SPE-172185-MS

Foamability and Foam Stability of Several Surfactants Solutions: The Role of

Screening and Flooding

Azmi Belhaij, King Saud University, Abdulrahman AlQuraishi, King Abdulaziz City for Science and Technology,
Osama Al-Mahdy, King Saud University
Copyright 2014, Society of Petroleum Engineers

This paper was prepared for presentation at the SPE Saudi Arabia Section Annual Technical Symposium and Exhibition held in Al -Khobar, Saudi Arabia, 21-24 April 2014.

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
reviewed by the Society of Petroleum Engineers and are subject to correction by the author(s). The material does not necessarily reflect any position of the Society of Petroleum Engineers, its
officers, or members. Electronic reproduction, distribution, or storage of any part of this paper without the written consent of the Society of Petroleum Engineers is prohibited. Permission to
reproduce in print is restricted to an abstract of not more than 300 words; illustrations may not be copied. The abstract mus t contain conspicuous acknowledgment of SPE copyright.

Abstract
Foamability and foam stability are of main concerns in foam displacement for enhanced oil recovery. This work presents the
output of systematic laboratory screening of foamability and foam Stability of several surfactants. The surfactants examined
were Brij 700, Triton X-100, Triton X-405, Zonyl FSO, Hitenol H-10, Hitenol H-20, Noigen N-10 and Noigen N-20. Foam
was generated by sparging Carbon Dioxide gas at a fixed flow rate through surfactants solutions and R5 parameter as
suggested by Lunkenheimera and Malysa (2003) were used for foam stability testing. The results indicate the foamability of
all surfactants except for Triton X-405. Zonyl FSO and Hitenol H-10 were superior in term of foam stability with more
stability as surfactants concentration increases. Equivalent optimum foam volumes were obtained for both surfactants but at
higher concentrations of Hitenol H-10.
Foam stability and oil displacement efficiency were tested with different concentrations of Zonyl FSO and Hitenol H-10
solutions. The presence of oil at the volume fraction implemented, affect the stability of the foam columns. The effect depends
on the surfactant-type and surfactants concentrations where stability decreases at low Zonyl FSO concentration range and at all
concentrations range tested of Hitenol H-10. In case of Zonyl FSO observations indicate that oil stayed in the lamellas skeleton
and plateau boarders with no drain out. To the contrary, Hitenol H-10 was able to lift good portion of the oil column but oil
was drained out of the foam structure within a short period of time.
Flooding tests on Berea cores proved the ability of Zonyl FSO and Hitenol H-10 in controlling gas mobility and improving the
displacement efficiency. Hitenol H-10 was more efficient as indicated by the incremental oil recovery obtained and the higher
pressure drop encountered. Hitenol H-10 Foam injection on tertiary gas flooded reservoirs improves residual oil recovery
indicating the potential of the process even at late stages of gas injection.

Introduction
The declining trend of new discoveries coupled with the high demand for energy, directed the industry to the importance of
enhanced oil recovery (EOR) processes in low recovery efficiency reservoirs. Gas flooding is a common method implemented
for improved oil recovery. Despite the favorable characteristics of dense carbon dioxide in displacing oil from reservoir rocks,
viscous fingering, gravity override and reservoir heterogeneity are the main disadvantages of CO 2 floods. Foam injection as an
EOR method was first introduced in 1958 by Bond and Holbrook (1958). Later, Fried (1961) proved that foam can act as gas
blocking agent. Foam displays favorable flow characteristics to EOR process including favorable mobility, selective blocking
of thief zones and flow diversion to lower permeability regions. (Bernard, et al. 1980; Seright and Liang, 1995; Nguyen, et al.
2000; Farajzadeh, et al. 2012).
Foams are usually formed in systematic hexagonal texture as a result of gas dispersion through a continuous surfactant
solution (Schramm and Wassmuth, 1994). It is thermodynamically unstable and they are stabilized by surfactants to prevent
bubble coalescence. Foams are generally described in terms of their foamability defined as the capacity of the surfactants to
form foam irrespective of the special foam properties, and foam stability describing the variations of foam height or volume
with time, immediately after foam generation (Malysa and Lunkenheimer, 2008). Foamability and foam stability are
interrelated and the more stable the foam films the greater is the solution's foamability.
Foam generation generally increases with increasing surfactant concentration up to the critical micelle concentration (CMC)
above which surfactant concentration has little effect (Chiang, et al. 1980). Marsden and Khan (1966) found that foam
apparent viscosity increases with increasing surfactant concentration. Foam stability is dependent on electric double-layer
SPE-172185-MS 2

repulsion (Israelachvili, 1991; Schramm and Wassmuth, 1994), gravity drainage, capillary suction, surface elasticity,
dispersion force attraction, steric repulsion and surface and bulk viscosity (Schramm and Wassmuth, 1994). An increased
surface and bulk viscosity do not contribute directly to film stabilization. They rather act as resistances to the film thinning and
rupturing processes.
Foam stability in presence of oil is related to foam-oil interaction. Literatures indicated the role of oil presence on foam
stability (Aveyard, et al. 1993; Garrett, 1993; Bergeron, et al. 1993; Schramm and Wassmuth, 1994; Denkov, 2004). Wasan et
al. (1988) indicated that foam stability in presence of oil is related to pseudo emulsion film between oil drops and gas.
Vikingstad et al. (2005) performed static foam tests and observed that foam stability in presence of oil is related to surfactant
ability to solubilize oil molecules. Oils characterized with higher molecular weight can stabilize the generated foam compared
to lower molecular weight oils.
Three major mechanisms have been considered for the antifoaming property of the dispersed oils. These are aqueous film
thinning rate during oil entry, oil spreading on the water surface, and thin water film bridging (Nikolov, et al. 1986; Lau and
O’Brien, 1988). Simjoo et al. (2013) suggested that foam decay in presence of oil starts as small and rapid decay dominated by
gravity drainage, followed by a stabilized foam volume, and then a second continuous decay due to bubble coalescence over a
relatively long time. The oil foam destabilization is more pronounced for oils with a smaller molecular weight. Farajzadeh et
al. (2012) showed that CO2 injection below the gas minimum miscibility pressure hardly foams in the oil zone of the porous
medium.
This work aimed to screen several surfactants investigating their foamability and foam stability in absence and presence of
Saudi light crude oil. The efficiency of the most effective surfactants in controlling the gas mobility is tested in porous
medium.

Materials
Several surfactants were screened. These surfactants are nonionic (Brij 700, Triton X-100, Triton X-405, and Zonyl FSO,
Noigen N-10 and Noigen N-20), and anionic (Hitenol H-10, Hitenol H-20). Surfactant solutions of different concentrations
were prepared by diluting them in brines of 4% salinity. Table 1 lists the compositions of brine solutions. Oleic phase was
light Saudi crude (31.5 API, 9 cp) while high purity Carbon Dioxide gas was used as gaseous phase. Porous medium were
homogeneous Berea sandstone core samples 10 cm long with 3.8 cm diameter.

Table 1: Composition of 4 % brine

Component Weight (%)

NaCl 3.06

KCl 0.029

CaCl2 0.54

MgCl2.6H2O 0.26

Na2SO4 0.30

H2O 95.81

Experimental Procedure
Foam stability of surfactant solutions were examined using the R5 method proposed by Lunkenheimera and Malysa (2003).
The setup used (Figure 1) consists of a glass column 100 cm long with 1.6 cm inner diameter equipped with glass frit placed at
the base of the column. A syringe was used for gas supply into the solution in order to generate the required foam. The
experiments are conducted by slowly pouring surfactant solution (12.5 mL) into the glass column and manual introduction of
Carbon Dioxide gas (50 mL) into solution within a period of 20 seconds. After gas introduction, the stopcock connecting the
column with the syringe is immediately closed, and the initial foam and solution heights are measured. Foam height and
solution level are then measured at five minutes time in order to determine the R5 parameter defined as the ratio of foam
height at five minutes time to initial foam height. The test was conducted for each surfactant at different concentrations in
absence of oil. The most effective surfactants were determined and their foamability and stability were further investigated in
presence of crude oil.
A series of flooding runs were conducted using Core Flooding System - CFS 200 (Figure 2) in order to test the foam efficiency
in improving oil recovery. It consists of core holder capable of housing core samples up to 30.5 cm. The core holder is tapped
with equally spaced high precession pressure transducers for pressure measurements across the core length. Fluids (brine, oil
and surfactant solutions) are injected using ISCO positive displacement pump while gas (CO 2) is flown through flow
controller/meter. Confining pressure was applied using hydraulic pump while pore pressure is implemented at the core outlet
SPE-172185-MS 3

using dome type back pressure regulator. All experiments were conducted at room temperature and confining and pore
pressures of 1000 psi and 200 psi respectively.
Flooding experiment starts with core sample inserted in the core holder. Confining and pore pressure are applied and the
sample is evacuated and pressure saturated for porosity measurement. The sample is flown with brine solution at different
rates and pressure drop across the core samples are reordered and Darcy law is used to determine the core permeability.
Sample is then injected with oil to irreducible water saturation and left overnight. The sample is then secondary flooded with
brine until oil production ceases. Tertiary flooding is started by injecting a slug of 0.2 pore volumes of surfactant solutions
followed by continuous injection of CO2 gas. Recovery and pressure drop is monitored and recorded to test the generated foam
efficiency in controlling gas mobility and improving recovery. To test the potential of foam injection in tertiary gas flooded
reservoir, one more run was conducted subjecting core sample to secondary water flooding and tertiary gas injection. The
residual oil was targeted by slug of 0.2 pore volume of most efficient foaming agent followed by continuous gas injection.

Figure 1: Schematic of foamability and foam stability experiment apparatus.

Figure 2: Schematic of flooding unit.

SPE-172185-MS 4

Results and Discussion

To investigate the foam stability during the foam formation, each surfactant concentration was introduced with gas volumes of
25 and 50 cc during time period of 20 seconds. This corresponds to average volumetric rates of 4.5 and 9 L/hr. Figure 3 is an
example plot of initial foam height of Hitenol H-10 surfactant solutions as a function of surfactant concentration. The figure
shows a two times greater foam height when gas injection was doubled from 4.5 L/hr to 9 L/hr indicating an initial foam
volume equivalent to the dispersed gas and solution volumes lifted by the foam generated. Hence, a stable foam structure was
formed with no significant rupture. Figure 4 summarizes the results for all surfactants solution investigated. All can be
described with good foamability during foam column formation except for Triton X-405 where foam height was increased by
only 50% when gas rate of injection was doubled.

30

25
Foam height, cm

20

15

10

0
0 500 1000 1500 2000 2500
Concentration, ppm

50 cc 25 cc
Figure 3: Foam height versus surfactant concentration of 4% salinity Hitenol H10 solutions at 25 and 50 cc of gas injection.

30
24.3 24 24.5
25
22
Foam Height, cm

20 18.5 18.5

15 13 12.2
12
11 11
10 9

0
Triton X- Triton X- Zonyl FSO Hitenol H- Noigen N- Noigen N-
100 405 10 10 20

25 cc 50 cc

Figure 4: Foam height versus surfactant concentration of 4% salinity surfactant solutions at 25 and 50 cc of gas injection.

The half time decay (t1/2) of foam column is the most common method used to test foam stability. This method can be time
consuming, hence R5 method was used for quick evaluation of foam stability. Figure 5 plots the R5 values as a function of
surfactants concentrations for all surfactants solutions. Except for the Zonyl FSO and Hitenol H-10, all tested surfactants
solutions are characterized as poor stability foamers with full foams rupture at a very short time frame of less than 5 minutes.
Zonyl FSO provided a constant R5 value of 65% at 200 ppm surfactant concentrations and above. Hitenol H-10 surfactant
SPE-172185-MS 5

solutions indicate a low R5 values below 50 ppm concentrations with a sharp increase in R5 between 50 ppm and 150 ppm and
a constant R5 value around 60% above 150 ppm. Accordingly both surfactants are considered metastable as indicated by R5
values above 50% with transition from low stability to high stability within a range of surfactant concentrations. Zonyl FSO
required a wider range of concentrations to reach stability compared to Hitenol H-10 and that can be related to the different
surface activities of the two surfactants.

80
70
60
50
R5 (%)

40
30
20
10
0
1 10 100 1000 10000
Concentration, ppm
Triton X100 Triton x405 Noigen N10
Noigen N20 Zonyl FSO Hitenol H10

Figure 5: Variation of R5 as a function of surfactant concentration of different tested surfactants.

A major concern when applying foam for mobility control is its stability in the presence of oil. Foam stability of Zonyl FSO
and Hitenol H-10 solutions at 4% salinity were tested in presence of light crude oil. Results obtained were compared with
those obtained previously in absence of oil. Figures 6 and 7 compare the foam stability of Zonyl FSO and Hitenol H-10
respectively in presence and absence of crude oil. In presence of oil, Zonyl FSO solutions provide lower foam height at lower
concentrations (Figure 6). No effect was seen at concentrations above 100 ppm. Observations indicate a good foam height but
with some gap in the lower portion of the foam column and low oil lift at concentrations on the range 100 to 300 ppm. Above
600 ppm a good foam structure was obtained with good stability and efficiency in lifting good portion of the oil at the lamellas
skeleton and plateau boarders with no drainage as shown in Figure 8. Figure 7 showed drastic lower foam height for Hitenol
H-10 with very week stability in which foam vanishes as gas injection ceases at concentrations around 100 ppm. As
concentration increases within the range of 150 to 300 ppm, good foam height was observed but with week structure in which
foam vanishes completely within the first minute. As concentration increases above 1000 ppm we obtained a good foam height
with reasonable stability and oil displacing efficiency. Figure 8 presents a snapshot showing oil phase distribution inside the
foam structure accumulating at the plateau borders indicating the strength of Hitenol H-10 foam films. However, lifted oil
drained out of the foam structure within short time frame.
Presence of oil, at the volume fraction implemented, affect the stability of the foam columns. The effect depends on the
surfactant-type and surfactant concentration where stability decreases at low concentrations of Zonyl FSO and at all
concentrations range tested of Hitenol H-10.
SPE-172185-MS 6

80
70
60
50

R5 (%) 40
30
20
10
0
1 10 100 1000 10000
Zonyl - FSO Concentration, ppm

With oil Without oil

Figure 6: Variation of R5 as a function of surfactant concentration of Zonyl FSO in presence and absence of oil.

70

60

50

40
R5 (%)

30

20

10

0
1 10 100 1000 10000
Hitenol - H10 Concentration, ppm

With oil Without Oil

Figure 7: Variation of R5 as a function of surfactant concentration of Hitenol H-10 in presence and absence of oil.

Zonyl FSO Hitenol H10

Figure 8: Effect of oil presence on foam structure and stability at 1000 ppm surfactant concentration diluted in 4% brine.
SPE-172185-MS 7

Now that Zonyl FSO and Hitenol H-10 were selected as the most effective foaming agents, these two surfactants were
investigated in flooding runs. Figure 9 is a plot of oil recovery and total pressure drop across the core sample for water
secondary flooding followed by slug of 1000 ppm Zonyl FSO solution and tertiary gas flooding. Similarly, Figure 10 plots the
oil recovery and pressure drop for water secondary flooding followed by a slug of 1000 ppm Hitenol H-10 and tertiary gas
flooding. The figures indicate that gas injection in presence of surfactant slug improved oil production by 18.5% original oil in
place (OOIP) for Hitenol H-10 compared to 14.71% OOIP for Zonyl FSO. That is equivalent to 31.57% and 28.37% of
residual oil in place for Hitenol H-10 and Zonyl FSO respectively. Comparing the pressure drop across the core for the two
runs, Figure 11 explains the relative improved Hitenol H-10 foaming performance as indicated by the higher pressure drop at
the experimental conditions applied.
One more experiment was conducted on core sample subjected to secondary water and tertiary gas flooding where residual oil
was targeted with 0.2 pore volume of Hitenol H-10 as foaming agent and continuous gas injection. Figure 12 indicates
relatively low incremental oil recovery obtained by tertiary gas injection (9% OOIP) and the role of foaming agent in reducing
the gas mobility and improving the displacement efficiency, producing an additional oil recovery of 14% OOIP. The total
incremental oil recovery from this mode of injection was 23% OOIP, equivalent to 44% ROIP. Comparing this run with the
previous one for Hitenol H-10 discussed earlier, we notice a good performance proving the potential of foam flooding in
tertiary gas flooded reservoirs.

70 40
CO2 Flooding

60 Surfactant Slug
Oil Recovery (% /OOIP)

Water Flooding 30
50

Pressure Drop (psi)

40 4
3 20
30 2
1
20
10
0
10 0 2 4 6 8 10

0 0
0 2 4 6 8 10 12 14
Pore Volume Injected (PVI)

Recovery dPt 6 per. Mov. Avg. (dPt)

Figure 9: Oil recovery and pressure drop at water flooding, 0.2 PV Zonyl FSO and CO2 injection in presence of light crude oil.
SPE-172185-MS 8

70 40
CO2 Flooding
Surfactant Slug
60
Oil Recovery (% /OOIP) 30
50 6

Pressure Drop (psi)

Water Flooding
5
40 4
3 20
30 2
1
20 0
10
0 2 4 6 8 10
10

0 0
0 2 4 6 8 10 12 14
Pore Volume Injected (PVI)
Recovery dPt 6 per. Mov. Avg. (dPt)

Figure 10: Oil recovery and pressure drop at water flooding, 0.2 PV Hitenol H-10 and CO2 injection in presence of light crude oil.

20
18
16
14
12
dP (psi)

10
8
6
4
2
0
0 2 4 6 8 10
Pore Volume Injected (PVI)

Hitenol H-10 Zonyl FSO

Figure 11: Pressure drop across the core during foam injection for Hitenol H-10 and Zonyl FSO.
SPE-172185-MS 9

80 30
CO2 Flooding
70 Surfactant Slug

Oil Recovery (% /OOIP) 60

Pressure Drop (psi)

Water Flooding 6 20
50 CO2 Flooding
5
4
40 3
2
1
30 0
10
0 2 4 6 8 10 12
20

10

0 0
0 2 4 6 8 10 12 14
Pore Volume Injected (PVI)

Recovery dPt

Figure 12: Oil recovery and pressure drop at water flooding, CO2 injection, 0.2 PV Hitenol H-10 and CO2 injection in presence of light
crude oil.

Conclusions
Foamability and foam stability of several anionic and nonionic surfactants were investigated. Foam characteristics were
studied at different surfactants concentrations in absence and presence of crude oil. Based on the screening process, the most
efficient foaming agent (surfactant) was tested in flooding experiments to test their performance in porous medium. The
following are the main outcomes of the work:
1- All surfactants except Triton X-405 showed good formability but Zonyl FSO and Hitenol H-10 surfactants provided
the highest foam longevity in absence of oil.
2- Foamability and foam stability enhances as surfactants concentrations increases.
3- High concentration solutions were characterized by fine and fairly uniform distributed bubble size whereas lower
concentrations clearly reveals a different foam texture with larger bubble sizes and broad distribution.
4- In presence of oil, lower concentration Zonyl FSO solutions provided lower foam stability. Foam stability was not
affected at concentrations above 100 ppm. On the other hand, lower stability was noticed at all concentration range
tested of Hitenol H-10.
5- Hitenol H-10 surfactant was able to carry good portion of the oil but that oil drained out of the foam structure. To the
contrary, oil phase was distributed inside the foam structure of Zonyl FSO accumulating at the plateau borders
indicating the strength of foam films.
6- Foam generation in porous medium provided good tertiary recovery controlling gas mobility and enhancing the
displacement efficiency. More recovery and higher pressure drop were obtained with Hitenol H-10 indicating its
efficiency.
7- Hetinol H-10 Foam injection on tertiary gas flooded reservoirs improves residual oil recovery indicating the potential
of the process even at late stages of gas injection.

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