZ oil but with slightly less maturity levels.
– Paleo oil have the same API range as the MPZ oil and same light volatile, thermally distilled and
cracked components. It also showed similar apparent viscosities.
– The simulated distillation analysis showed that lighter components in paleo oil are less abundant
than MPZ oil while medium to heavy components are relatively similar.
– Fourier Transform Ion Cyclotron Resonance (FT-ICR) study, which zoomed into the heavier
components, revealed that paleo oil has less aromaticity than MPZ oil and lacks aromatic sulfur and
di-sulfur compounds, negligible amount of nitrogen compounds, and no resin type components.
– The differences were only visible when special tests were employed.
– The results explain possible trapping mechanism caused by fluids in place.
– The study employed several methods and tools to confirm the conclusions and ensure repeatability
of results.

Nomenclature
EOR Enhanced Oil Recovery
FWL Free Water Level
GOR Gas-Oil-Ratio
HPHT High-Pressure/High-Temperature
IOR Improved Oil Recovery
MPZ Main Pay Zone
NMR Nuclear Magnetic Resonance
OWC Oil Water Contact
PFWL Paleo Free Water Level
PPM Parts Per Million
PV Pore Volume
PVT Pressure, Volume, and Temperature
ROZ Residual Oil Zone
SE-SPI Spin Echo Single Point Imaging
Sor Residual Oil Saturation
Swc Connate Water Saturation
T2-D T2-Diffusion
TDS Total Dissolved Solids
TZ Transition Zone

Acknowledgement
The authors would like to thank Saudi Aramco and EXPEC Advanced Research Center (ARC) for the
permission to publish this paper. Special thanks to Andreas Fuhrmann and Syed Bukhari for their help in
this research.

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