PRODUCT ENGINEERING AND CHEMICAL TECHNOLOGY

Chinese Journal of Chemical Engineering, 18(3) 511514 (2010)

Visco-elastic Properties of VES Diverting Acid for Carbonate Reservoirs
*

ZHAO Zengying ()** and L Guocheng ()
China University of Geosciences (Beijing), Beijing 100083, China
Abstract Storage modulus and loss modulus is the main performance index of visco-elastic properties. In this
paper the storage modulus and loss modulus of a new diverting acid and their influencing factors were systemati-
cally investigated. Besides, the constitutive equations of the diverting acid at different temperatures were elicited
from shearing experiments, which show that the visco-elastic surfactant (VES) acid system is a non-Newtonian
power law fluid at low temperature and a Newtonian fluid at high temperature. The storage modulus and loss
modulus at different temperatures, pH, and VES content in the acid are critical for the design of acid stimulation for
oil well, especially when the VES acid is used in this field only on trial and the basic data are in urgent needed for
the design and construction of the acidification stimulation.
Keywords storage modulus, loss modulus, visco-elastic surfactant, oil field acidification, diverting acid
1 INTRODUCTION
Hydrocarbons are obtained from a subterranean
geologic formation by drilling a well that penetrates
the hydrocarbon-bearing formation. There must be a
flowpath from the formation rock to the wellbore for
the crude oil to be pumped out [1-3]. When the forma-
tion is naturally tight, one can perform a stimulation
technique by injecting acids through the wellbore into
the formation to dissolve portions of the formation to
create alternative flowpaths for the hydrocarbon,
which is called as acidification or acid stimulation.
There have been several acids used in the acid
stimulation field. Recently visco-elastic surfactant
(VES) acid is introduced in North Kuwait and
Zhongyuan Oil Field of China on trial [4-6]. The
visco-elastic surfactants used in the oil field acidifica-
tion are usually the chemicals with the visco-elastic
properties, such as an amine, an amine salt, or a qua-
ternary ammonium salt having the formula

with R
1
to R
4
, an aliphatic group or the ramification of
an aliphatic group same or different with each other.
The VES in this paper is one of these chemicals pre-
pared from alkyl amine and named alkylamidopropyl
betaine having the formula

It is adequate for use in oil field because of its supe-
rior visco-elastic properties. However, the study on the
fundamental mechanism of VES acid has been
dropped behind its application on spot, especially the
basic studies on the relation between shear rate and
shear stress, the constitutive equations, and the storage
modulus and loss modulus of the VES acid system.
2 MATERIALS AND METHODS
2.1 Materials and instrument
The typical chemical process to synthesize the
visco-elastic surfactant has been described in former
paper [7]. The VES acid containing 1%-7% (mass
percent, similarly the undermentioned) of VES and
20% of HCl was prepared. Rheostess-600 and
CSL2-500 rheometers are the products of Thermo
Haake Inc. and TA Instruments Inc., respectively. The
test condition is VES%: 5%, shear rate: 170 s
1
, tem-
perature: 20 C if no special instructions.
2.2 Experimental procedure
The viscoelasticity performance of the VES acid
system was tested by the methods of the Small Am-
plitude Oscillation (SAO). HCl acid or VES acid are
reacted with analytically pure CaCO
3
to simulate the
reaction of acid with formation carbonates. The vis-
cosity, storage modulus, loss modulus, etc. of the re-
sulting acid systems were tested with the rheometers.
3 RESULTS AND DISCUSSION
3.1 Constitutive equation
At the beginning, VES is 5% (mass percent,
similarly hereinafter) in the VES acid system with
acid content of 20%. After reacted with analytically
pure CaCO
3
, the acid was consumed with an increase
in viscosity of the VES acid system and formation of

Received 2009-09-30, accepted 2010-02-03.
* Supported by the Acidification for Heterogeneous Carbonate Reservoirs Program of Petro China Company Limited.
** To whom correspondence should be addressed. E-mail: zhaozy@cugb.edu.cn
Chin. J. Chem. Eng., Vol. 18, No. 3, June 2010 512
VES gel. The relation between shear rate and shear
stress are shown in Fig. 1.

Figure 1 Variation of measured shearing stress with
shearing rate at 30 C
+ shearing stress with shearing rate at 30 C;
fitting line 1 with fitting equation 49.12 /(51.26 ) = + ;
fitting line 2 with fitting equation
0.53
2.66 =
The fitting lines as shown in Fig. 1 can be fitting
out by different mathematical versions, that is, formu-
las (1) and (2) from the data of shear rate and shear
stress at 30 C. For engineering convenience, formula
(2) is always used in the design of oil field acidifica-
tion because of its explicit physical meaning, espe-
cially when shear rate is below 200 s
1
. In the formula
(2) the exponent as an indication of the fluid types is
0.53, showing that the VES acid gel is a shear thinning
fluid since it is less than 1. This is because that the
fitting line 2 and the mathematical expression of the
fitting line, i.e. the formula (2), accords with the con-
stitutive equation of non Newtonian power law fluid,
n
k = (n<1, k: a constant). Therefore, the formula
(2) means that at 30 C the VES acid system is a kind
of non Newtonian power law fluid [8]. Although the
formula (1) fits the relation between shear rate and
shear stress more exactly, it is scarcely ever used in
the design of acidification because it has no obvious
physical meaning.
49.12
51.26

=
+
(R
2
= 0.9992) (1)
0.53
2.66 = (R
2
= 0.9648) (2)
As shown in Fig. 2, when the temperature grew
from 30 C to 75 C, the VES acid fluid changes from
a non Newtonian power law fluid to a linear Newto-
nian fluid [9]. At the temperature of 75 C, the rela-
tionship of shear stress and shear rate has changed to a
straight line and can be described by k = (k: a
constant) as its constitutive equation.
As to the relation between viscosity and shear
rate, the results show that the viscosity of the VES
acid system is inversely proportional to shear rate at
temperature of 30 C as shown in Fig. 3, which is just
the characteristics of viscosity-shear rate relation of
non Newtonian power law fluid.
The results show that the shear stress at a high
temperature of 75 C is in direct proportion to shear
rate when the shear rate is in a range of acidification
(between about 20 s
1
to 200 s
1
), and the viscosity is
almost a constant value with the changing of the shear
rate. It means that at higher temperatures (60 C or
75 C) the VES acid system fluid is almost a kind of
linear Newtonian fluid.
3.2 Storage modulus and loss modulus at differ-
ent pH
Storage modulus G and loss modulus G can be
used to indicate the viscoelasticity performance of a
VES acid system [10]. For pure viscous fluids, storage
modulus G equals to zero, while for pure elastomers
loss modulus G is zero. CSL2-500 rheometer was
used to determine their value during the reaction
process between the VES acid and carbonate forma-
tion (with the changing of pH of the system at differ-
ent reaction stages). When the pH of the acid system
increases from about 0 to 4.44, the storage modulus G
changes from 20 Pa to 80 Pa, indicating an obvious
increase in viscosity of the acid system. The loss
modulus G is a small value at a low pH, showing that
the VES acid system has a low viscosity. When pH
grows to 0.01 or more, the G increases obviously
with VES gel formation at this moment as shown
in Fig. 4.

Figure 2 Variation of measured shearing stress with
shearing rate at different temperatures
temperature/C: + 30; 45; 60; 75

Figure 3 Variation of measured viscosity with shearing
rate at different temperatures
temperature/C: + 30; 45; 60; 75

Chin. J. Chem. Eng., Vol. 18, No. 3, June 2010 513

Figure 4 Variations of measured storage modulus G and
loss modulus G with oscillation frequence at different pH
G at pH= 4.44; G at pH= 0.01; G at pH= 0.05;
G at pH= 4.44; G at pH= 0.01; G at pH= 0.05
The ratio of G and G, tg, shows the viscidity
and elasticity of the VES acid system at the same time.
A small value of tg of the VES acid system indicates
a better elastic performance related to viscosity. Fig. 5
shows that tg decreases with the growing of the pH
of the VES acid system at the same oscillation fre-
quence. Therefore, the increase of the pH can result in
the enhancement in the elasticity of the VES acid sys-
tem related to viscosity since the VES gel has been
formed at this stage.

Figure 5 Variations of measured tg with pH
pH: 0.50; 0.01; 4.44
3.3 G and G with different percent of VES in
the acid system
VES results in the high viscoelasticity of the acid
system, therefore, the content of VES in the acid sys-
tem has an obvious effect on the viscosity and the
elasticity of the acid system. Figs. 6 to 8 show the dif-
ferent storage modulus G, loss modulus G, and com-
plex modulus G* with the changes of the VES content
in the acid system. Fig. 6 shows that at a fixed oscilla-
tion frequence, when the VES content changes from
3% to 6%, the storage modulus G increases obviously,
which means the augmentation of the elasticity of the
acid system. It is the same for the loss modulus G
and complex modulus G*, indicating that both the
viscosity and elasticity of the acid system increase
with increasing amount of the VES in the acid system.
Moreover, Fig. 8 shows that when the content of VES
increased from 5% to 6% in the acid system, the com-
plex modulus G* has just a limited increase. Consid-
ering the amplification of the viscoelasticity because
of the addition of VES and the cost of the VES acid,
5% of the VES content in the acid is suitable in the
practice usage.
3.4 The influence of the temperature to the vis-
coelasticity of the VES acid
The storage modulus G and loss modulus G

Figure 6 Variations of measured storage modulus G with
different VES contents
3%VES; 4%VES; 5%VES; + 6%VES

Figure 7 Variations of measured loss modulus G with
different VES contents
3%VES; 4%VES; 5%VES; + 6%VES

Figure 8 Variations of measured complex modulus G*
with different VES contents
3%VES; 4%VES; 5%VES; + 6%VES

Chin. J. Chem. Eng., Vol. 18, No. 3, June 2010 514
were tested at 20 C, 40 C, 60 C and 80 C, then the
ratio of G and G, tg, was calculated. A small tg of
the VES acid system indicates that it has better elastic
performance related to viscosity, and inversely a better
viscosity than elasticity. The relation of tg and tem-
perature is shown in Fig. 9. When the temperature
changed from 20 C to 80 C, tg increased at first,
then decreased to a value even lower than that at the
low temperature. The change of the tg value shows
that the elasticity of the acid system decreases at first,
then increases to a higher level than the value at the
beginning after the temperature grow to about 45 C.
In other words, the viscosity increases at first, then
decreases, which means that the changing trend of tg
is consistent with the relation between viscosity and
temperature.

Figure 9 Variations of measured tg with temperature
tg; fitting line
4 CONCLUSIONS
In this paper, the main parameters of viscoelas-
ticity performance of a new VES acid system were
investigated by the method of Small Amplitude Oscil-
lation dynamic examination. The constitutive equation
for the VES acid system has been elicited out from the
tests. The VES acid fluid is a non Newtonian power
law fluid at low temperature and it changes to a linear
Newtonian fluid at high temperature. The storage
modulus G, loss modulus G etc. have been measured
and the results show that the VES acid system has
viscosity and elasticity simultaneously. The viscoelas-
ticity of the VES acid was increased with an addition
of the VES. The viscosity increases at first and then
decreases with increasing temperature, while the elas-
ticity of the acid system is just the opposite.
NOMENCLATURE
G storage modulus
G loss modulus
G* complex modulus
tg ratio of G and G
shear stress, Pa
shear rate, s
1

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