Chapter 10

Surfactants
Surface active agents are included in most aqueous treating fluids to improve the
compatibility of aqueous fluids with the hydrocarbon-containing reservoir. To
achieve a maximal conductivity of hydrocarbons from subterranean formations
after fracture or other stimulation, it is the practice to cause the formation
surfaces to be water-wet.
Alkylamino phosphonic acids and fluorinated alkylamino phosphonic acids
adsorb onto solid surfaces, particularly onto surfaces of carbonate materials in
subterranean hydrocarbon-containing formations, in a very thin layer. The layer
is only one molecule thick and thus significantly thinner than a layer of water
or a water-surfactant mixture on water-wetted surfaces (Penny, 1987a,b; Penny
and Briscoe, 1987).
These compounds so adsorbed resist or substantially reduce the wetting of
the surfaces by water and hydrocarbons and provide high interfacial tensions
between the surfaces and water and hydrocarbons. The hydrocarbons displace
injected water, leaving a lower water saturation and an increased flow of
hydrocarbons through capillaries and flow channels in the formation.

PERFORMANCE STUDIES
The primary purpose of surfactants used in stimulating sandstone reservoirs is
to reduce the surface tension and the contact angle thus to provide control of
the fluid loss. However, many of the surfactants are adsorbed rapidly within
the first few inches of the sandstone formations. In this way, their effectiveness
with respect to deeper penetration is reduced.
Experimental and field studies of various surfactants used in the oilfield have
been described (Paktinat et al., 2007).
Several different surfactants were investigated to determine their adsorption
properties when injected into a laboratory sandpacked column. In addition,
field data were collected from Bradford, Balltown, and Speechley sandstone
formations. The correlation between laboratory and field data was confirmed.
Reservoirs that were treated with microemulsion fluids demonstrate
exceptional water recoveries when compared with conventional surfactant
Hydraulic Fracturing Chemicals and Fluids Technology. http://dx.doi.org/10.1016/B978-0-12-411491-3.00010-8
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treatments. These investigations are considered to serve as case studies and

can be used to minimize formation damage (Paktinat et al., 2007).

VISCOELASTIC SURFACTANTS
Typical viscoelastic surfactants are N-erucyl-N,N-bis(2-hydroxyethyl)-Nmethyl ammonium chloride and potassium oleate, solutions of which form
gels when mixed with corresponding activators such as sodium salicylate and
potassium chloride (Jones and Tustin, 2007).
A methyl quaternized erucyl amine is useful for aqueous viscoelastic
surfactant-based fracturing fluids in high-temperature and high-permeability
formations (Gadberry et al., 1999).
A problem associated with the use of viscoelastic surfactants is that stable
oil-in-water emulsions are often formed between the low-viscosity surfactant
solution, i.e., the broken gel and the reservoir hydrocarbons. As a consequence,
a clean separation of the two phases may be difficult to achieve, complicating
the cleanup of wellbore fluids. Such emulsions are believed to form because
conventional wellbore fluid viscoelastic surfactants have little or no solubility
in organic solvents (Jones and Tustin, 2007).

Cationic Surfactants
A number of cationic surfactants, based on quaternary ammonium and
phosphonium salts, are known to exhibit solubility in water and hydrocarbons
and are frequently as such used as phase-transfer catalysts (Starks et al., 1994).
However, the particular cationic surfactants which form viscoelastic
solutions in aqueous media are poorly soluble in hydrocarbons, and are
characterized by partition coefficients K o,w for a surfactant in oil and water
close to zero.
The partition coefficient of a substance is the ratio of the concentrations in
equilibrium in two non-miscible fluids, such as oil and water.
K o,w =

co
.
cw

(10.1)

The partition coefficient can be determined by various analytical techniques

(Sharaf et al., 1986).
For example, cyclic voltammetry has been used for the determination of
the critical micelle concentration of surfactants, self-diffusion coefficient of
micelles, and the partition coefficient (Mandal and Nair, 1991). Also, highperformance liquid chromatography is a suitable technique (Terweij-Groen
et al., 1978).
Typically, the high solubility of a cationic surfactant in hydrocarbon solvents
is promoted by multiple long-chain alkyl groups attached to a head group, as can

CHAPTER | 10 Surfactants

123

be found in hexadecyltributylphosphonium ions and trioctylmethylammonium

ions.
In contrast, cationic surfactants which form viscoelastic solutions generally
have only one long straight hydrocarbon chain per surfactant head moiety (Jones
and Tustin, 2007).

Anionic Surfactants
A few anionic surfactants exhibit a high solubility in hydrocarbons but low
solubility in aqueous solutions. A well-known example is sodium bis (2ethylhexyl) sulfosuccinate (Manoj et al., 1996). This compound does not form
viscoelastic solutions in aqueous media. So, the addition of a salt causes
precipitation. Thermodynamic studies suggest that the micellization process
is endothermic in nature so that it is mainly an entropy governed process.
The solubility of a surfactant in hydrocarbon tends to increase as the size
of the side chain decreases. It is believed that this occurs because smaller
side chains cause less disruption to the formation of inverse micelles by the
surfactant in the hydrocarbon, such inverse micelles promoting solubility in the
hydrocarbon (Jones and Tustin, 2007).
By altering the degree and type of branching from the principal straight
chain, the surfactant can be tailored to be more or less soluble in a particular
hydrocarbon. Preferably the side chain is bonded to the -carbon atom. By
locating the side chain close to the charged head group promotes the most
favorable combinations of viscoelastic and solute properties. The synthesis of
a -branched fatty acid is shown schematically in Figure 10.1.
Preparation 10.1. Synthesis of 2-methyl methyl oleate (Jones and Tustin,
2007): Sodium hydride is washed with heptane and then suspended in
tetrahydrofuran. 1,3-Dimethyl-3,4,5,6-tetrahydro-2(1H)-pyrimidinone is then
added and the mixture is stirred in a nitrogen atmosphere. Then methyl oleate
O
O

CH3

CH3CuLi
CH3 O
O

CH3

OH-, H+
CH3 O
OH
FIGURE 10.1

Synthesis of -branched fatty acids (Jones and Tustin, 2007).

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O
O

NaH
CH3

CH3

CH3
O

OH-

CH3

CH3
O
OFIGURE 10.2

Synthesis of 2-methyl methyl oleate (Jones and Tustin, 2007).

is dropwise added over a period of 2 h and the resulting mixture is heated to

reflux for 12 h and then cooled to 0 C.
Further, methyl iodide is added dropwise and the reaction mixture is again
heated to reflux for a further 2 h. Afterwards the reaction mixture is cooled
to 0 C and quenched with water, concentrated in vacuo and purified by
column chromatography to give the end product 2-methyl methyl oleate as a
yellow oil.

The synthesis of 2-methyl methyl oleate and the subsequent hydrolysis of
the ester is shown in Figure 10.2. A rigid gel is formed when a 10% solution of
potassium 2-methyl oleate is mixed with an equal volume of a brine containing
16% KCl.
Contacting this gel with a representative hydrocarbon, such as heptane,
results in a dramatic loss of the viscosity and the formation of two low-viscosity
clear solutions:
1. An upper oil phase.
2. A lower aqueous phase.
The formation of an emulsion was not observed. Thin-layer chromatography
and infrared spectroscopy showed the presence of the branched oleate in both
phases.
The gel is apparently broken by a combination of micellar rearrangement and
dissolution of the branched oleate in the oil phase. Consequently the breaking
rate of the branched oleate is faster than that of the equivalent linear oleate. This
is demonstrated in Figure 10.3 which is a graph of gel strength against time
at room temperature for an unbranched potassium oleate gel and a branched
potassium 2-methyl oleate gel.
Both gels were prepared from 10% solutions of the respective oleate mixed
with equal volumes of a brine containing 16% KCl. Each gel was then contacted
with an equal volume of heptane.

CHAPTER | 10 Surfactants

125

Potassium oleate
2-Methyl potassium oleate

Gel strength code

3.5
3
2.5
2
1.5
1
0

10

12

14

Break time/[h]
FIGURE 10.3

Gel strength versus time (Jones and Tustin, 2007).

'

TABLE 10.1 Gel Strength Codings (Jones and Tustin, 2010)

Number

Description

1
2

Original viscosity
Weak flowing gel

3
4

Tonguing gel
Deformable nonflowing gel

&

The gel strength is a semiquantitative measure of the flowability of the

surfactant-based gel relative to the flowability of the precursor fluid before
addition of the surfactant. There are four gel strength codings. These codings
are summarized in Table 10.1.
Using infrared spectroscopy, the value of K ow for the potassium 2-methyl
oleate of the broken branched gel was measured as 0.11. In contrast the value
of K ow for the potassium oleate of the broken unbranched gel was measured as
effectively zero.
The rapid breakdown of the branched oleate surfactant gels, with little or no
subsequent emulsion, leads to the expectation that these gels will be particularly
suitable for use as wellbore fluids, such as fluids for hydraulic fracturing of oilbearing zones. Excellent cleanup of the fluids and reduced impairment of zone

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Hydraulic Fracturing Chemicals and Fluids Technology

matrix permeability can also be expected because emulsion formation can be

avoided (Jones and Tustin, 2007).

Anionic Brominated Surfactants

In the case of ionic surfactants, an excess of counterions reduces the repulsive
interaction between the charged head groups. The surfactant molecules at both
ends of such cylindrical aggregates bear an excess of energy in comparison to
the molecules in the inner of the cylindrical part. This excess energy is addressed
as end cap energy and it is the driving force for the linear growth of cylindrical
micelles. Subsequently, the micelles entangle with each other, which results in
a viscoelastic behavior (Lee et al., 2010).
A problem associated with the use of such surfactants is the potential
formation of stable oil in water emulsions during a cleanup operation. This
behavior arises due to the limited solubility in hydrocarbon of conventional
viscoelastic surfactants.
However, it has been demonstrated that a conventional surfactant, such as
potassium oleate, can be brominated and in this way the properties are improved
(Lee et al., 2010). The bromination of oleic acid is done in a hexane solution to
which a solution of HBr in acetic acid is added. In this way 9-bromo stearate is
obtained.
The partition coefficient and the gel break time for various concentrations
of 9-bromo stearate and potassium oleate in 8% KCl solution are shown in
Table 10.2. As can be seen from Table 10.2, the bromination causes a significant
change in the partition coefficient, but does not change the gel break time.
Furthermore, the bromination of the hydrocarbon chain keeps the
viscoelasticity of the surfactant. Thus, the essential property for oilfield
applications is maintained. When the shear stress is removed in the formation,
the solution reverts to its viscous state. However, the bromination reduces the
zero shear viscosity from 528 Pa s to 180 Pa s. In contrast, the shear viscosity
at 100 s1 is reduced from 0.48 Pa s to 0.16 Pa s by the bromination at a
concentration of 5% in 8% KCl.

'

TABLE 10.2 Partition Coefficient and Gel Break Time (Lee et al., 2010)
Concentration (%)

Partition (%)
BST
OLE

Gel Break Time (h)

BST
OLE

1
5
10

17.1
13.28
13.49

12
82
94

BST 9-Bromo stearate and OLE Oleate.

&

0
0
0

14
84
98

CHAPTER | 10 Surfactants

127

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