SPE 109017

Development of an Ultra-Low Interfacial Tension Surfactant in a System

with No-Alkali for Chemical Flooding
D.M.Wang, SPE, Daqing Oilfield Co. Ltd.; C.D.Liu, Research Inst. Petroleum Exploration and
Development;W.X.Wu, SPE, Daqing Petroleum Inst.; G.Wang, SPE, Daqing Oilfield Co.Ltd.
Copyright 2008, Society of Petroleum Engineers
This paper was prepared for presentation at the 2008 SPE/DOE Improved Oil Recovery Symposium held in Tulsa, Oklahoma, U.S.A., 1923April2008.

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
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Abstract
The development and evaluation of a series of betaine amphoteric surfactants which have been synthesized
recently is introduced in this paper.
This series of products were synthesized by adjusting the structure of the lipophilic group. A product of this
series was comprehensively evaluated. The results show that interfacial tension (IFT) between this betaine
amphoteric surfactant solutions and Daqing crude oil can reach an ultralow value (10
-3
mN/m ~ 10
-4
mN/m) with
no alkali or weak alkali (Na
2
CO
3
) and at ultra-low concentrations of surfactants of only 10 ~ 3000 ppm (wt). When
the salinity of the make up water is 0 ~ 153,700 mg/L, concentration of divalent ions 0 ~ 1,500mg/L and
concentration of polymer 0 ~ 2,000 mg/L, it hardly effects the IFT value, the IFT of the surfactant solutions with
crude oil maintains an ultra-low value. Experiments in cores indicate that the displacement efficiency of the
compound solution composed of polymers and surfactants (0.1% concentration) is higher than that of
alkali/polymer/surfactant (ASP) solution (surfactant concentration 0.3%) used in the oil field now, the total
recovery can reach 70 % OOIP or higher. It is shown that the IFT of the fluid gathered at the outlet of the cores,
when flooding by 0.35 PV of this type of surfactant (0.2 % concentration), can still be in the range of 10
-3
mN/m ~
10
-4
mN/m, this means that the entire volume of the core is flooded by ultra-low IFT fluid, which is seldom seen
when using other types of surfactants. It is also shown that the surfactant can change the wettability and increase
the recovery efficiency in micro-visual oil displacement experiments.
The above results show that this is a very promising surfactant for ultra-low IFT chemical flooding. It can be
used in a wide range of reservoir conditions (both low and high salinities, divalent ion contents, temperatures, clay
contents, different alkali etc.) to significantly increase the oil recovery. Since it only needs a very low
concentration of surfactant to obtain an ultra-low IFT, the economics of chemical flooding using this type of
surfactant should be better than that using conventional ones.

Introduction
Amphoteric surfactants are a special type of surfactant that contains both cation hydrophilic group(s) and anion
hudrophilic group(s). Betaine types surfactant is one of them, it is a natural subsistence first separated by Kruger
from beets. It is a surfactant derived after one of its CH
3
is replaced by a long chain alkyl. Due to its special
hydrophilic group structure, it has advantages of low irritation (to people), good hard water resistance feature and
wide applicability. Therefore, it is widely used in the daily use chemical industry. There are few reports about
using betaine surfactants in enhancing the recovery of crude oil. A study to optimize the molecular structure of
betaine surfactants was made, and a betaine surfactant which has a special structure was synthesized. In no
alkali or weak alkali conditions, the interfacial tension (IFT) between betaine surfactant solution and Daqing crude
oil can reach an ultra low level (less than 10
-3
mN/m), and the results of core flooding tests and micro visualization
experiments obtained good results.


Chemical Structure of Betaine Surfactant
2 SPE 109017

R is a lipophilic group that has a special structure to match the specific crude oil and form an ultra low IFT.

Appraisal of the IFT of the New Betaine Surfactant Solutions
Experimental Conditions
Experimental crude oil: dehydrated crude oil of XWZ well of Daqing oil field, flash point is 60, pour point
38, density (20) 0.8659g/m
3
, kinetic viscosity 50.59mm
2
/s, paraffin content 21.2%, resin content 21.5%,
sulfur content 0.071%, remnant carbon 2.72%, ash 0.04%.
Water composition: Produced water of XWZ of Daqing oil field, salinity is 3700mg/L, containing Ca
2+

56.1mg/L, Mg
2+
36.46 mg/L.
Chemicals used: Na
2
CO
3
, NaCl, CaCl
2
are analysis grade reagents; the surfactant used was synthesized in
this study, it was named BS11, it has a Kraft temperature of 50.
Instruments used: a Texas 500 type IFT instrument was used to determine the IFT.

Experiment Results and Discussion
The effects of surfactant concentration on IFT
Figure 1 shows the relation of IFT and BS11 concentration. According to Figure 1, sulfonated betaine
surfactant BS11, in a produced water solution, can cause the IFT to XWZ crude oil to reach an ultra low level
(less than 10
-3
mN/m), on condition of no alkali and at very low concentrations (0.005%). Furthermore, the
concentration range to form an ultra low IFT is quite wide, which indicates that the surfactant is very effective
in reducing the IFT.

Effects of sodium carbonate concentration on IFT



SPE 109017 3

Figure 2 and Figure 3 show separately the changes of IFT as the concentration of BS11 changes and
when the sodium carbonate concentration is 0.1% and 0.5%. According to Figure 2, with a concentration of
sodium carbonate at 0.1%, the IFT can reach an ultra low level (the lowest being 10
-4
mN/m) when the
surfactant concentration is in the range of 0.001%-0.3%. Comparing this to Figure 1 (the conditions of no
alkali), it can be seen that there is no obvious changes in the IFT, which means that a 0.1% concentration of
sodium carbonate does not effect the IFT, but it might lower the absorption rate of surfactants in some
reservoirs. From Figure 3 it can be seen that with a sodium carbonate concentration of 0.5%, it affects the IFT
when the concentration of surfactant is low, but not when it is high.

Effects of Temperature on IFT


Figure 4 shows the changes in IFT of XWZ crude oil and the new surfactant as the temperature changes
when the concentrations of the surfactant are 0.01%, 0.1% and 0.3%. According to the Figure, the IFT of
surfactant solution and produced water can be maintained at an ultra low value when the temperature is
between 45 and 80, indicating that the surfactant solution can still maintain an ultra low IFT at rather high
temperatures.

Effects of Salinity and Divalent Ions on IFT
4 SPE 109017



Figures 5 and 6 show the effect of salinity and divalent ions on IFT of surfactant in produced water
solution and XWZ crude oil at 45 when the surfactant concentration is 0.05% and 0.3%. It can be seen that
when the salinity is lower than 153,700mg/L, and the divalent ion concentration is less that 1,500mg/L, there
is little change in the IFT. This shows that this new sulfonated betaine surfactant is very salinity and high
concentration calcium ion tolerant.

Core Flooding Tests of New Sulfonated Betaine Surfactant
Flooding Tests
Test Conditions:
Cores: two dimensional artificial cores (slightly oil wet), both homogenous and heterogeneous, outer
diameter 4.54.530 (cm), permeability to air 1.0 m
2
.
Experimental oil: XWZ crude oil mixed with kerosene to form a simulated oil which has a viscosity of
10mPa.S at 45 .
Experimental Water: all the water used is synthetic brine. For connate water the salinity is 6778 mg/L;
when water flooding, the salinity is 3700 mg/L.
Chemicals used: Sulfonated Betaine Surfactant (BS11) and Alkylbenzene Sulfanate Sy; polymer is
produced by Daqing Refinery Co., molecular weight 2510
6
Daltons; analytical grade NaOH and Na
3
PO
4
.
Flooding Systems and Sequences in the Tests: The surfactant system (3 types) is the first slug, the
polymer solution is the follow up slug. The 3 surfactant systems are (1) Betaine surfactant plus polymer
solution (with no alkali) binary system, it is composed of 2,000 mg/L BS11 surfactant plus 2,500 mg/L
polymer. This system is called for short the binary system; (2) The above binary system with a small amount
(4,000 mg/L) of Na
3
PO
4
, It is called for short the Na
3
PO
4
added binary system; (3) The ASP system used in
Daqing Oil Field, it contains 10,000 mg/L NaOh plus 3,000 mg/L Sy plus 2,500 mg/L polymer. It is called for
short the ASP system; the polymer system is a 1,000 mg/L polymer solution.
SPE 109017 5
Test Procedures
After on vacuum for 3.5 hours, the core is saturated with synthetic brine; porosity is measured; the
saturated with brine core is put in a incubator at 45 for one hour; flood with oil until all movable brine is
driven out; determine the original oil saturation; water flood the core at flow velocity of 1m/d until the water cut
is above 98%; calculate the water flood recovery efficiency; flood with 0.35 PV surfactant (on one of the
above mentioned systems) slug followed by 0.20 PV polymer slug, then continue to flood with brine until the
water cut is above 98%; calculate the chemical flood incremental recovery and total recovery.

Test Results and Discussion
Homogeneous Artificial Core (slightly oil wet) Flood
The recoveries of the binary system, the Na
3
PO
4
added binary system and the ASP system were
tested and calculated; the total costs of the different chemicals used were equal for each system and used as
a norm to determine their actual amount. The results are shown in Table 1. The ASP system has a rather high
viscosity (82.1 mPa.s at 45), ultra low IFT and good emulsion forming characteristics in the core, therefore
its volumetric sweep efficiency and displacement efficiency are all quite high, causing the incremental
recovery to be quite high (25% original oil in place-OOIP). Because no alkali is added, the binary system has
an even higher viscosity (135 mPa.s at 45), therefore the volumetric sweep efficiency is even higher, the
IFT is about the same and displacement efficiency should be about the same, but its emulsion forming
characteristics are not as good as that of ASP systems, the total results is the incremental recovery being
about the same as that of ASP systems (25% OOIP). For the Na
3
PO
4
added binary system, its viscosity (110
mPa.s at 45) is in between the values of the ASP system and the binary system, its IFT is the lowest of the
three systems (the Na
3
PO
4
added into the system caused the surface active film at the oil-water interface to
be more compact), therefore it has the highest incremental recovery (27% OOIP).
Table 1 Artificial homogeneous core flooding test results
Recovery
ratio %
Test group
Core
numbers
Permeabil-
ity to Gas
/m
2


Porosity%

Oil
Saturation/%
Flooding system
Water flood
Surfactant
flood
Total









12-1
13-1
average

12-6
12-4
average

15
16
average
1.079
1.156
1.118

0.988
0.923
0.956

1.032
1.086
1.059
26.1
28.9
27.5

26.7
25.9
26.3

27.6
28.1
27.9
72.4
71.6
72.0

70.0
70.5
70.3

73.5
75.8
74.7
Binary system + polymer

Na
3
PO
4
added in binary
system + polymer

Alkali ASP system +
polymer
46.3
45.5
45.9

44.4
45.1
44.8

45.0
45.8
45.4
25.9
25.7
25.8

27.5
27.0
27.3

25.9
25.5
25.7
72.2
71.2
71.7

71.9
72.1
72.0

70.9
71.3
71.1


Floods on Artificial Heterogeneous Cores
In order to further study the displacement efficiency of no alkali binary system, composed of
sulfonated betaine surfactant and polymer fluid, flood tests were performed on 2 dimensional heterogeneous
cores, the Dystra-Parson coefficient is 0.65. The results of the floods are shown in Table 2. From Table 2 it
can be seen that the displacement efficiency of no alkali binary systems and the binary systems with a small
amount of Na
3
PO
4
added as a sacrificial agent is respectively 26.7% OOIP and 27.7% OOIP. The strong
alkali ASP system has a displacement efficiency of about 26% OOIP. All three systems have similar
displacement efficiencies and they are all higher than 25 % OOIP. This result is similar to that of
homogeneous cores.



6 SPE 109017
Table 2 Artificial heterogeneous core flooding test results
Recovery ratio/%
Core numbers

Permeability
to Gas /m
2


Porosity
%

Oil
Saturation
/%
Flooding system
Water flood
Chemical
flood
Total
1116B-8 1075 26.8 71.5 Binary system + polymer 42.0 26.2 68.2
1116B-1 1074 27.9 70.2
Na
3
PO
4
added binary
system + polymer
42.0 27.7 69.7
1116B-11 1089 26.5 70.2
Alkali ASP system +
polymer
41.3 26.1 67.4

Produced Fluid IFT from Flood Tests
The IFT of the produced fluid at the outlet of the flooded core was measured. The flooding system
was a binary system containing sulfonated betaine surfactant. The results are shown in Figures 7 and 8. It
can be seen that for both duality systems (with and without Na
3
PO
4
added as a sacrificial agent) after first
injecting 0.3 PV of surfactant fluid followed by 0.2 PV of polymer fluid and then water, after injecting a total of
0.8 PV, the IFT between oil and brine all were lowered to less than 10
-3
mN/m. This test was performed on
artificial cores, therefore the surfactant absorption on the core surface could be low. Therefore the actual
absorption of the surfactant in this system on natural cores still has to be tested.



Tests of New Surfactant on Visualization Cores
Test Process
Test Equipment
SPE 109017 7
Flood tests were performed on etched glass core models; image gathering system was used to
transform the flood images into electronic signals; image analysis techniques were used to study the progress
of the displacement process.
Test Cores and Chemicals Used
The test core was a glass etched transparent model (area of 40mm40mm), silicon oil was used
to change its wetness. The oil used was Daqing crude oil taken at the well head and with kerosene added to
form simulated oil (with the same viscosity as the reservoir crude). The surfactant solution was prepared
using water with a salinity of 3,700 mg/L, the brine for water flooding had a salinity of 508 mg/L. The
surfactant systems used were (1) Betaine surfactant, concentration 0.1% at 30, the IFT to simulated oil was
5.1210
-3
mN/m; (2) Alkyl-benzene-sulphonate surfactant, concentration 0.3% at 30, the IFT to simulated oil
was 4.1110
-2
mN/m .
Test Results
Residual Oil in Oil Wet Dead Ends
The flooding results are shown in Figures 9 and 10. From the two figures, it can be seen that after
water flooding, the oil was not or only partially driven out of the dead end; when flooding with surfactant
solutions, the residual oil decreased. The displacement efficiency was higher for betaine surfactant compared
to alkyl-benzene sulfonate surfactant, this might be because the IFT of the betaine solution was lower, and it
might also be because that by flooding with a betaine solution, the wettability changed more to water wet. The
wattability of the dead ends changed from oil wet towards water for all two surfactant solutions, however more
so for the betaine surfactant solution.





8 SPE 109017
The flooding progress of betaine surfactant in dead ends and its effect on the wettability and resifual oil is
shown in Figure 11 (the flood direction is from right to left). It can be seen that when flooding with surfactants,
the oil seems to be gradually pulled out of the dead end (the residual oil is actually pushed out at its
protruding portion), the residual oil decreases and when the surfactant absorbs on the surface of the rock,
the pore systems wettability changes from oil wet to water wet.

Flooding of Film Type Residual Oil
When film type residual oil is contacted by betaine surfactant solutions, the equilibrium of forces at the oil-
water-rock surface is destroyed. The resistance to flow due the capillary forces are greatly reduces (the IFT is
much lower); the core surface changes from oil wet to water wet, therefore the adhesion force to oil at the
core surface changes from positive to negative, pushing the oil film away from the core surface, resulting in
the oil film being much easier to move; the pressure gradient of the fluid flow is about the same as that of
water flooding. Therefore it can be seen that the total resistant forces to flow has decreased, and the driving
forces are about constant (compared to water flooding). This is beneficial to the movement (mobilization) of
the oil film. The actual process is seen in Figure 12.


The oil film forms a bulge (protruding portion) at the front of the oil film to generate a capillary
force to counteract the driving forces; the fluid flow changes direction at the bulge, therefore increasing the
micro driving forces (caused by the change in fluid flow momentum), which will push the bulge forward to form
a separate oil droplet that flows downstream. The amount of oil in the oil film decreases. At the same time,
the change in wettability increases the contact angle, causing a larger change in fluid flow direction, and a
corresponding increase in micro forces. By the combined effect of the above two reasons, the oil in the
protruding portion of the film mobilizes, the remaining oil in the film replenishes the bulge in the front. The
SPE 109017 9
above process repeats until eventually the film disappears or decreases.

Flooding of Column Type Residual Oil
The mobilization of column type residual oil in an oil wet core by betaine surfactant solution is
shown in Figure 13.

Due to the lowering of the IFT, the surfactant fluid pushes the oil column, a bulge (protruding portion) is
formed in front to generate a capillary force to counteract the driving force; fluid flowing past this bulge will
generate a larger micro force which will further push the bulge sideways until the bulge detaches itself form
the oil column to form a new oil droplet and move forward. The oil in the column replenishes the oil in front
(that has decreased due to the forming of the new oil droplet) and forms a new bulge. This process repeats
until the entire oil column turns into individual oil droplets and is mobilized (or it is partially mobilized when the
capillary force at the bulge is larger that the driving force).

Conclusions
1. With no alkali and at a very low concentration (0.005%) of surfactant, the IFT between the new sulfonated
betaine surfactant solution (with Daqing produced water as the water phase) and Daqing crude oil can reach
an ultra low IFT.
2. At a temperature range of 45--80, change in temperature practically does not affect the IFT, the IFT
maintains an ultra low value.
3. After adding a small amount (0.1%) of Na
2
CO
3
as a sacrificial agent, there is practically no influence on the
IFT when the concentration of surfactant is in a range of 0.001%-0.3%, the IFT maintains an ultra low value;
when 0.5% of Na
2
CO
3
is added as a sacrificial agent, it effects the IFT of the low concentration surfactant
solution, not the higher concentration ones.
4. The new betaine surfactant is quite tolerant to high salinity and high concentration divalent ions.
5. When flooding homogeneous or heterogeneous artificial cores by no alkali binary systems, or when adding
a small amount of Na
3
PO
4
as a sacrificial agent to the binary system, and by ASP systems with strong alkali
added, the incremental recoveries over water flooding are all higher than 25% OOIP.
6. The effluent from the surfactant flooded cores all attained an IFT lower than 10
-3
mN/m.
7. From micro visualization cores, betaine surfactant flooding decreased film, column and in dead end
type residual oil. It also changed the wettability of the core surface from oil wet to water wet.

References:
1. Liang. M, The Characteristics of Surfactants and Detergents, Beijing Scientific Press, 1990.
2. Wang. X, Cosurfactants for the Textile Industry, Jiangsu Scientific Press, 2004.
3. Fang. Y, Amphoteric Surfactants, Beijing Light Industry Press, 2001.