SPE 123060

Effect of Some Physicalchemical Variables on the Formation and Stability

of Foam in an Oil-Air System and Their Correlation With the Formation of
Foamy Crude Oil
L. Marcano, SPE, X. Gutierrez, SPE, PDVSA Intevep; B. Perez, UNEXPO; E. Martínez; PDVSA Intevep

Copyright 2009, Society of Petroleum Engineers

This paper was prepared for presentation at the 2009 SPE Latin American and Caribbean Petroleum Engineering Conference held in Cartagena, Colombia, 31 May–3 June 2009.

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
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Abstract

There are crude oil reservoirs, in Venezuela, where the foam generation or production combined with the crude oil has
become a problem. Consequently the net volume of produced crude oil decreases and the problem is more severe in some
reservoirs than in others. So far any effective techniques or methods have not been created in order to solve this problem.
Neither there has been any systematic study which may explain why the foamy crude oil is produced, or why some foamy
crude oil are more stable than others. The purpose of this paper was to find out the mechanism of formation and stabilization
of the foam in the crude oil. The initial investigation was related to study a engine oil (Diesel)-air system which simulated the
crude oil-gas system and the formation and stabilization variables, which affect the foam production. Finally the results were
correlated with the crude oil-gas system, through exposition of hypothesis. Afterward we will work with the crude oil-gas
systems. The method used to create or produce foam consisted in bubbling air in the engine oil phase containing surfactant,
alcohol and water different concentrations. The tests basically were carried out to different air flow in order to determine
the static stability or the lifetime of the foam produced. The foamability and stability foam were plotted as a function of the
air flow. The results indicated that the foam production in the oil is not affected by the increase in the surfactant
concentration, but it is improved with the increase of the dispersed water content in the oil. However, the favorable effect of
the dispersed water on the foamability is related to the alcohol concentration dissolved in the oil. The most important
conclusion is that the presence of dispersed water in the oil is responsible of the foam formation.

Introduction
Most of the petroleum reservoirs contain mixed water and gas with the crude oil, which is necessary to have production
methods that separate the water and the gas of the crude oil. In general, the petroleum producing countries have methods to
control and to separate the water of the crude oil. However, in the case of gas control and separation, it is different, since the
methods used in their majority are empirical. This is because the mechanism of foam formation and stabilization in the crude
oil is not known clearly. The necessity to know this mechanism in the crude oil-gas system is because with this information
could be known the crude oil will produce stable or unstable foam, and consequently to propose methods to inhibit or to
break the formed foam.
There are many crude oil reservoirs in Venezuela that produce foamy crude oil, which originates a series of problems
throughout the petroleum production chain, such as; problems of dehydration, quantification of production, spill of
petroleum, delivery of specifications outside products. In order to solve these problems, techniques and/or procedures are not
had that inhibit or break the foam when it appears. Therefore, in this investigation it was studied the mechanism of formation
and stabilization nonaqueous foams, in order to obtain techniques and procedures that help to eliminate the problem of the
foamy crude oil production. In order to develop this objective, a cleaner system that the crude oil-gas system, as is the
engine oil (Diesel)-air system was evaluated, through study of foam formation and stabilization some variables. The results
were correlated with crude oil-gas systems, through exposition of hypothesis. The crude oil-gas systems will be studied in
later investigations.

There is much literature on the formation and stability of foam at the water-air systems or aqueous foam, but little
information on nonaqueous foam. In general, the same theory is used to explain the aqueous and nonaqueous systems. The
main theories on foams are related to the effect of a surfactant on the surface tension and surface viscosity1-3. In the case of
2 SPE 123060

foamy crude oil, is reported in the literature that the Natural Surfactants as the asphaltenes help in the foam formation and
stabilization in the heavy crude oil4,5. However, it is difficult to study and to understand the interfacial phenomena at the
crude oil- asphaltenes -gas system through studies of surface tension, because, in this system there are not two phases with
hydrophobic and hydrophilic characteristics clearly defined. Therefore, the surfactant cannot be adsorbed efficiently at the
crude oil -gas interface with its polar group towards the hydrophilic phase and its nonpolar group towards the hydrophobic
phase. Literature reports that the air phase can be considered as a hydrophobic phases similar to the oil phase6. The
hypothesis that the presence of a aqueous phase at the crude oil-gas system is necessary so that it facilitates the foamy crude
oil formation and stabilization is propose in this investrigacion. There is little information in literature on the variation of
the foamability with the phases humidity in a nonaqueous foam. Masatoshi et al7 studied the effect of the humidity on the
foamability and stability of the some systems and the results showed that in the nonaqueous foam formation, there is a
nonaqueous foam layer that contains water in the surface or within the layer. In addition, in this study was observed that there
was an optimal water concentration in which the foam stability improved. Other authors as Shrestha et al.8 have studied the
effect of added water on the foaming properties of diglycerol fatty acid ester nonionic surfactant system. The surfactant could
not foam in nonpolar oils squalane and hexadecane at normal room temperature. Homever, addition of a small amount of
water induces a dramatic change in foaming properties. Both the foamability and foam stability increases with the amount of
added water within the studied concentration range. On the other hand, Callaghan et al.9-13 have observed that crude oil foam
lifetime is related to bulk viscosity and to surface rheology properties. They associate foam stability with short-chain
carboxylic acids and phenols that are present in the crude oil, with a molecular weight ≤ 400. Most people during the daily
activities have contact with foam, can be said that different methods exist to form a foam, from most common and
unconscious like when the clothes, plates, the hair and the teeth are washed until the controlled technical methods like the
Rosse Miles method12, the Bickerman method13 and the methods by gas bubbling. Independently of the method used, three
(3) components are basically required to form a foam: a liquid phase, a gaseous phase and a chemical substance with surface
activity.

The structure of a foam is composed of lamellae or thin films joined together to form distorted polyhedral shaped cells. In a
foam, the gas bubbles or cells are separated from each other by thin films of liquid. These films or lamellae have thin layers
of “bulk” liquid sandwiched between two liquid-gas interfaces. The liquid-gas interfaces could be described as a two-
dimensional metastable phase1. The degree of stability of the film depends on the bulk liquid viscosity and the effects due to
the adsorption of a surfactant at the liquid-gas interface3.

When three or more gas bubbles meet, the lamelae are curved, concave to the gas cells, forming what is called the Plateau
border or Gibbs triangles1. From this point of view, a foam can be considered as a complex capillary system, where the
Plateau border form a liquid column three-dimensional network of triangular form and interconnected.

Experimental Study
The system used to simulate the crude oil-gas system and to produce foamy crude oil, was a engine oil (Diesel) containing
high concentration of aromatic compounds (36% w/v), compressed air as the gas phase and a surfactant that is a fatty acids
mixture (C16-C18) and its salts generated by the reaction with the Monoethanolamine (MEA). This surfactant was used to
simulate the Natural Surfactants (NS) presents in most of the Venezuelans crude oil, which are acids crude oil. With this
system was generated the foam in presence and absence of the surfactant, water and an alcohol of short chain as the
Hexanol different concentrations. The surface tension of the crude oil-surfactant-air system was determined using the
Wilhelmy plate method.

Description of the Equipment Used to Measure Foamability and Foam Stability at the Solutions.
The foam is formed in an equipment ( figure 1) which consists of a cylinder that contains compressed air to 1500 psi, and a
pressure controller is put in the exit of the cylinder, to regulate the pressure of unloading towards the equipment. The air that
go out the cylinder is dried, making pass it through a filter and a packing of Silica. After the air flow pass through a glass
tube, which has a part submerged in the solution to foam and a porous glass filter in the inferior part to facilite the formation
of the bubbles. The solution is contained in a glass column, volumetrically calibrated and to atmospheric pressure. The tests
consisted in bubbling air to different flows for each surfactant concentration, through porous glass filter submerged in the
solution. The solution is formed by the Diesel, the fatty acids and its salts surfactant mixture, in presence and absence of
water and alcohol.

Determination of the Solution Foamability and Foam Stability.

In order to determine the foamability and stability of the solution, the following tests were carried out: a) Bubbling of air to
the Diesel solutions, using the following rates of flow: 20, 60, 100, 160 and 200 ml/min, in presence and absence of
surfactant different concentrations, (0.1 - 5) % v/v. The volume of the Diesel solution was of 500 ml. b)Bubbling of air to
the Diesel solution containing a constant concentration of surfactant (7%w/v Fatty acids mixture/0.7% w/v MEA ) and
alcohol (1% w/v), in the presence of water different concentrations ((0-5% v/v). c) b)Bubbling of air to the Diesel solution
SPE 123060 3

containing a constant concentration of surfactant (7% Fatty acids mixture/0.7% MEA ) and varying the water/alcohol
relation. The rates of air flow used in (b) and (c) tests were same to (a) test.

In order to measure the solution foamability and foam stability, during the tests was registered the volume corresponding to
the maximum height that reaches the foam, the solution volume that did not produce foam, the time to reach the maximum
height (formation time), time of foam rupture (lifetime) and the pressure of air injection in the solution. The foamability is
calculated by the equation:
φ = [(Vmax – Vsol)/ Vmax]*100
Where:
φ:foamability ,%
Vmax: Volume corresponding to the maximum height reached in the column
Vsol: Volume initial in the column

Analysis of the Results

Surface Tension: The Table 1 shows the variation of the surface tension with the surfactant concentration at the Diesel-air
system, and can be observed that the surface tension varies very little with the increase of the surfactant concentration. This
result is in agreement with the literature that reports that at an oil-air interface, the air is considered as a hydrophobic phase
similar to the oil. Consequently, the polar part of the surfactant does not find a hydrophilic phase to interact and the
surfactant adsorption at the oil-air interface will be very deficient6.

Foamability

The figure 2 shows the variation of the foamability with the air flow to the Diesel solutions in presence and absence of
surfactant differents concentrations and can be observed that the foamability varies very little with the surfactant
concentration. The results are in agreement with the result of the surface tension (Table 1), where is observed that the surface
tension of the Diesel-surfactant-air system not vary with the surfactant concentration and therefore the capacity of system
foamability remain constant.
The figure 3 shows the variation of foam lifetime with the air flow to the Diesel solution, in presence and absence of
surfactant differents concentrations and can be observed that the stability of the foam does not vary with the surfactant
concentration. Theoretically the foam stability depends of the effects due to the adsorption of a surfactant at the liquid-gas
interface, by example, the surface viscosity1. Therefore, at the Diesel-surfactant-air system is hoped that the foam stability
remains constant since the surface tension vary little with the surfactant concentration.

The figure 4, shows the variation of the foamability with the injected air flow to the Diesel-surfactant-Water/Alcohol
solution, containing water differents concentrations and keeping constant the surfactant and alcohol concentration. The
results show that the solution foamability improvement when the water concentration is increased and the effect is more
remarkable between 2 to 5% of water.

In order to explain the results of figure 4, the hypothesis propose is the following: when the water is present in the system,
the bubbles formed will be surrounded by water and dispersed in the Diesel , originating an air/water/Diesel multiple
emulsion stabilized by the surfactant. In the figure 5 is shown a hypothetical diagram, where the air is dispersed in the water
forming the bubbles, and these bubbles are dispersed in the Diesel. As the surfactant is a fatty acids mixture (C16-C18) of
different molecular weight and its salts generated with MEA, the salts of lower molecular weight can be desorbed towards the
water and adsorbed at the air– water interface, with its hydrophobic part interacting with the air and the hydrophilic part
interacting with the water. The acids and salts of higher molecular weight will be adsorbed at the Diesel-water interface. This
same mechanism could be happening in the crude oil– air system, since by the general in the crude oil reservoirs are presents
the crude oil, air and water interacting among them. The Natural Surfactants, for example, the differents molecular weight
carboxylics acids presents in the crude oil could promote the formation and stabilization of the foam, through the multiple
emulsion formation. If this is thus, to understand the mechanism by which the foam and multiple emulsion are formed could
help to break or to inhibit the formation of the foam.

The results reported in the figure 6, support previously discussed and the proposed scheme to explain the results of the figure
4, since in the figure 6 it is observed that the foam stability improves with the increase of the water concentration.

The figure 7 shows the obtained results of the foamability solution with water:alcohol differents relations and can be
observed that the water:alcohol relation affects the foamability solution. For example, when the water:alcohol relation is
equal to 1, the foamability diminishes in comparison to when the water:alcohol relation is greater than 1. These results can be
4 SPE 123060

explained considering that the alcohol can behave in the system as a cosolvent and/or cosurfactant, depending on the
water:alcohol relation existing. Probably when in the system the water:alcohol relation is equal to 1, the alcohol acts as a
cosolvent, helping the water to dissolve in its interior to the lower molecular weight salts presents in the surfactant mixture.
Consequently the effective adsorption of these salts at the air-water interface diminishes, inhibiting the foam formation. On
the other hand, when the water:alcohol relation is greater than 1, the alcohol could act as a cosurfactant adsorbing at the air-
water interface together with the lower molecular weight surfactants, promoting the diminution of the surface tension, and
allowing the foam formation more efficiently. A hypothetical diagram is shown in the figure 8. The given discussion
considers the hypothesis of the air-water-oil multiple emulsion formation when is present the water in the system, as it was
discussed previously. These last results could help to understand because in the crude oil-air-water system; the alcohols can
work as a antifoaming and/or defoaming (foam breakers)13. However, can be that it depends of the alcohol concentration.

Conclusions

1. Stable foam can not be obtained when the air is bubbled on a Diesel solution, if the dispersed water concentration in the
solution is lower that 2%.
2. The foamability of the Diesel-surfactant solution improvement with the increase of the dispersed water concentration in
the Diesel.
3. The n-Hexanol can promote or inhibit the foamability of the Diesel-surfactant solution depending of the water:n-hexanol
relation that exists in the solution.

Nomenclature

NS Natural Surfactant
MEA Monoethanolamine
φ Foamability
Vmax Volume corresponding to the maximum height
reached in the column
Vsol Volume initial in the column
PM Pressure measurer
PR Pressure controller
MF Measurer of flow

References

1. Schmidt, D.: “Nonaqueous Foams”, Foams: Theory, Measurement and Appications”. (R.K.Prud’homme and S.A. Khan, eds.), Marcel
Dekker, New York/ USA, 1996, pp.287-314.
2. Schramm, L (ed).: Foams, Fundamentals and Applications in the Petroleum Industry ACS Symp. Serie. 242 American Chemical
Society, Washington DC USA 1994.
3. Langevin, D.: “Foams, Foam Films, and Monolayers”. Adsorption and Aggregation of Surfactants in Solution. (K.L. Mittal and D.O.
Shah., Eds). Marcel Dekker, New York/ USA,2003, pp. 453-464.
4. Bauget, F., Langevin, D. and Lenormand, R: “Dynamic Surface Properties of Asphaltenes and Resins at the Oil-Air Interface”.
Journal of Colloid and Interface Science. 239, 501-508 (2001).
5. Cassani, F., Ortega, P., Davila, A., Rodriguez, W., and Serrano, J. “Evaluation of Foam Inhibitors at the Jusepin Oil/Gas Separation
Plant, El Furrial Field, Eastern Venezuela”. SPE Paper 23681, Second Latin American Petroleum Engineering Conference, II LAPEC,
Caracas, Venezuela, 1992.
6. Rosen, M.: “Reduction of Surface and Interfacial Tension by Surfactants”.Surfactants and Interfacial Phenomena. (Wiley Interscience,
2nd ed), 1989, pp 207-238.
7. Masatoshi, S.,Michiyo, T., Teiji, K. and Noburo, S.: “Foaming Ability of Nonaqueous Fluid with Dextrin Fatty Acid Esters Having
Different Carbon Chains”. Journal of the Japan Society of Colour Material. Vol 76; Nº 3. pp, 93-96, 2003.
8. Shrestha, L.,Shrestha, R., Solans, C. And Aramaki, K.: “Effect of water on Foaming Properties of Diglycerol Fatty Acid Ester-Oil
Systems”. Langmuir 2007, 23, 6918-6926.
9. Callaghan, I., Gould, C., Reid, A., Callaghan, I., and Seaton, D. “Crude Oil Foaming Problems at the Sullom Voe Terminal”. J. Pet.
Technol. 1985, 2211.
10. Callaghan, I., and Neustadter, E., “Foaming of Crude Oils: A Study of Non-Aqueous Foam Stability”. Chem. Ind. January, 53, 1981.
11. Callaghan, I., Mckechenie, A., Ray, J., and Wainwright, J., “Identification of Crude Oil Components Responsible for Foaming”. Soc.
Pet. Eng. J. April, 171, 1985.
12. Ross, J. and Miles, G ., Am. Soc. for Testing Materials, Method D1173-53, Philadelphia, PA, 1953; Oil and Soap 18, 99, 1941.
13. Bikerman, J., Foams, Springer-Verlag, New York USA, 1973.
14. Pugh, R.,: “Foaming, Foam films, Antifoaming and Defoaming”. Advances in Colloid and Interface Science. 64, pp. 67-142, 1996.
SPE 123060 5

Surfactant, % Surface Tension, Dynes/cm

0 28,175
0,1 27,700
0,5 28,492
1,0 28,458
2,0 27,923
5,0 28,192

Table 1. Variation of the surface tension as a function of the Fatty acids mixture surfactant

PM PM

packing of silice
PM 250 Ml/min
MF
PR
Filter air 0

PM PM

Air

PM:pressure measurer
PR:pressure controller Diesel Oil-
MF:Measurer of flow Surfactant

Fig 1. Schematic diagram of the equipment used to form the foam and to determine its properties
6 SPE 123060

45,00

40,00

35,00
Foamability, %

30,00

25,00

20,00

15,00
Surfactant Concentration (ppm
10,00

5,00 0 1.000 5.000 10.000 20.000 50.000

0,00
0 50 100 150 200 250

Air Flow, mL/min

Fig 2. variation of the foamability as a function of the air flow for Diesel oil solutions in presence and absence
of surfactant differents concentrations

5 0 ,0 0
4 5 ,0 0
S u rfa c ta n t C o n c e n tra tio n (p p m
4 0 ,0 0 0 1 .0 0 0 5 .0 0 0 1 0 .0 0 0 2 0 .0 0 0 5 0 .0 0 0
3 5 ,0 0
Lifetime, sec

3 0 ,0 0
2 5 ,0 0
2 0 ,0 0
1 5 ,0 0
1 0 ,0 0
5 ,0 0
0 ,0 0
0 50 100 150 200 250
A i r F l o w , m l /m i n
Fig 3. variation of foam lifetime as a function of the air flow for the Diesel oil solution, in presence and absence of surfactant
differents concentrations
SPE 123060 7

100,00
90,00
80,00
Foamability, %

70,00
60,00
50,00
40,00
30,00
20,00 Water Concentration, % v/v
10,00 0 0,5 1 1,5 2 3 5
0,00
0 50 100 150 200 250
Air Flow, ml/min

Fig 4.Variation of the foamability as a function of the air flow at the Diesel oil-surfactant-Water-Alcohol solution, containing water
differents concentrations and keeping constant the surfactant and alcohol concentration.

Oil

Surfactant of lower molecular weight adsorbed at the air-water interface

Air
Surfactant of higher molecular weight adsorbed at the oil-water interface

Water

Oil

Fig 5. Hypothetical diagram to illustrate the multiple emulsion formation without taking into account the alcohol effect.
8 SPE 123060

700,00
600,00
500,00
Lifetime, sec
W ater Concentration, %v/v
400,00
0 0,5 1 2 3 5
300,00
200,00
100,00
0,00
0 50 100 150 200 250
Air Flow, ml/min

Fig 6. Variation of foam lifetime as a function of the air flow at the Diesel oil solution, in presence and absence of water differents
concentrations

100,00
90,00
80,00
Foamability, %

70,00
60,00
50,00
40,00
30,00
20,00 W ater/Alcohol relation, %
10,00 2:2 1:1 5:1 2:1
0,00
0 50 100 150 200 250
Air Flow, ml/min
Fig 7. Variation of the foamability as a function of the air flow at the solution diesel oil containing, varying the water/alcohol relation
and a constant concentration of surfactante.
SPE 123060 9

Oil Surfactant of lower molecular weight adsorbed at the air-water interface

Surfactant of higher molecular weight adsorbed at the oil-water interface

Air

Water Cosurfactant (Alcohol) adsorbed at the aire-water interface

Oil

Fig 8. Hypothetical diagram to illustrate the multiple emulsion formation taking into account the alcohol effect.