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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
2013 Elsevier Inc. All rights reserved.
121
122
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)
CHAPTER | 10 Surfactants
123
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
124
NaH
CH3
CH3
CH3
O
OH-
CH3
CH3
O
OFIGURE 10.2
CHAPTER | 10 Surfactants
125
Potassium oleate
2-Methyl potassium oleate
3.5
3
2.5
2
1.5
1
0
10
12
14
Break time/[h]
FIGURE 10.3
'
Description
1
2
Original viscosity
Weak flowing gel
3
4
Tonguing gel
Deformable nonflowing gel
&
126
'
TABLE 10.2 Partition Coefficient and Gel Break Time (Lee et al., 2010)
Concentration (%)
Partition (%)
BST
OLE
1
5
10
17.1
13.28
13.49
12
82
94
&
0
0
0
14
84
98
CHAPTER | 10 Surfactants
127
REFERENCES
Gadberry, J.F., Hoey, M.D., Franklin, R., Del Carmen Vale, G., Mozayeni, F., 1999. Surfactants
for hydraulic fracturing compositions. US Patent 5 979 555, assigned to Akzo Nobel NV, 9
November 1999.
Jones, T.G.J., Tustin, G.J., 2007. Surfactant comprising alkali metal salt of 2-methyl oleic acid
or 2-ethyl oleic acid. US Patent 7 196 041, assigned to Schlumberger Technology Corp.,
Ridgefield, CT, 27 March 2007. <http://www.freepatentsonline.com/7196041.html>.
Jones, T.G.J., Tustin, G.J., 2010. Process of hydraulic fracturing using a viscoelastic wellbore fluid.
US Patent 7 655 604, assigned to Schlumberger Technology Corp., Ridgefield, CT, 2 February
2010. <http://www.freepatentsonline.com/7655604.html>.
Lee, L., Salimon, J., Yarmo, M.A., Misran, M., 2010. Viscoelastic properties of anionic brominated
surfactants. Sains Malays. 39 (5), 753760.
Mandal, A.B., Nair, B.U., 1991. Cyclic voltammetric technique for the determination of the
critical micelle concentration of surfactants, self-diffusion coefficient of micelles, and
partition coefficient of an electrochemical probe. J. Phys. Chem. 95 (22), 90089013.
http://dx.doi.org/10.1021/j100175a106.
Manoj, K.M., Jayakumar, R., Rakshit, S.K., 1996. Physicochemical studies on reverse micelles of
sodium bis(2-ethylhexyl) sulfosuccinate at low water content. Langmuir 12 (17), 40684072.
http://dx.doi.org/10.1021/la950279a.
Paktinat, J., Pinkhouse, J.A., Williams, C., Clark, G.A., Penny, G.S., 2007. Field case studies:
damage preventions through leakoff control of fracturing fluids in marginal/low-pressure gas
reservoirs. SPE Prod. Oper. 22 (3), 357367.
Penny, G.S., 1987a. Method of increasing hydrocarbon production from subterranean formations.
US Patent 4 702 849, 27 October 1987.
Penny, G.S., 1987b. Method of increasing hydrocarbon productions from subterranean formations.
EP Patent 234 910, 2 September 1987.
Penny, G.S., Briscoe, J.E., 1987. Method of increasing hydrocarbon production by remedial well
treatment. CA Patent 1 216 416, 13 January 1987.
Sharaf, M.A., Illman, D.L., Kowalski, B.R., 1986. Chemometrics. Wiley, New York.
Starks, C.M., Liotta, C.L., Halpern, M., 1994. Phase-transfer catalysis: fundamentals, applications,
and industrial perspectives. Chapman & Hall, New York.
Terweij-Groen, C.P., Heemstra, S., Kraak, J.C., 1978. Distribution mechanism of ionizable
substances in dynamic anion-exchange systems using cationic surfactants in high-performance
liquid chromatography. J. Chromatogr. A 161, 6982. http://dx.doi.org/10.1016/S0021-9673
(01)85213-4.