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88      Hybrid Enhanced Oil Recovery using Smart Waterflooding

          surfactant EOR process are the sulfonated hydrocar-  where n h is the number of hydrophilic groups; H h is the
          bons such as alcohol propoxylate sulfate and alcohol  value of the hydrophilic groups; n l is the number of
          propoxylate sulfonate.                        lipophilic groups; and H l is the value of lipophilic
                                                        groups.
          Hydrophile-lipophile balance
          There are a number of methods to characterize surfac-  Critical micelle concentration, Krafft
          tants. One of the methods is the estimation of  temperature, and cloud point
          hydrophile-lipophile balance (HLB), which describes  Another important characteristic is the critical micelle
          the tendency to solubilize in oil or water. The HLB value  concentration (CMC), which is defined as the concen-
          indicates the tendency of surfactant to form water-in-oil  tration of surfactants when the micelles spontaneously
          or oil-in-water emulsion. The HLB is defined using a  form. The addition of surfactant reduces the interface
          couple of approaches. The studies (Graiffin, 1954;  energy and removes the hydrophobic groups of the sur-
          Griffin, 1949) have defined the HLB value using the  factant from contact with water (Fig. 4.18A). As a result,
          molecular mass of hydrophilic relative to the total mo-  the free energy of the system decreases. When the surfac-
          lecular mass as shown in Eq. (4.12), and the HLB value  tant concentration subsequently increases in the system,
          varies from 0 to 20.                          the surfactant molecules start to aggregate with other
                                                        molecule and micelles form (Fig. 4.18B). The formation
                               20MW h
                          HLB ¼                 (4.12)  of micelles sharply reduces the free energy of the system
                                MW
                                                        by decreasing the contact between the hydrophobic
                                                        groups of the surfactant and water, until the surfactant
          where HLB indicates the value of HLB; MW h is the mo-
                                                        concentration reaches the CMC. The increasing concen-
          lecular mass of the hydrophilic portion of the molecule;
                                                        tration of surfactant above the CMC results in more for-
          and MW is the total molecular mass of the molecule.
                                                        mation of micelles but hardly reduces the free energy of
            The zero of HLB value indicates the completely hy-
                                                        the system. Another factor to be related to CMC is Krafft
          drophobic molecule of surfactant, and the value of 20
                                                        temperature or critical micelle temperature, which is
          corresponds to the completely hydrophilic/lipophilic
          molecule of surfactant. The other approach proposed  defined as a minimum temperature where surfactants
          by Davies (1957) considers the degree of the effect of  can form micelles. Below the Krafft temperature condi-
          hydrophilic group and defines the HLB value with Eq.  tion, no micelles form regardless of the concentration of
          (4.13).                                       surfactant. The cloud point is another parameter to
                                                        illustrate the behavior of nonionic surfactant. It is
                       HLB ¼ 7 þ n h H h   n l H l  (4.13)  defined as the temperature, at which the phase




















                FIG. 4.18 Description of distribution of surfactant molecules (A) below and (B) above CMC. (Caption: From
                Sheng, J. (2011). Modern chemical enhanced oil recovery: Theory and practice. Amsterdam, Boston, MA: Gulf
                Professional Pub.)
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