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    RE V I E W A RT I CL E

    A Review of Gemini Surfactants: Potential Applicationin Enhanced Oil Recovery

    Muhammad Shahzad Kamal1

    Received: 16 May 2015 / Accepted: 7 December 2015/ Published online: 26 December 2015 AOCS 2015

    Abstract Gemini surfactants are a group of novel sur-

    factants with more than one hydrophilic head group andhydrophobic tail group linked by a spacer at or near the

    head groups. Unique properties of gemini surfactants, such

    as low critical micelle concentration, good water solubility,

    unusual micelle structures and aggregation behavior, high

    efficiency in reducing oil/water interfacial tension, and

    interesting rheological properties have attracted the atten-

    tion of academic researchers and field experts. Rheological

    characterization and determination of the interfacial ten-

    sion are two of the most important screening techniques for

    the evaluation and selection of chemicals for enhanced oil

    recovery (EOR). This review deals with rheology, wetta-

    bility alteration, adsorption and interfacial properties ofgemini surfactants and various factors affecting their per-

    formance. The review highlights the current research

    activities on the application of gemini surfactants in EOR.

    Keywords Gemini surfactants Enhanced oil recovery

    Rheology Interfacial tension Surface tension

    Introduction

    Background of Enhanced Oil Recovery (EOR)

    Enhanced oil recovery (EOR) or tertiary oil recovery is a

    technique to recover additional oil remaining in reservoirs

    after primary and secondary recovery processes. In primary

    oil recovery, oil is recovered using natural pressure of oil

    reservoirs, while in secondary recovery water is injected todisplace the oil. The EOR methods that have been used are

    summarized in Fig.1. Thermal EOR, gas injection, and

    chemical EOR (cEOR) are the most commonly used EOR

    methods. In cEOR, a high recovery rate can be achieved by

    increasing the dimensionless capillary number, which is

    defined as the ratio of viscous forces to inertial forces [1

    3]. An ultra-low interfacial tension (IFT) in the range of

    10-3 mN/m is required to obtain a capillary number high

    enough for effective oil displacement from reservoir rock

    and pore spaces [412]. Such a low interfacial tension can

    be achieved by using a suitable surfactant and/or a com-

    bination of surfactants [1316]. As indicated by the patentsgranted, the use of surfactants in EOR began almost

    80 years ago [17]. Surfactants used in the early 1960s were

    made by the direct sulfonation of crude oil or organic

    synthesis of alkyl/aryl sulfonates [17]. Even though the use

    of surfactants in EOR has been researched extensively, the

    number of surfactant EOR projects decreased significantly

    due to the low oil prices from late 1980s to early 2000.

    However, the depletion of oil reserves, the advancement of

    technologies, increasing demand for oil, and high oil prices

    have encouraged researchers to focus on surfactant EOR

    [1821].

    The majority of the reported surfactants used in EOR are

    ethoxylated and propoxylated sulfates and sulfonates. Even

    though the displacement efficiency of sulfonates with a

    higher equivalent weight is better [22], sulfonates with high

    equivalent weights are insoluble in water, and thus sul-

    fonates with lower equivalent weights have to be used as

    sacrificial agents and solubilizers. Therefore, mixtures of

    surfactants are used in EOR formulations. This type of

    formulation, however, may lead to chromatographic sepa-

    ration in the reservoir during displacement. Hence, in

    & Muhammad Shahzad [email protected]; [email protected]

    1 Center for Integrative Petroleum Research, King FahdUniversity of Petroleum and Minerals, Dhahran 31261,Saudi Arabia

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    J Surfact Deterg (2016) 19:223236

    DOI 10.1007/s11743-015-1776-5

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    conventional surfactant formulations, interfacial tension is

    either not reduced sufficiently to remove trapped oil or the

    slug may lose its integrity during flooding [22]. High-temperature and high-salinity conditions of reservoirs are

    another major challenge in the application of surfactant

    flooding. Surfactants can precipitate by interacting with

    divalent cations present in the reservoir brine [23,24], and

    can thermally degrade at high-reservoir temperatures [25].

    Surfactant retention in the reservoirs has an adverse effect

    on the economics of EOR. In summary, an ideal candidate

    surfactant for EOR must be compatible with the reservoir

    brine, must be able to generate ultra-low interfacial tension

    between water and oil, has low retention on reservoir rock,

    and has long-term thermal stability under reservoir

    conditions.

    Background of Gemini Surfactants

    A novel class of surfactants referred to as gemini sur-

    factants has drawn the attention of EOR experts lately due

    to their unique properties. They have been used in a range

    of applications due to their unique properties [2634].

    Gemini surfactants were first identified by Bunton et al. and

    named in 1991 by Menger and Littau [3538]. They con-

    tain more than one hydrophilic head group and

    hydrophobic tail group linked by a spacer at or near the

    head groups [3947]. A schematic representation of agemini surfactant is shown in Fig. 2. The attachment of the

    spacer group increases the hydrophobicity of gemini

    surfactants relative to that of the constituent monomeric

    units [48]. The most widely studied gemini surfactants are

    m-s-m type containing quaternary ammonium, where s and

    mrepresent the number of carbon atoms of the spacer and

    the alkyl chain, respectively [49, 50]. For example, the

    gemini surfactants alkanediyl-a,x-bis(dodecyldimethyl-

    ammonium bromide) with alkanediyl spacer groups C2H4

    and C8H20, are referred to as 12-2-12, and 12-8-12,respectively [48]. The hydrophilic head group can be

    cationic, non-ionic, anionic, or zwitterionic. The

    hydrophobic tail can be short or long and the spacer group

    can be polar (polyether) or non-polar (aliphatic or aro-

    matic), and rigid (benzene) or flexible (methylene) [51].

    Length of the spacer group, which maintains and controls

    the separation between the two head groups, can vary

    between C2 and C12. Most of the work on gemini sur-

    factants has focused on their physicochemical properties

    such as high solubilization capacity [52, 53], unique

    micelle structure and aggregation behavior [45], high sur-

    face activity [37], and interesting rheological properties[5456].

    Shukla and Tyagi reviewed anionic gemini surfactants,

    their synthesis, and properties such as the CMC, surface

    activity, and foaming properties [51]. Zana reviewed the

    behavior of dimeric and oligomeric surfactants in aqueous

    solution [43]. Kumar and Tyagi reviewed the applications

    of dimeric surfactants in genetics, cosmetics and personal

    care, paints, and textile industries [57]. Hait and Moulik

    reviewed the synthesis, structure, CMC, and the surface

    active properties of gemini surfactants [58]. A large num-

    ber of experimental studies on the properties of aqueous

    solutions of gemini surfactants have been reported. Thedetermination of the properties of the liquidliquid inter-

    face, particularly the oilwater interface, is the main area

    of research in laboratories conducting research on gemini

    surfactants [5962]. This review highlights the interfacial

    properties, adsorption, and rheological behavior of gemini

    surfactants under different conditions. As it is not possible

    to perform expensive and time-consuming oil recovery

    experiments for each surfactant under different conditions,

    IFT measurements, adsorption, and rheological character-

    ization are used as screening tools for the selection of EOR

    chemicals in the oil industry. Data obtained from adsorp-

    tion experiments, and rheological and interfacial mea-

    surements are widely used as guidelines for the selection of

    suitable surfactants and optimum surfactant formulations.

    Increases thecapillary number

    Polymer

    Viscosifies thedisplacing fluid

    EOR

    Improves themobility ratio

    ChemicalThermal

    Surfactant

    Alters the wettability

    Decreasesinterfacial tension

    Gas

    Alkali

    Fig. 1 Types of EOR methods

    Fig. 2 Schematicrepresentation of a geminisurfactant [161]

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    Fundamentals of Gemini Surfactants

    Structure

    In the last decade, a rich variety of cationic, anionic,

    zwitterionic, and nonionic gemini surfactants have been

    developed and commercialized. Structures of some of the

    typical gemini surfactants are given in Table1. Gemini

    surfactants can have phosphate, sulfonate, carboxylate,

    sulfate, ethyl ammonium, methyl ammonium [63], pyrro-

    lidinium [64], hexahydropyridine [64], and imidazolium[64] head groups. Common spacers of gemini surfactants

    are given in Table2. Oligostyrene [65], oligo (ethylene-

    propylene glycol), and poly (dimethyl siloxane) [66] are

    some typical examples of hydrophobic tail groups. Gemini

    surfactants have widespread applications in the fabrication

    of high-porosity materials [67], textiles, emulsifiers, wet-

    ting processes, leather-finishing, and skin and personal care

    products [68].

    Comparison of Gemini Surfactants

    with Conventional Surfactants

    Before comparing gemini surfactants with conventional

    surfactants, it is important to have an understanding of the

    fundamental properties of surfactants which are used to

    characterize them. An understanding of the critical micelle

    Table 1 Typical structures ofrepresentative geminisurfactants

    Structure of surfactant Type References

    Cationic [64]

    Anionic [155,162]

    Zwitterionic [163]

    Nonionic [164]

    Table 2 Common spacers of gemini surfactants

    Entry Spacer References

    1 Azobenzene [156]

    2 Ethylene oxide [147]

    3 Perylene tetracarboxylic diimide [65,165]

    4 Stilbene [65]

    5 Tetracarboxylic diimide [65]

    6 Polyoxyethylene [166]

    7 2-Butynyl [38]

    8 Methylene [51]

    9 Polyether [51]

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    concentration (CMC), hydrophilic/lipophilic balance

    (HLB), Krafft temperature, and the molecular packingparameter can greatly aid in understanding the performance

    of surfactants. R ratio and the solubilization ratio of sur-

    factants are also used for surfactant characterization.

    CMC is the concentration of a surfactant above which

    the formation of micelles takes place [69]. In solution

    chemistry, CMC is widely used to compare the effective-

    ness of surfactants for their desired applications [70].

    Critical micelle concentrations of gemini surfactants are

    typically 10100 times lower than the corresponding value

    for conventional monomeric surfactants [71]. CMC of a

    range of conventional and gemini surfactants are given in

    Table3. Among the gemini surfactants, anionic surfactantshave a lower CMC compared to their cationic counterparts.

    The Krafft temperature, also referred as the critical micelle

    temperature, is defined as the minimum temperature at

    which micelle formation takes place. Below the Krafft

    temperature, CMC is not attained and thus, micelles cannot

    form [72]. A surfactant is considered soluble if its Krafft

    temperature is below room temperature [51] and for gemini

    surfactants it is much lower than that of monomeric sur-

    factants [43]. Krafft temperatures below 0 C have been

    reported for many gemini surfactants containing both

    hydrophobic and hydrophilic spacers [7381].The HLB value of surfactants is a measure of the degree

    of hydrophilicity or lipophilicity. An HLB value of 1

    corresponds to a completely hydrophobic molecule,

    whereas a completely hydrophilic molecule has an HLB

    value around 40. Although high hydrophilicity assists in

    the dissolution of surfactants, it adversely affects the per-

    formance of surfactants in reducing IFT [17]. HLB values

    of surfactants used for oil displacement are typically in the

    range of 69 [82]. The HLB value can be adjusted by

    changing the tail length and modifying the head group.

    The structure of surfactants can be correlated with their

    interfacial performance using the packing parameter [82].The packing parameter (P) depends on the relative area of

    the surfactant head group (ao) and the tail group (VH/lc) and

    their relationship is shown by Eq. 1. When P approaches

    one, the area of the hydrophilic groups will be equal to the

    area of lipophilic groups and the surfactant will be com-

    pactly arranged at the interface minimizing the IFT. Typ-

    ically, the P value of a conventional surfactant is between

    0.3 and 0.6, which is not suitable for oil displacement.

    P value of potential surfactants for EOR applications

    Table 3 CMC values of conventional and gemini surfactants

    Entry Surfactant CMC/mM References

    1a C12H25N?(CH3)3 Br

    - 16 [39]

    2 C12H25N?(CH3)3 Cl

    22 [39]

    3 C16H33N?(CH3)3 Br

    1 [39]

    4 C12H25OSO3 Na? 8 [39]

    5 C2H4(C12H25N?Me2 Br-)2 0.84 [48]

    6 C3H6(C12H25N?Me2 Br

    -)2 0.87 [48]

    7 C4H8(C12H25N?Me2 Br

    -)2 1.09 [48]

    8 C6H12(C12H25N?Me2 Br

    -)2 1.01 [48]

    9 C8H16(C12H25N?Me2 Br

    -)2 0.83 [48]

    10 C10H20(C12H25N?Me2 Br

    -)2 0.63 [48]

    11 C12H24(C12H25N?Me2 Br

    -)2 0.37 [48]

    12 C12H25N?(CH3)2(CH2)16N

    ?(CH3)2C12H25 2Br- 0.12 [39]

    13 C16H33N?(CH3)2(CH2)2N ?

    (CH3)2C16H33 2Br- 0.003 [39]

    14 C12H25N?(CH3)2(CH2)2O(CH2)2N

    ?(CH3)2C12H25 2Cl- 0.5 [39]

    15 C16H33N?(CH3)2(CH2)5N

    ?(CH3)2C16H33 2Br- 0.009 [39]

    16 C16H33N?(CH3)2(CH2)2O(CH2)2N

    ?(CH3)2C16H33 2Br- 0.004 [39]

    17 C16H33N?(CH3)2CH2(CH2OCH2)3CH2N

    ?(CH3)2C16H33 2Br- 0.02 [39]

    18 C12H25N?(CH3)2CH2CH(OH)CH2N

    ?(CH3)2C12H25 2Br- 0.8 [39]

    19 C12H25N?(CH3)2CH2C6H4CH2N

    ?(CH3)2C12H25 2Br- 0.03 [39]

    20 C12H25N?(CH3)2CH2CH(OH)CH(OH)CH2N

    ?(CH3)2C12H25 2Br- 0.7 [39]

    21 C12H25N?(CH3)2CH2CH(OH)CH2N

    ?(CH3)2CH2CH(OH)CH2N?(CH3)2C12H25 3Cl

    - 0.5 [39]

    22 C12H25OPO2-O(CH2)6OPO2

    -OC12H25 2Na? 0.4 [39]

    23 C10H21OCH2CH(OSO3-)CH2O(CH2)2OCH2CH(OSO3

    -)CH2OC10H21 2Na? 0.01 [39]

    a Entries 14 are for conventional surfactants

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    should be adjusted to one, which can be accomplished by

    increasing VH, and by decreasing lc and ao. The value oflccan be deceased by increasing the degree of branching and

    aocan be decreased by using a week hydrophilic group or a

    zwitterion [82].

    P VH

    lc ao1

    In addition to the above mentioned properties, gemini

    surfactants have better wetting and foaming properties,

    unusual aggregation morphologies, better solubilizing

    properties, better foaming properties, and better rheological

    properties compared to conventional surfactants [73, 83

    92]. Gemini surfactants are three orders of magnitude more

    efficient in lowering the surface tension of water, and more

    than two order of magnitude more dynamic in the inter-

    facial performance compared to conventional surfactants

    [57]. Due to the unique properties of gemini surfactants,

    they have been referred to as a new generation of surfac-

    tants and have shown great promise for industrial appli-cations [93].

    The following sections highlight those properties of

    gemini surfactants which are used for screening them for

    EOR applications.

    Interfacial Tension

    This section highlights the interfacial properties of gemini

    surfactants and various factors affecting IFT. Interfacial

    evaluation can be used to determine the suitability of sur-

    factants for chemical EOR. If the IFT between surfactantsolution and crude oil is high, the surfactant can be ruled

    out at the initial stages.

    Gao et al. investigated sulfate based gemini surfactants

    and demonstrated that they have an extraordinary tolerance

    of salinity [17]. Even with a brine of 20 % NaCl and 5 wt%

    CaCl2 no phase separation or precipitation was observed.

    In addition, it was found that the interfacial tension is ultra-

    low towards the higher end of salinity, which is extremely

    desirable in high-temperature and high-salinity environ-

    ments. As the synergy between gemini surfactants and

    conventional surfactants provide mutual benefits, they can

    be used as co-solvents and co-surfactants.At low surfactant concentrations, surfactant molecules

    remain flat at the interface. However, with increasing sur-

    factant concentration they tend to orient themselves at the

    interface. At concentrations close to the CMC, surfactant

    molecules associate into larger aggregates of molecules

    also known as micelles. A further increase in the surfactant

    concentration will only increase the rate of formation of

    micelles and there will be no further adsorption of the

    surfactant at the interface. Gemini surfactants decrease IFT

    with increasing concentration and it is important to note

    that gemini surfactants achieve the minimum IFT at very

    low concentrations, which will have a positive impact on

    the economics of surfactant flooding. Gemini surfactants

    can achieve IFT in the range of 10-3 mN/m at 0.02 %

    concentration whereas conventional surfactants will require

    0.22 wt% [17]. At a gemini surfactant concentration of

    0.423 mml/L an IFT lower than 10-4 mN/m can beachieved [94]. However, it has been reported that the

    decrease in the interfacial tension with increasing surfac-

    tant concentration is limited to a particular concentration

    range. Further increase in the surfactant concentration can

    increase the IFT. At lower concentrations, HLB of the

    interface changes due to the adsorption of gemini surfac-

    tants at the interface, which results in the lowering of IFT.

    Increasing the concentration of the surfactant above a

    particular concentration can increase the rigidity of inter-

    face film, which increases the IFT. However further

    investigations are required to understand the mechanism

    [22].Due to adsorption and desorption of the surfactant at the

    interface, it will take some time to achieve the equilibrium

    IFT value. Gemini surfactants achieve equilibrium IFT val-

    ues in a shorter time compared to conventional surfactants.

    Although the addition of polymers increase the equilibrium

    time, equilibrium IFT values are not affected by their addi-

    tion [17]. Temperature can also affect the dynamic IFT, and

    time required to achieve the equilibrium IFT can be reduced

    at high temperature [44]. For example, a gemini surfactant

    took 50 min to achieve the equilibrium IFT value at 45 C,

    whereas the same takes only 15 min at 70 C [44].

    Temperature has a strong effect on the IFT, and IFTgoes through minima with increasing temperature for most

    gemini surfactants. An initial decrease and then an increase

    in the IFT are associated with a change in the distribution

    of surfactants in oil, water, and emulsions. Emulsions may

    invert from oil-in-water to water-in-oil with the variation of

    temperature. The temperature corresponding to a minimum

    in interfacial tension is known as the phase inversion

    temperature (PIT) [44]. At temperatures below the PIT,

    adsorption of the surfactant increases with increasing

    temperature resulting in the lowering of IFT. However, at

    temperatures above the PIT, further increase in the tem-

    perature may lead to the diffusion of the surfactant away

    from the interface into the oil phase resulting in an increase

    of the IFT.

    Performance of a surfactant can be improved through

    the synergistic interaction with another surfactant. Gemini

    surfactants can have excellent synergy with other gemini

    surfactants and conventional surfactants when the interac-

    tions are attractive. Ye et al. showed that the temperature

    effects on IFT can be diminished by using a mixture of

    gemini surfactants [44]. This is attributed to the formation

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    of mixed micellar aggregates with a compact arrangement.

    Such a surfactant can be used as a co-solvent, which can

    enhance the solubility of the main surfactant or the co-

    surfactant improving their performance.

    Gemini surfactants are more effective in reducing the IFT

    of the kerosene-water interface in salt solutions as compared

    to salt-free solutions. This is due to the modification of HLB

    of the interface and compression of the electrical double

    layer due to the added salts. However, gemini surfactants

    showed similar behavior in salt-free and salt solutions in

    decreasing the IFT of the hexadecane and water interface

    [22]. Thus, the nature of the lipophilic phase, i.e., crude oil, is

    also important in the decrease in IFT.

    In summary, gemini surfactants are more effective in

    decreasing the IFT under varying conditions compared to

    monomeric surfactants. Regarding EOR applications, the

    most important property of gemini surfactants is achieving

    ultra-low interfacial tension at low surfactant concentra-

    tions. Low surfactant concentration reduces the required

    amount of surfactant and the cost of surfactant flooding,

    which is the ultimate goal of any EOR process.

    Wettability Alteration

    Wettability is defined as the tendency of a liquid to pref-

    erentially adhere or stick to a solid surface in the presence

    of other liquids [95], which is the major factor controlling

    the location and flow of oil in reservoirs. An oil reservoir

    can be water-wet, oil-wet, or mixed-wet depending upon

    the nature of the oil and the type of the formation. The fact

    that the maximum amount of oil can be recovered from

    water-wet reservoirs is well established; however, majority

    of the carbonate reservoirs is oil-wet to mixed-wet. Wet-

    tability is normally determined by measuring the contact

    angle between a solid surface and an oil droplet. Data inTable4show that only 8 % of the carbonate reservoirs are

    water-wet and the remaining are intermediate-wet to

    strongly oil-wet reservoirs. Surfactants alter the wettability

    of rocks from oil-wet to water-wet and enhance the spon-

    taneous imbibition [96,97].

    Wettability alteration takes place by ion-pair formation

    and adsorption of the surfactant on the rock surface [ 98,

    99]. When electrostatic interactions exist between the head

    group of the surfactant and the adsorbed crude oil

    components, ion-pair formation is the main mechanism of

    wettability alteration. However, in the absence of electro-

    static interactions, hydrophobic interactions between the

    tail of the surfactant and the adsorbed crude oil components

    are responsible for wettability alteration [98]. Effectiveness

    of a surfactant in altering the wettability depends on the

    ionic nature of the surfactant. In the oil-wet core of chalk

    reservoirs, cationic surfactants perform better than anionicsurfactants in altering the wettability [96,100]. The authors

    hypothesized that the wettability alteration is due to ion-

    pair formation between the head of the cationic surfactant

    and certain components of the crude oil. On the other hand,

    anionic surfactants form a monolayer on the surface of

    carbonate rock through hydrophobic interactions between

    the tail of the surfactant and crude oil components. Ion-pair

    interactions are much stronger compared to hydrophobic

    interactions; therefore, cationic surfactants are more

    effective in altering the wettability of carbonate rock.

    Efficacy of gemini surfactants in altering the wettability

    was investigated by several researchers [101,102]. Salehiet al. investigated the effects of anionic gemini surfactants

    on wettability alteration of Berea sandstone and compared

    the results with those obtained using a conventional sur-

    factant [101]. They found that ion-pair formation is the

    main mechanism of wettability alteration, which can be

    improved by increasing the charge density on the head

    groups (Fig. 3). Contrary to carbonate rock, ion-pair for-

    mation is the main mechanism involving anionic surfac-

    tants in the case of sandstone rock. Due to the presence of

    two hydrophilic head groups and two hydrophobic tails,

    gemini surfactants can further improve the wettability

    alteration. Research on the wettability alteration of car-bonate rocks by gemini surfactants is limited and needs

    more experimental investigation.

    Adsorption

    Adsorption of surfactants on reservoir rock surfaces, which

    decreases the concentration of the surfactant in the flooding

    liquid, is a major hurdle that has to be overcome [103

    Fig. 3 Ion-pair formation between crude oil components and ananionic gemini surfactant [101]

    Table 4 Distribution of carbonate reservoirs [95]

    Contact angle () Reservoirs (%)

    Water-wet 080 8

    Intermediate-wet 80100 12

    Oil-wet 100160 65

    Strongly oil-wet 160180 15

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    106]. Adsorption of cationic, non-ionic, anionic, and

    amphoteric surfactants on sandstone and carbonate rock

    surfaces has been studied widely and the mechanism of

    adsorption has been discussed in a number of publications

    [16,107109]. Adsorption of surfactants on reservoir rock

    surfaces depends on the charge on the surfactant,

    hydrophobicity of the surfactant, charge on the rock sur-

    faces, pH, salinity, temperature, and interactions betweenthe surfactant and the rock surfaces [110]. Static and

    dynamic adsorption tests are performed to screen chemi-

    cals for EOR applications. Static adsorption tests are sim-

    ple and normally used for initial screening of EOR

    chemicals. In static adsorption tests, a small amount of a

    crushed rock sample is shaken in a surfactant solution for a

    specific time. The adsorption density is found by the dif-

    ference in concentration of the surfactant before and after

    equilibration. Surfactant concentration can be determined

    by conductivity measurements, surface tension measure-

    ments, gas chromatography, total carbon analysis (TOC),

    two phase titration, UV spectroscopy, gel permeationchromatography, and high performance liquid chromatog-

    raphy (HPLC) [16,111117]. As crushed rock has a higher

    surface area than a consolidated core, static adsorption tests

    give higher values of adsorption than dynamic adsorption

    tests [118]. Dynamic adsorption tests are typically per-

    formed using core flooding experiments, which are time

    consuming and used only for selected promising surfac-

    tants. For EOR applications, surfactant adsorption density

    should be less than 1 mg/g-rock [119].

    Behrens studied the adsorption of the anionic gemini

    surfactant Aerosol OT on kaolinite using the surfactant

    concentration determination method [110]. Adsorption ofthe anionic gemini surfactant on kaolinite increases with

    increasing salinity due to the increased ionic strength. Gao

    and Sharma investigated the adsorption behavior of sulfate

    gemini surfactant on Berea sandstone rock in the presence

    of 10,000 mg/L of NaCl [17]. They found that the Lang-

    muir adsorption model can be used to describe the

    adsorption behavior of the anionic gemini surfactant,

    similar to that of a conventional surfactant. The adsorption

    process of the gemini surfactants can be divided roughly

    into three regions. At low surfactant concentration (region

    I), the adsorption of the gemini surfactants increases lin-

    early and obeys Henrys Law. The surfactant molecules are

    adsorbed as individual ions and interactions do not take

    place between adsorbed molecules. Only electrostatic

    interactions between the head groups and the charged sites

    are present. In Region II, adsorption takes place much

    faster due to lateral interactions between the tail groups of

    the surfactant molecules, in addition to the electrostatic

    interactions. A plateau is obtained in Region III and further

    increase in the surfactant concentration has little or no

    effect on the adsorption density. This is due to the

    formation of micelles that act as chemical sinks for addi-

    tional surfactant. Anionic gemini surfactants also show

    lower equilibrium adsorption compared to conventional

    surfactants on Berea sandstone. Alkyl chain length and the

    spacer have a strong influence on the adsorption of gemini

    surfactants. Surfactants with longer alkyl chains and spacer

    groups have a higher adsorption due to their lower solu-

    bility and stronger interactions with the rock surface.Pahi et al. compared the adsorption of the alkylbenzene

    monomeric and gemini surfactants [120]. They also

    observed that gemini surfactants have similar adsorption

    behavior but with a lower equilibrium adsorption compared

    to conventional monomeric surfactants. The maximum

    amount of adsorbed gemini surfactants was found at the

    CMC. Rosen and Li studied the adsorption of two cationic

    gemini surfactants on limestone and clay (Na-montmoril-

    lonite) [121]. They found that the adsorption of the gemini

    surfactants on clay is similar to that of a conventional

    surfactant with similar hydrophilic and hydrophobic

    groups.Gao and Sharma studied the adsorption behavior of the

    anionic disulfate gemini surfactant and the various factors

    affecting the adsorption on a Berea sandstone core [118].

    The adsorption process of the sulfate gemini surfactant is

    also characterized by three distinct regions. The disulfate

    gemini surfactant has a lower adsorption density compared

    to the corresponding conventional single tail surfactant

    under similar conditions. The adsorption density depends

    on the hydrophilicity and the dual-head group structure of

    gemini surfactants. Due to their higher hydrophilicity, the

    gemini surfactants have a higher tendency to go into the

    aqueous phase as compared to conventional surfactants,and therefore, they have a lower tendency to adsorb on

    solid surfaces. One gemini molecule can interact with more

    than two adsorption sites and saturate the surface more

    efficiently due to the presence of two head groups. They

    also observed that the adsorption density of the gemini

    surfactant increases in the presence of salts. The increase in

    the adsorption density in the presence of salts is due to the

    suppression of electrostatic interactions between the head

    group and double layer formed at the surface by the added

    sodium ions, the promotion of various aggregates, and

    reduction in the solubility [118]. The molecular structure of

    gemini surfactants also affects their adsorption on reservoir

    rock surfaces. An increase in the length of the tail of the

    surfactant increases the lateral interactions and thus,

    increases the adsorption density. In addition, longer

    hydrocarbon chains also reduce the solubility in the bulk

    aqueous phase, thus, increasing the tendency of adsorption

    on solid surfaces.

    In summary, the adsorption behavior of gemini surfac-

    tants depends mainly on the molecular structure, salinity,

    temperature, and the type of interactions between the

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    surfactant molecules and the solid surface. Due to their

    higher hydrophilicity and the dual headgroup, they have

    lower adsorption densities compared to conventional single

    tail surfactants.

    Rheology

    Rheology is another important property that can be used for

    the selection of chemicals for EOR. Water-soluble poly-

    mers are used to prepare displacing fluids with a high

    viscosity, which are required to displace reservoir oil [122

    131]. Due to their unique aggregation behavior, gemini

    surfactants can also improve the rheological properties of

    displacing fluids. This approach has the advantage of using

    a single slug of gemini surfactants instead of a combination

    of surfactants and polymers. Both steady shear and

    dynamic rheology are important for EOR applications.

    Elasticity of a material has been proven recently to assist in

    the recovery of residual trapped oil [132137].A large amount of research has been conducted on steady

    shear rheology, extensional rheology, and rheo-scattering of

    worm-like micelles [138]. Gemini surfactants have better

    rheological properties compared to conventional surfactants.

    Although dilute solutions of ionic and non-ionic conven-

    tional surfactants behave as a Newtonian fluid with viscosity

    slightly higher than that of water, dilute solutions of gemini

    surfactants are much more viscous. Gemini surfactants form

    aggregates that are less curved compared to corresponding

    monomeric surfactants. Gemini surfactants form worm-like

    micelles which are also referred to as giant, rod-like, thread-

    like, or polymer-like micelles [139145]. They have a net-work structure similar to polymers, except that these

    micelles continuously break and reform [49]. When worm-

    like micelles are subjected to stress, they undergo two types

    of stress relaxation processes. They may undergo reptile-like

    motion or reversible scissions that occur at two time scales

    known as the reputation time and scission time. The vis-

    coelastic behavior of worm-like micelles canbe described by

    the Maxwell model [49]. Aggregate curvature decreases

    with increasing concentration of the surfactant, and electron

    micrographs show that these micelles may be several

    micrometers long [83,146]. However, micelles of conven-

    tional surfactants remain spherical even at considerably high

    concentrations [147]. Micelles of gemini surfactants trans-

    form from spherical to worm-like with increasing concen-

    tration, and both types coexist as the transformation is not

    abrupt. However, with increasing concentration, the number

    of spherical micelles per unit volume decreases. Therefore,

    the solution shows viscous behavior due to the formationof a

    transient network [83], which has been confirmed by others

    [84]. Length of the worms varies from 100 to 400 nm while

    diameter is normally the same for each worm-like micelle.

    While for the 12-s-12 series surfactants the shape of micelles

    change from elongated to spherical [45], for the 16-s-16

    series surfactants, worm-like and spherical micelles co-exist

    at specific concentrations. Micelles change from elongated

    to spherical when the length of the spacer is increased [ 148,

    149]. In general, gemini surfactants are capable of producing

    worm-like micelles as well as spherical micelles [150].

    Gemini surfactants with longer carbon chains have higherviscosity compared to those with shorter carbon chains [83].

    Gemini surfactants with long saturated alkyl chains have a

    high Krafft point. In some cases, the Krafft temperature is

    even higher compared to the corresponding monomeric

    surfactant. For example, the Krafft temperature of16-2-16is

    45 C, while the Krafft temperature for the corresponding

    monomeric surfactant cetyltrimethyl ammonium bromide is

    24 C [151]. While the Krafft temperature for 22-s-22 can be

    as high as 80 C, it is very low (\0 C) for surfactants with

    an unsaturated chain [150]. Surfactants with a long unsatu-

    rated chain have an excellent ability to enhance viscosity.

    Surfactants with long unsaturated chains, such as hydrox-yethyl methyl ammonium chloride (EHAC), show strong

    viscoelastic properties. The viscoelastic solution made from

    EHAC is referred to as a clean fracturing fluid which can be

    used in EOR applications [152,153].

    The properties of the spacer group are the most impor-

    tant internal parameter controlling the rheological behavior

    of gemini surfactants. Gemini surfactants with relatively

    short spacer groups have a significantly high viscosity [54,

    154, 155]. Gemini surfactants with very short spacer

    groups, have a very small head area consisting of the two

    head groups, and therefore, are more suitable for forming

    worm-like micelles [45, 156158]. In the case of surfac-tants with longer spacer groups, the packing parameter,

    which facilitates the formation of spherical micelles, will

    be small and thus the viscosity will be low. Danino et al.

    reported micelle formation behavior of12-s-12quaternary

    ammonium gemini surfactants for a range ofs values [45].

    If s is between 6 and 12, the distance between the head

    groups is similar due to the space occupied by the head

    groups, and similar aggregates (spherical) as in the case of

    the corresponding monomeric surfactant are formed.

    However, if s[14 the spacer adopts a looped structure

    similar to a gemini (dimeric) surfactant [48]. If s B5, the

    head groups are in close proximity to each other, leading to

    aggregates with a lower curvature. The rigidity of the

    spacer is also important in determining the viscoelastic

    behavior. A rigid spacer like azobenzene restrains the two

    alkyl tails from drawing close to each other, and hence

    increases the packing parameter. However, 22-4-22and18-

    3-18are more efficient in enhancing viscosity compared to

    22-3-22 and 18-2-18 [83].

    Gemini surfactants possess the useful property of the

    ability to change the shear rate. They can be shear-thinning

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    or shear-thickening depending on the concentration, tem-

    perature, and the applied shear rate. Shear-thinning occurs

    when the rate of deformation of the network is higher and

    the time required to regain equilibrium is long [49].

    Near the Krafft temperature of a surfactant, a network or

    worm-like micelles form. However, if the temperature is far

    below or far above the Krafft point, worm-like micelles will

    transform to spherical micelles. Therefore, near the Krafftpoint the viscosity of a surfactant will be a maximum, which

    decreases if thetemperature is above or belowthe Krafftpoint.

    This phenomenon is not common in most surfactants [84].

    Guo et al. investigated the interactions between gemini sur-

    factants and polymers (partially hydrolyzed polyacrylamide)

    [159]. Combination of anionic gemini surfactants and non-

    ionic conventional surfactants can widen the surfactant con-

    centration window with increased viscosity. The investi-

    gated gemini surfactant and the polymer has a synergistic

    effect on theIFT reduction. TheIFT of the surfactant-polymer

    solution is lower compared to the IFT of the pure surfactant.

    Similar results were reported by Tang et al. [93].In general, gemini surfactants have unique rheological

    properties, which are useful for EOR applications. These

    rheological properties are associated with interesting

    aggregation behavior. High viscosity in combination with

    ultra-low interfacial tension can make gemini surfactants

    ideal candidates for EOR applications.

    Field Applications and Future Prospects

    Chemicals must be evaluated using a series of evaluation

    methods prior to their use any in field applications. Otherthan good rheological and interfacial properties, a

    surfactant must be tolerant to harsh reservoir conditions,

    must be thermally stable, and should have lower retention

    on rock surfaces. Due to the high charge density and closer

    packing of molecules, their tendency to adsorb on nega-

    tively charged rock surfaces is very low [160]. In addition,

    gemini surfactants have high tolerance to divalent cations,

    which make them ideal candidates for EOR applications.

    Only few reports are available on oil recovery experimentsusing gemini surfactants. Up to 39 % of oil recovery has

    been reported from core flooding experiments by the

    injection of gemini surfactants [35]. Salehi et al. compared

    gemini surfactants with conventional surfactants and

    observed that oil recovery from gemini surfactants is

    almost doubled that from conventional surfactants [101],

    which is due to better packing leading to stronger inter-

    actions of the surfactant with adsorbed molecules. Labo-

    ratory core flooding data of a range of gemini surfactants is

    given in Table5. In summary, a large research effort is

    underway on the laboratory scale and high recovery rates

    have been reported using gemini surfactants. However, todate gemini surfactants have not been used in field appli-

    cations. Nevertheless, considering the number of publica-

    tions and the extent of the laboratory scale evaluation

    concerning gemini surfactants, they will be future candi-

    dates for EOR applications.

    Concluding Remarks

    Adsorption, rheology, wettability alteration, and interfacial

    properties of gemini surfactants are reviewed together with

    their potential applications in EOR. A rich variety ofanionic, non-ionic, cationic, and zwitterionic gemini

    Table 5 Oil recovery data for gemini surfactants

    Gemini surfactant Class Ta (C) Recovery (%) Rock b References

    Ethanediyl-a,b bis(cetyldimethylammonium bromide) Cationic Ng 68 Ng [102]

    Quaternary ammonium based Cationic Ng 14.96 Ng [59]

    Ethylene-bis(dodecyl benzene sulfonate) Anionic 40 16.78 S [167]

    2,2-Bis(4-decaaldoxy-3-sodium sulfophenylate) propane Anionic 55 19.1 Ng [94]

    AN12-4-12 Anionic Ng 10.4 S [93]

    C74

    H154

    O28

    N2P2

    Zwitterionic 80 39.6 S [35]

    C34H74O8N2P2 Zwitterionic 80 36.7 S [35]

    DMES-14 Anionic 65 42.4 (SP)c S [168]

    GA124-12 Anionic Ng 11.7 S [169]

    Fatty acid disulfonate Anionic 65 32 (SP) S [170]

    Xylene di-C14/C16-sulfonate Anionic 90 49 Td S [101]

    aTexperimental temperature

    bS is for sandstone formation and Ng if information is not provided

    c The surfactant is used with some polymer in injection slugd Recovery reported with letter T is total oil recovery while other values are addition oil recovery

    J Surfact Deterg (2016) 19:223236 231

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    surfactants are available. Low CMC, better wetting prop-

    erties, good foaming properties, ability to reduce surface

    tension, unique aggregation behavior, ability to achieve

    ultra-low interfacial tension at low concentration make

    them ideal candidates for EOR applications. Despite the

    fact that the number of laboratory evaluations on gemini

    surfactants have increased and encouraging results have

    been obtained, no field data on flooding with gemini sur-factants are available. Most likely, this is due to fact that

    gemini surfactants are a comparatively new class of sur-

    factants and in the future they will definitely replace con-

    ventional monomer surfactants, particularly if the

    economics of these surfactants improve.

    Acknowledgments This project was funded by the National Planfor Science, Technology, and Innovation (MAARIFAH)KingAbdulaziz City for Science and Technologythrough the Scienceand Technology Unit at King Fahd University of Petroleum & Min-erals (KFUPM)the Kingdom of Saudi Arabia, award number13-ENV1968-04. I would like to thank the Center for Integrative

    Petroleum Research at the King Fahd University of Petroleum andMinerals for providing facilities to access various literature sources.

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    Muhammad Shahzad KamalReceived his B.Sc. (2008) in chemicalengineering and M.Sc. (2010) in polymer engineering from UETLahore. He completed his Ph.D. in chemical engineering at the King

    Fahd University of Petroleum and Minerals (KFUPM), Saudi Arabia.Currently he is working as a research engineer in the Center forIntegrative Petroleum Research at KFUPM.

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