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Summary
Viscoelastic surfactants (VESs) are used as diverting agents in
carbonate matrix acidizing. However, these surfactants can
adversely affect the wettability around the wellbore.
Receding contact angles were measured with the conventional
method to study the effect of spent-acid solutions with an amphoteric amine-oxide VES and the mutual solvent ethylene glycol
monobutyl ether (EGMBE) on the wettability of Austin cream
chalk rocks. The conventional method involves the injection of
oil droplets into the surfactant solution. However, contact angles
could not be measured when oil droplets were injected into spentacid solutions with VES and EGMBE, because low oil/acid interfacial tensions (IFTs) cause them to spread on the rock surface.
A new procedure was used for these contact-angle measurements. Rocks were centrifuged in spent-acid solutions with VES
and EGMBE, so that the surfactant changed the interfacial properties of the rock. Then, contact angles were measured in spent acid
with hydrochloric acid (HCl) only, to prevent VES and EGMBE
from reducing the oil/acid IFT. The effect of the surfactants in the
spent acid on the acid/rock and acid/oil IFT, which is the wettability, is shown by the difference in contact angles before and after
centrifuging.
With the new procedure, a spent-acid solution with HCl, 1
vol% of VES, and 10 vol% of EGMBE made an oil-wet rock
water-wet and a water-wet rock strongly water-wet at 25 C. This
suggests that an EGMBE post-flush enhances the relative permeability to oil, under the parameters investigated.
Contact angles are a function of the oil/rock, acid/rock, and
oil/acid IFTs. However, the wettability of the rock is a function of
the oil/rock and acid/rock IFT only. The new procedure measures
contact angles in such a way that the surface-active agents change
the oil/rock and acid/rock IFT only so that spreading, an artifact
caused by oil/acid IFT reduction, may not occur.
Introduction
The new procedure was necessitated by the need to study the
effect of spent-acid solutions with an amphoteric amine-oxide
VES, used in carbonate matrix acidizing, on wettability. A US
patent and the rheological properties for the VES were described
by Caweizel (2007) and Li et al. (2010, 2011), respectively. Field
applications were described by Nasr-El-Din et al. (2006a, 2006b,
2006c).
Matrix acidizing is used to improve production from oil and
gas wells and to improve injection into injection wells. An acid or
solvent is injected into the reservoir below the fracturing pressure
to create channels that bypass the damage in carbonates. Carbonate reservoirs are stimulated primarily with HCl. Diversion is
needed because of permeability contrasts and lithological differences in the reservoir (Taylor et al. 2004). Without diverting
C 2014 Society of Petroleum Engineers
Copyright V
This paper (SPE 160876) was accepted for presentation at the 2012 SPE Saudi Arabia
Section Technical Symposium and Exhibition, AlKhobar, Saudi Arabia, 811 April 2012, and
revised for publication. Original manuscript received for review 22 March 2013. Paper peer
approved 5 March 2014.
365
Concentration (mg/L)
NaCl
CaCl22H2O
MgCl26H2O
BaCl2
Na2SO4
NaHCO3
SrCl26H2O
Oil Properties
Density at 70 C (g/cm3)
Viscosity at 50 C (cp)
Total acid number (mg KOH/g)
Total base number (mg HCl/g)
127 523.3
109 162.66
35 657.7
15.16
159.69
483.26
3149.41
0.8015
7.1615
0.18
<0.01
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PC
Optical cell
Light source
Digital camera
Compressed N2
Oil
Accumulator
Syringe pump
Fig. 1The HP/HT tensiometer was used to measure contact angles and IFTs between oil and spent acid with HCl only. This schematic is from Alotaibi et al. (2011).
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VES (vol%)
EGMBE
(vol%)
Contact Angle
(degrees)
Wettability
25
60
80
110
25
110
25, 50, 80, 110
1,2,3,4,6
3
1
1
1
1
No VES
0
0
0
0
1,5
5,10
No EGMBE
Indeterminate
Indeterminate
Indeterminate
Indeterminate
Indeterminate
Indeterminate
Water-wet to oil-wet
50C
110C
Rock
Oil droplet
Spent acid with
HCl only
= 154
= 127
= 106
= 52
Increasing water-wetness
Fig. 2The conventional procedure for contact-angle measurements was effective for spent-acid solutions with HCl only. The
wettability of Austin cream chalk changed from oil-wet (154 ) to water-wet (52 ) as temperature increased.
August 2014 SPE Reservoir Evaluation & Engineering
ID: jaganm Time: 15:49 I Path: S:/3B2/REE#/Vol00000/140020/APPFile/SA-REE#140020
367
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Rock
Spent acid with
HCl, VES and
EGMBE
Oil
Droplet
3s
Fig. 3The conventional procedure was not effective for spent-acid solutions with HCl, VES, and EGMBE (in this instance with
HCl, 1 vol% of VES, and 1 vol% of EGMBE) because oil droplets spread on the rock surface.
30
Rock surface
Spent acidrock IFT, ws
Oil-Rock,
rock IFT, os
Rock-fluid
interface
IFT (mN/m)
25
24.5 mN/m
20
15
10
5
Oil
0.75 mN/m
0
Oil-Spent acid
IFT, ow
Spent acid
50
0.016 mN/m
100
150
200
Time (minutes)
Spent acid with HCl only
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Fig. 6Wettability alteration can be achieved by placing rocks in contact with solutions with surface-active agents. Aging rocks in
crude oil caused a wettability change from water-wet (30 to 45 , left) to oil-wet (140 , right) at 25 C.
HCl has the same pH and CaCl2 concentration as spent acid with
VES and EGMBE.
Experimental Studies. The new procedure was applied to study
the effect of wettability of spent-acid solutions with HCl only and
with HCl, VES, and EGMBE. The following steps were followed:
1. Contact angles were measured in spent-acid solutions with
HCl only to determine the initial wettability.
2. The rock samples were centrifuged at 5,000 rev/min for 2
hours in the following:
a. Spent-acid solutions with HCl only.
b. Spent-acid solutions with HCl and 1 vol% of VES and 10
vol% of EGMBE.
The surfactants in the spent acid caused changes in the wettability
of the rock (i.e., changes in the oil/rock and acid/rock IFT).
3. Contact angles were measured in spent-acid solutions with
HCl only to determine the final wettability.
4. The effect of surface-active agents in the spent acid on wettability was determined by comparing contact angles before and
after centrifuging.
Experiments were conducted at 500 psi and 25 C.
Results
Spent-Acid Solutions with 1 Vol% of VES and 10 Vol% of
EGMBE Were Water-Wetting. An oil-wet rock with a contact
angle of 155 became water-wet with a contact angle of 41 after
it was centrifuged in a spent-acid solution with 1 vol% of VES
and 10 vol% of EGMBE (Fig. 7).
Rock surface
Oil droplet
Oil-wet before
centrifuging:
Contact angle = 155
Oil droplet
Water-wet after
centrifuging:
Contact angle = 41
369
Contact Angle ()
160
120
Before centrifuging
After centrifuging
42
40
40
0
oil-wet water-wet
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155
80
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0
water-wet strongly water-wet
Fig. 8The new procedure was effective for studying the effect
on wettability of spent acid with VES and EGMBE. Spent-acid
solutions with 1 vol% of VES and 10 vol% of EGMBE made oilwet rocks water-wet (left) and water-wet rocks strongly waterwet (right).
Limitations. Surfactant desorption from the surface of the centrifuged rock into the solution may change the IFT between oil/acid
and rock and consequently change the wettability (Adejare et al.
2012). Steps to remove the weakly adhered surfactant (such as
more centrifuging) may prevent a study of the effect of the originally adsorbed surfactant layer on wettability, by removing some
or all of it. In addition, if IFTs above the critical spreading tension
vary as a result of varying surfactant or brine concentrations
(Vijapurapu and Rao 2004), the effect of the different IFTs on
contact angles and wettability is unknown. Another concern is the
effect on the wettability of exposing the rocks to air when transferred to and from the tensiometer between centrifuging stages.
In spite of these potential limitations, applying the new procedure can yield many benefits. One can gain new insights on the
effect of surfactants on wettability (Adejare et al. 2012) if contact
angles are measured in a way that ensures that the oil/liquid IFT
does not affect the results.
Conclusions
A new procedure was presented for contact-angle experiments for
surfactants that reduce the IFT between oil and the surfactant solution, such as spent-acid solutions with VES and EGMBE. The
conventional method cannot be used with these surfactants
because low IFTs make oil droplets unstable on the rock surface.
1. The conventional procedure for contact-angle measurements, in
which the tested solutions are injected into the optical cell, is
effective for solutions with no surfactants (Fig. 2).
2. In contrast, the conventional procedure is not effective for surfactant solutions, such as with VES and EGMBE, which reduce
the oil/acid IFT below the critical spreading tension (Fig. 5),
because oil droplets spread (Fig. 3 and Table 2).
3. The new procedure involves centrifuging the rock in surfactant
solutions, so that the surface-active agents alter the interfacial
properties of the rock. Contact angles were then measured in a
surfactant-free fluid with a high oil/liquid IFT. The difference
in contact angles before and after centrifuging indicates the
effect of the surfactant on wettability.
Rock surface
Oil droplet
Centrifuge in
spent acid with
HCl only
Oil-wet before
centrifuging
Contact angle = 155
Rock surface
Oil droplet
Oil-wet after
centrifuging
Contact angle = 133
Before
centrifuging
160
Contact Angle ()
155
120
After
centrifuging
133
80
40
40
40
0
oil-wet oil-wet
water-wet water-wet
Fig. 10Spent acid with only HCl did not change the wettability
of oil-wet and water-wet rocks. This was the control experiment
for the new procedure.
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