SCA2006-57 1/6

IMPACT OF A NOVEL SCALE INHIBITOR SYSTEM ON

THE WETTABILITY OF PALEOZOIC UNAYZAH
SANDSTONE RESERVOIR, SAUDI ARABIA

T.M. Okasha, H.A. Nasr-El-Din, H.A. Saiari, A.A. Al-Shiwaish, and F.S. Al-Zubaidi
Saudi Aramco Research and Development Center, Dhahran, Saudi Arabia

This paper was prepared for presentation at the International Symposium of the
Society of Core Analysts held in Trondheim, Norway 12-16 September, 2006

ABSTRACT
Central Arabia oil field was developed and oil production started in August 1994. The main
producing reservoir is Paleozoic Unayzah sandstone reservoir. Water injection started in
early 1995, using peripheral water injection pattern to maintain reservoir pressure. A
decline in oil production was noted in some wells and attributed to the formation of
calcium carbonate scale. The scale was covering gravel pack screens, pump intake and the
impellers of submersible pumps.

A novel scale inhibitor treatment was developed to mitigate the scale in this field. An
emulsified-type scale inhibitor (phosphonate-type) treatment was developed and
successfully applied in more than 35 wells.

The objective of this work is to assess the impact of the emulsified scale inhibitor on the
wettability of the sandstone reservoir. Extensive laboratory studies were conducted to
evaluate wettability behavior before and after scale treatment. The effect of the scale
inhibitor on oil/brine interfacial tension (IFT) was also investigated. Preserved core plugs
from Unayzah reservoir were used in Amott wettability tests. Natural rock plates and pure
quartz crystals were used as solid substrates in contact angle measurements to evaluate
wettability at reservoir conditions (T =90
o
C and P =2,500 psi).

Amott results revealed no significant changes in wettability indices/state before and after
the addition of the scale inhibitor. Amott-Harvey wettability index ranged from 0.19 to 0.5
for samples tested without inhibitor and from 0.12 to 0.49 for those tested with the scale
inhibitor. These indices reflect slightly to water-wet characteristics of tested core plugs.
Contact angle data showed that rock plate and quartz crystal surfaces become more water-
wet (positive alteration) by addition of the scale inhibitor. Results of IFT for both oil-brine
and oil-scale inhibitor systems indicated that addition of scale inhibitor leads to 20%
decrease in IFT values at reservoir conditions. Positive wettability alterations and reduction
in IFT highlighted an unexpected benefit of using scale inhibitors (phosphonate-type) to
mitigate scale in sandstone reservoirs. This paper will discuss various techniques used to
measure wettability and relate lab data with field results.

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INTRODUCTION AND BACKGROUND
Wettability of hydrocarbon reservoirs has a profound effect on oil production in oil fields,
which are being produced by waterflood and water-drive mechanisms. Therefore, it is
necessary to determine the preferential wettability of the reservoir, whether this be to water,
or oil or somewhere between two extremes i.e. intermediate. The importance of wettability
has been realized by a number of researches when water-driven systems were evaluated
(Amott, 1959; and Donaldson et al., 1969). Due to this importance, many reviews of
wettability and its effect on oil recovery have been published (Cuiec, 1991, and Buckley,
1998).

In Saudi Arabia, oil production from Unayzah sandstone reservoir started in August 1994
and shortly thereafter in 1995 a peripheral water injection was started to maintain reservoir
pressure (2,500 psi). Many of the oil wells started producing wet crude shortly after oil
production started. In 1998, decline in oil production of some wet wells was noted. This
decline was attributed to scale formation, which was found covering the producing gravel
pack screens, pump intake, and on the impellers of the electrical submersible pumps. R&D
scientists introduced the most effective scale inhibitor (diethylene triamine pentamethylene
phosphonic acid or DTPMP) to prevent scale formation and more than 35 wells were
successfully treated (Nasr-El-Din et al., 2003).

This study was conducted to assess the impact of the emulsified scale inhibitor on the
wettability of the Unayzaah sandstone reservoir. Extensive laboratory tests were conducted
on preserved core materials recovered from Unayzah reservoir evaluate wettability
behavior before and after scale treatment. The effect of the scale inhibitor on oil/brine
interfacial tension (IFT) was also investigated.

EXPERIMENTAL APPROACH
Fluids and Material
The scale inhibitor used is DTPMP. The recipe consists of 30 vol% diesel phase (water-in-
oil) and 70 vol% aqueous phase. The aqueous phase consist of 47 vol% of calcium chloride
(8 wt% CaCl
2
), 47 vol% scale inhibitor (penta-phosphonate as received) and 6 vol% HCl
(31 wt%). Stock tank crude oil samples produced from Unayzah reservoir represented the
oleic phase. Synthetic brine was prepared based on geochemical analysis of the produced
water, and filtered through 0.2 m filter paper. Chemical analysis of synthetic brine and
scale inhibitor mix with brine are shown in Table 1.

Preserved core plugs from Unayzah reservoir were used in Amott wettability test. Pure
quartz plates and natural rock plates were used as solid substrates in contact angle
measurements to evaluate wettability using contact angle method.

Amott Wettability Test
Wettabilities of preserved core plugs were measured by modified Amott method (Amott,
1959). The samples were flushed with brine to establish immobile oil saturation. The
Amott test compares the quantity of oil or brine that spontaneously enters the core
(spontaneous imbibition) with the amount of oil or brine that can be forced into the core
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(dynamic imbibition). The displacement volumes (both spontaneous and total) are
measured for both oil and water. The ratio of the spontaneously displaced volume to the
total displaced volume is calculated for both the oil and water phases. The Amott-Harvey
wettability index is the displacement-by-water ratio minus the displacement-by-oil ratio.

Contact Angle Test
The contact angle measurements were made with Unayzah reservoir oil-brine/rock and oil-
brine/rock quartz systems at reservoir conditions (90
o
C and pressure of 2500 psig).
Contact angles were measured on a smooth substrate using pendent drop apparatus. The
system permitted measurements of the angle made by an oil drop pending on the brine-
solid interface. Quartz was chosen since it represented the major component of Unayzah
reservoir.

Interfacial Tension Test
The pendent-drop tensiometer was used to determine the IFT of oil/brine interface.
Detailed procedure of IFT measurement could be obtained in work published by Okasha,
T. M. (2004).

RESULTS AND DISCUSSION
Amott Wettability Results
Samples selected for the Amott tests were flushed with synthetic brine (200-300 cm
3
) to
remove drilling fluid contaminants and to establish residual oil saturations. Wettabilities of
preserved core plugs were measured by a modified Amott method using dynamic flow-
through displacement (Amott, 1959). The method combines spontaneous imbibition and
dynamic displacement performed under ambient conditions with simulated formation brine
or scale inhibitor and stock tank oil. If a sample spontaneously imbibes only brine, it is
considered water wet. Similarly, if it imbibes only oil, it is considered oil wet. If the
sample imbibes neither, it is described as neutrally wet. The modified Amott-Harvey index
combines oil and water indices into a single wettability index that varies from +1 for
strongly water wet to 1 for strongly oil wet.

Amott wettability data and wettability state for samples tested with synthetic brine only and
with scale inhibitor are listed in Tables 2 and 3, respectively. The wettability results, in
Tables 2 and 3, indicated that samples tested with brine were slightly to water-wet in
character Amott varied between 0.19 to 0.5. The Amott index for samples tested with scale
inhibitor changed from 0.19 to 0.49 which reflect slightly to water-wet characteristics. The
distribution of wettability index with depth is shown in Figure 1. The figure indicates that
Unayzah core material tended to be water-wet in character with a tendency for increasing
water-wet characteristics with depth. It also shows that in most cases samples tested with
scale inhibitor reflected less water-wet characteristic than those tested with brine only.

Contact Angle Results
The contact angle is a measure of the relative strength of adhesion of fluids to solid. It is
commonly used to measure the wetting properties of the solid surface with respect to two
immiscible fluids. It has a major influence on the hydrocarbon distribution as well as water
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within reservoir rock. The range of contact angles has been rather arbitrarily divided into
three regions. From 0 to 75
o
is termed water-wet, 75 to 105
o
neutrally-wet, and 105 to 180
o

oil-wet.

In this study both pure quartz plate and natural rock plate were used as substrates in contact
angle measurements. The plots in Figure 2 showed the effect of temperature and scale
inhibitor on contact angle values for both systems. Plots in Figure 3 indicate a general
trend of little increase in contact angle values with increase of temperature for both
systems. It is seen that addition of scale inhibitor decreases contact angle values for both
systems. The range contact angle (79 82
o
) for Unayzah oil-brine/rock system reflects
neutral wetting behavior. Addition of scale inhibitor decreases the range of contact angle
(64 70
o
), which alters wettability positively to water wet behavior.

The results obtained from Amott and contact angle methods are in agreement. Both
methods indicated that no significant changes in wetting conditions after adding scale
inhibitor (DTPMP). Moreover, there is a positive wettability alteration due to change of
wetting character from neutral state to water-wet behavior as could be observed from
contact angle values (Figure 3). The insignificant changes of the contact angle after
addition of scale inhibitor is due to low adsorption of scale inhibitor chemicals on
sandstone surface. Also control of pH values higher than 8 helps in stability of wetting
conditions. These findings are in agreement with results and observation published by
Guan et el., 2003. They examined changes in surface wettability in a series of static scale
inhibitor (DETPMP) adsorption tests using environmental scanning electron microscopy
(ESEM) and they reported insignificant change of wetting characteristic on micro-scale.

Interfacial Tension Results
The interfacial tension (IFT) between Unayzah oil and synthetic brine was measured at
various temperatures (up to 90
o
C) and reservoir pressures (2,500 psia). Figure 2 shows
plots of IFT versus temperature for oil/brine system and oil/scale inhibitor system,
respectively. The plots indicate a general trend of increasing IFT with increase of
temperature. Comparing plots in Figure 3 indicates that adding scale inhibitor to brine
reduces IFT values oil/scale inhibitor system. For example, at temperature of 75
o
C the IFT
value of oil/brine system was 20.5 dyne/cm at 2,500 psia; while for oil/scale Inhibitor
system decreased to 16.4 dyne/cm at the same pressure. The reduction of IFT as a result of
adding scale inhibitor will lead to improvement in oil relative permeability and
consequently in oil recovery. The decrease of IFT values at higher temperature can be
attributed to the weakening of intermolecular forces at the oil/brine interface. These results
are, in general, consistent with results published by Hjemeland and Larrondo, 1983.

It can be stated that the developed emulsified scale inhibitor system by R&D Center to
mitigate scale in Unayzah reservoir leads to more water-wet conditions, which may help to
explain successful field treatments in more than 35 wells.

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SUMMARY
1. Amott wettability results showed that ranges of Amott indices for samples (Unayzah
reservoir) tested with brine and samples interacted with scale inhibitor varied from 0.19
to 0.5 and from 0.12 to 0.49, respectively. This indicates no significant changes in
wettability conditions for samples interacted with scale inhibitor. The wettability
conditions of core plugs were slightly to strongly water-wet.
2. Contact angle data showed that rock plate and quartz crystal surfaces become more
water-wet (positive alteration) by addition of the scale inhibitor.
3. Contact angle values for both oil-brine and oil-scale inhibitor systems increased with
increasing temperature.
4. Interfacial tension (IFT) results indicated that addition of scale inhibitor leads to a
considerable decrease in IFT values at reservoir conditions.

ACKNOWLEDGEMENTS
Appreciation is given to the Saudi Arabian Oil Company (Saudi Aramco) for granting
permission to present and publish this paper. The authors wish to thank the management of
Research and Development Center.

REFERENCES
Amott, E. (1959): Observation Relating to the Wettability of Porous Rock, Pet. Trans. AIME,
V. 216, 156-162.
Buckley, J. S. (1998): Evaluation of Reservoir Wettability and Its Effect on Oil Recovery
DOE/ID/13421, Report-DE98000472.
Cuiec, L.E.: Evaluation of Reservoir Wettability and Its Effect on Oil Recovery, Interfacial
Phenomena in Petroleum Recovery, N. R. Morrow (ed.), Marcell Dekker, New York City
(1991), 319-75.
Donaldson, E., Thomas, R., and Lorenz, P. (1969): Wettability Determination and Its Effect
on Recovery Efficiency, SPEJ, 113-20.
Guan, H., Graham, G. M., and Juhasz, A., (2003): Investigation of Wettability Alteration
Following Scale Inhibitor Adsorption onto Carbonate and Clastic Reservoir Core Material
Static Tests and ESEM Studies SPE 80231, presented at the SPE International
Symposium on Oilfield Chemistry held in Houston, Texas, USA.
Hjelmeland, O. S., and Larrondo, L. E., (1983): Experimental Investigation of the Effects of
Temperature, Pressure, and Crude Oil Composition on Interfacial Properties, Paper SPE
12124 presented at the SPE Annual Technical Conference and Exhibition, San Francisco,
CA, USA.
Nasr-El-Din, H.A., Saiyari, H.A., Hashem, M.K., and Bitar, G.E. (2003): Optimization of a
Novel Emulsified Scale Inhibitor System to Mitigate Calcium Carbonate Scale in a
Sandstone Reservoir in Saudi Arabia, Paper SPE 80389 presented at the 2003 SPE
Oilfield Scale, Aberdeen, Scotland.
Okasha, T. M., Al-Abbad M. A., and Al-Shiwaish A. A. (2004): Investigation of the Effect of
Temperature and Pressure on Interfacial Tension and Wettability of Lower Cretaceous
Arabian Carbonate reservoir, Saudi Arabia Paper presented at 6
th
International Conference
and Exhibition on Chemistry in Industry, Manama Kingdom of Bahrain.
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Table 1- Chemical analysis of synthetic
brine and scale inhibitor solutions.


Sodium 2579 2714
Chloride 4266 4469
Sulfate 1620 1740
Bicarbonate 178 113
Magnesium 89 92
Calcium 750 771
Variable
9482 9899
Synthetic
Brine
(mg/l)
Scale
Inhibitor
(mg/l)
Total
Dissolved
Solids



Table 2- Amott wettability indices and
wettability state for samples tested
with brine.

To Oil To Brine
OWI WWI
1 0.00 0.19 0.19 Slightly water-wet
2 0.00 0.50 0.50 Water-wet
3 0.00 0.35 0.35 Water-wet
4 0.00 0.20 0.20 Slightly water-wet
Amott Wettability Index
Amott-Harvey
Index
Wettability State
Sample
No


Table 3. Amott wettability indices and
wettability state for samples tested with
scale inhibitor.

To Oil To Brine
OWI WWI
5 0.00 0.49 0.49 Water-wet
6 0.00 0.32 0.32 Water-wet
7 0.00 0.19 0.19 Slightly water-wet
8 0.01 0.13 0.12 Slightly water-wet
Sample
No
Amott Wettability Index Amott-
Harvey
Index
Wettability State


8027.9
8036.9
8787.6
8871.3
8907.2
8910.1
8920.5
8927.2
D
e
p
t
h

(
f
t
)
-1 -0.75 -0.5 -0.25 0 0.25 0.5 0.75 1
Wettability Index
Scale Inhibitor
Brine
Neutral
Slightly
Water
Wet
Slightly
Oil
Wet
Water Wet Oil Wet


Figure 1- Amott wettability indices
distribution.


10
20
30
40
50
60
70
80
90
0 10 20 30 40 50 60 70 80 90 100
Temperature (
o
C)
C
o
n
t
a
c
t

A
n
g
l
e

Unayzah-Oil/Brine/Quartz Plate
Unayzah-Oil/Brine Rock Plate
Unayzah-Oil/Brine/Quartz Plate
Unayzah-Oil/Brine/Rock Plate
No Scale Inhibitor
With Scale Inhibitor

Figure 2- Effect of temperature and scale
inhibitor on contact angle at reservoir
pressure (2500 psi).


8.0
10.0
12.0
14.0
16.0
18.0
20.0
22.0
24.0
0 10 20 30 40 50 60 70 80 90 100
Temperature (
o
C)
I
n
t
e
r
f
a
c
i
a
l

T
e
n
s
i
o
n

(
D
y
n
e
/
c
m
)
No Scale Inhibitor
With Scale
Inhibitor
Pressure = 2500 psia

Figure 3: Effect of temperature and scale
Inhibitor on IFT for oil/brine system.