Progress in research of sulfobetaine surfactants used in tertiary oil recovery

The synthesis of sulfobetaine surfactants and their application in tertiary oil recovery (TOR) are summarized in this paper. The synthesis of sulfobetaine surfactants was classified into three categories of single hydrophobic chain sulfobetaine surfactants, double hydrophobic chain sulfobetaine surfactants and Gemini sulfobetaine surfactants for review. Their application in TOR was classified into surfactant flooding, microemulsion flooding, surfactant/polymer (SP) flooding and foam flooding for review. The sulfonated betaine surfactants have good temperature resistance and salt tolerance, low critical micelle concentration (cmc) and surface tension corresponding to critical micelle concentration (γ_cmc), good foaming properties and wettability, low absorption, ultralow interfacial tension of oil/water, and excellent compatibility with other surfactants and polymers. Sulfobetaine surfactants with ethoxyl structures, hydroxyl and unsaturated bonds, and Gemini sulfobetaine surfactants will become an important direction for tertiary oil recovery because they have better interfacial activity in high-temperature (≥90°C) and high-salinity (≥10⁴ mg/L) reservoirs. Some problems existing in the synthesis and practical application were also reviewed.     

Stabilization of natural gas foams using different surfactants at high pressure and high temperature conditions

Natural gas foam can be used for mobility control and channel blocking during natural gas injection for enhanced oil recovery, in which stable foams need to be used at high reservoir temperature, high pressure and high water salinity conditions in field applications. In this study, the performance of methane (CH₄) foams stabilized by different types of surfactants was tested using a high pressure and high temperature foam meter for surfactant screening and selection, including anionic surfactant (sodium dodecyl sulfate), non-anionic surfactant (alkyl polyglycoside), zwitterionic surfactant (dodecyl dimethyl betaine) and cationic surfactant (dodecyl trimethyl ammonium chloride), and the results show that CH₄-SDS foam has much better performance than that of the other three surfactants. The influences of gas types (CH₄, N₂, and CO₂), surfactant concentration, temperature (up to 110°C), pressure (up to 12.0 MPa), and the presence of polymers as foam stabilizer on foam performance was also evaluated using SDS surfactant. The experimental results show that the stability of CH₄ foam is better than that of CO₂ foam, while N₂ foam is the most stable, and CO₂ foam has the largest foam volume, which can be attributed to the strong interactions between CO₂ molecules with H₂O. The foaming ability and foam stability increase with the increase of the SDS concentration up to 1.0 wt% (0.035 mol/L), but a further increase of the surfactant concentration has a negative effect. The high temperature can greatly reduce the stability of CH₄-SDS foam, while the foaming ability and foam stability can be significantly enhanced at high pressure. The addition of a small amount of polyacrylamide as a foam stabilizer can significantly increase the viscosity of the bulk solution and improve the foam stability, and the higher the molecular weight of the polymer, the higher viscosity of the foam liquid film, the better foam performance.     

A New Series of Double-Chain Single-Head Sulfobetaine Surfactants Derived from 1,3-Dialkyl Glyceryl Ether for Reducing Crude Oil/Water Interfacial Tension

A new series of sulfobetaine surfactants with double-chain single-head structure were derived from 1,3-dialkyl glyceryl ethers and their performances in reducing Daqing crude oil/connate water interfacial tension (IFT) in the absence of alkali were studied. With a large hydrophilic head group and double hydrophobic chains, these surfactants are efficient at reducing crude oil/connate water IFT. Those with didecyl and dioctyl are good hydrophobic surfactants that can reduce Daqing crude oil/connate water to ultra-low IFT by mixing with a small molar fraction of various conventional single-chain hydrophilic surfactants, such as α-olefin sulfonates, dodecyl polyoxyethylene (10) ether, and cetyl dimethyl hydroxypropyl sulfobetaine. The asymmetric double-chain sulfobetaine derived from 1-decyl-3-hexyl glyceryl ether can reduce Daqing crude oil/connate water IFT to ultra-low solely over a wide concentration range (0.03–10 mM or 0.0017–0.58 wt.%), which allows for use of an individual surfactant instead of mixed surfactants to avoid chromatographic separation in the reservoir. In addition, formulations rich in sulfobetaine surfactants show low adsorption on sandstone, keeping the negatively charged solid surface water-wet, and forming crude oil-in-water emulsions. These new sulfobetaine surfactants are, therefore, good candidates for surfactant-polymer flooding free of alkali.     

Study of Foaming Properties and Effect of the Isomeric Distribution of Some Anionic Surfactants

Using different reaction conditions of photosulfochlorination of n-dodecane, two samples of anionic surfactants of sulfonate type are obtained. Their micellar behavior has been already reported and the relationship between their isomeric distribution and their chemical structures and micellar behaviors have been more thoroughly explored. In this investigation, we screened the foaming properties (foaming power and foam stability) by a standardized method very similar to the Ross–Miles foaming tests to identify which surfactants are suitable for applications requiring high foaming, or, alternatively, low foaming. The results obtained for the synthesized surfactants are compared to those obtained for an industrial sample of secondary alkanesulfonate (Hostapur 60) and to those of a commercial sample of sodium dodecylsulfate used as reference for anionic surfactants. The foam formation and foam stability of aqueous solutions of the two samples of dodecanesulfonate are compared as a function of their isomeric distribution. These compounds show good foaming power characterized in most cases by metastable or dry foams. The highest foaming power is obtained for the sample rich in primary isomers which also produces foam with a relatively high stability. For the sample rich in secondary isomers we observe under fixed conditions a comparable initial foam height but the foam stability turns out to be low. This property is interesting for applications requiring low foaming properties such as dishwashing liquid for machines. The best results are observed near and above the critical micellar concentrations and at 25 °C for both the samples.

The development of heat-resistant and salt-tolerant foam with betaine surfactants

A modified instrument was designed to evaluate foam properties under high temperature and pressure. The type and molar ratio of betaine surfactants were screened to develop the heat-resistant and salt-tolerant foam for Tahe oilfield (130°C, 220 g/L), and the effects of temperature and pressure on foam properties were also investigated. The synergism between surfactants and the enhanced oil recovery (EOR) mechanism of foam flooding in fractured-vuggy reservoirs were studied. Experimental results showed the developed foam had excellent foaming ability and foam stability when the lauramidopropyl hydroxyl sulfobetaine (LHSB): erucic amide propyl betaine (EAB) molar ratio ranged from 1:1 to 1:2 (initial foam volume was 392 ml when the molar ratio was 1:1, drainage half-time was 5.75 min and foam half-time was 72 min when the molar ratio was 1:2 at 130°C and 2 MPa). The synergistic effect was found to reach its maximum when the LHSB:EAB molar ratio ranged from 1:1 to 1:2 according to interaction parameters, which agreed with the results of foam properties. Foam stability was found to considerably increase with increasing pressure, but decrease with increasing temperature. However, temperature and pressure were found to have consistent effects on foaming ability, that is, the foaming ability increased with increasing temperature and pressure. The flooding test showed foam flooding exhibited better sweep efficiency and higher recovery ratio in the fractured-vuggy model than gas flooding and water flooding. This could be because injected foam did not channel through the top (or bottom) path due to its high viscosity and moderate density.     

Stability improvement of CO2 foam for enhanced oil‐recovery applications using polyelectrolytes and polyelectrolyte complex nanoparticles

CO₂ foam for enhanced oil‐recovery applications has been traditionally used in order to address mobility‐control problems that occur during CO₂ flooding. However, the supercritical CO₂ foam generated by surfactant has a few shortcomings, such as loss of surfactant to the formation due to adsorption and lack of a stable front in the presence of crude oil. These problems arise because surfactants dynamically leave and enter the foam interface. We discuss the addition of polyelectrolytes and polyelectrolyte complex nanoparticles (PECNP) to the surfactant solution to stabilize the interface using electrostatic forces to generate stronger and longer‐lasting foams. An optimized ratio and pH of the polyelectrolytes was used to generate the nanoparticles. Thereafter we studied the interaction of the polyelectrolyte–surfactant CO₂ foam and the polyelectrolyte complex nanoparticle–surfactant CO₂ foam with crude oil in a high‐pressure, high‐temperature static view cell. The nanoparticle–surfactant CO₂ foam system was found to be more durable in the presence of crude oil. Understanding the rheology of the foam becomes crucial in determining the effect of shear on the viscosity of the foam. A high‐pressure, high‐temperature rheometer setup was used to shear the CO₂ foam for the three different systems, and the viscosity was measured with time. It was found that the viscosity of the CO₂ foams generated by these new systems of polyelectrolytes was slightly better than the surfactant‐generated CO₂ foams. Core‐flood experiments were conducted in the absence and presence of crude oil to understand the foam mobility and the oil recovered. The core‐flood experiments in the presence of crude oil show promising results for the CO₂ foams generated by nanoparticle–surfactant and polyelectrolyte–surfactant systems. This paper also reviews the extent of damage, if any, that could be caused by the injection of nanoparticles. It was observed that the PECNP–surfactant system produced 58.33% of the residual oil, while the surfactant system itself produced 47.6% of the residual oil in place. Most importantly, the PECNP system produced 9.1% of the oil left after the core was flooded with the surfactant foam system. This proves that the PECNP system was able to extract more oil from the core when the surfactant foam system was already injected. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 44491.     

Screening of Surfactant Foaming Properties Using the Gas-Sparging Method: Design of an Optimal Protocol

Foaming properties of five model surfactants, namely, sodium laureth sulfate (SLES), sodium dodecylsulfate (SDS), polyoxyethylene 23 lauryl ether (Brij L23), polysorbate 20 (Tween 20), and polysorbate 80 (Tween 80), have been compared as a function of experimental conditions using the gas-sparging method. The influence of surfactant concentration relative to the critical micelle concentration (CMC) and three process parameters—frit porosity, gas flow rate, and preset volume of foam (or bubbling time)—was studied by means of a 2^4–1 factorial design. Three foaming properties were considered: foam capacity, foam stability, and maximal foam density. At the CMC, SLES, SDS, Tween 20, and Brij L23 were indistinguishable, all having very high foaming capacity and stability, regardless of process conditions. At 0.1 CMC, differences among them were highlighted especially at the lowest frit porosity coupled to the highest gas flow rate. Those conditions are thus recommended when a rapid screening of surfactant foaming performances is needed.     

Surfactant Crystals as Stimulable Foam Stabilizers: Tuning Stability with Counterions

The demands on foam stability are variable and changing, which is why design of foams that are both ultrastable and stimulable is important. We study foams stabilized using surfactant particles made through precipitation of sodium dodecyl sulfate with alkali chlorides. We have previously shown that depending on the concentrations of surfactant and salt, the foams can be ultrastable or age like common surfactant foams. We now show that the adsorption of surfactant crystals changes with the type of salt added and how the crystals are made, as well as the surfactant concentration. We see differences in foam stability if the crystals are made prior to foaming or if they are formed concomitantly with foaming. The adsorption of the crystals is improved if the crystals are made during generation, possibly because of their smaller size. The foams destabilize when heated above the Krafft boundary. We show that through tuning the surfactant concentration and salt type or concentration, we can modulate the melting temperature, and hence the destruction temperature of foam between 22 and 50 °C. Precipitated surfactant particles are versatile alternatives to stabilize ultrastable and stimulable foams.     

Synergism and Performance for Systems Containing Binary Mixtures of Anionic/Cationic Surfactants for Enhanced Oil Recovery

The surfactant structure–performance relationship and application properties in enhanced oil recovery (EOR) for binary mixtures of anionic and cationic surfactants are presented and discussed. A polyoxyethylene ether carboxylate anionic surfactant was blended with a quaternary ammonium chloride cationic surfactant and tested for a high-temperature, low-salinity, and high-hardness condition as found in an oil reservoir. These mixtures were tailored by phase behavior tests to form optimal microemulsions with normal octane (n-C8) and crude oil having an API gravity of 48.05°. The ethoxy number of the polyoxyethylene carboxylate anionic surfactant and the chain length of the cationic surfactant were tuned to find an optimal surfactant blend. Interfacial tensions with n-C8 and with crude oil were measured. Synergism between anionic and cationic surfactants was indicated by surface tension measurement, CMC determination, calculation of surface excess concentrations and area per molecule of individual surfactants and their mixtures. Molecular interactions of anionic and cationic surfactants in mixed monolayers and aggregates were calculated by using regular solution theory to find molecular interaction parameters β ^σ and β ^M . Morphologies of surfactant solutions were studied by cryogenic TEM. The use of binary mixtures of anionic/cationic surfactants significantly broadens the scope of application for conventional chemical EOR methods.     

低碳醇对氟碳与碳氢表面活性剂复配体系泡沫性能的影响

普通碳氢表面活性剂与磺基甜菜碱氟碳表面活性剂(FS)相比,泡沫性能和耐油性不好。醇通常强烈地影响表面活性剂的自组织行为,醇的加入能提高表面活性剂的泡沫性能。本文采用Ross-Miles法探讨了低碳醇对FS与阴离子碳氢表面活性剂(AOS)复配体系FS/AOS泡沫性能的影响。结果表明,当甲醇、无水乙醇、异丙醇浓度分别为5%、3%、3%,复配体系FS/AOS的起泡性能和泡沫稳定性仍较好,在加入醇之后,煤油含量60%～80%时起泡性能和泡沫稳定性仍较好。不同碳数的低碳醇对复配体系泡沫性能的影响规律为:发泡性能甲醇最好、异丙醇次之、无水乙醇最差,异丙醇的稳泡性能较甲醇和无水乙醇差。     

Formulation for chemical EOR: Development and evaluation of an ASP formulation In customer field conditions

Alkali surfactant polymer (ASP) flooding is an enhanced oil recovery (EOR) technology with an impressive potential for increasing incremental oil production from conventional hydrocarbon bearing reservoirs. A challenge to ASP application is the complexity of determining an effective formulation, typically requiring extensive laboratory screening of nearly countless combinations of surfactants and cosolvents. This paper focuses on demonstrating the utility of the hydrophilic–lipophilic deviation (HLD) concept for EOR application to simplify surfactant formulation workstreams seeking an economically viable ASP formulation for field application. In describing work performed for EOR application of ASP under customer conditions using crude oil, the discussion covers the initial evaluation of the promising surfactant formulation (interfacial tension and solubility), the improvement upon the formulation via HLD principles, and the evaluation of the improved surfactant formulation (coreflood studies). The final ASP formulation identified consisted of a 9 to 1 mixture of alkyl propoxy sulfate sodium salt (APS) to alkyl ethoxy sulfate sodium salt (AES) totaling 2000 ppm active surfactant content, 2.0 wt% Na₂CO₃, and 3000 ppm polyacrylamide polymer (all commercially available products). This formulation had ultra-low interfacial tension and favorable mixing behavior under reservoir conditions. In coreflood studies, the final formulation reproducibly achieved cumulative oil recovery of 96.4%–98.5% of original oil in place with only 0.3 PV of ASP injection with a chase alkali polymer injection.     

Effect of oil viscosity on recovery processes in relation to foam flooding

Laboratory experiments were conducted to determine the effect of oil viscosity on the oil-recovery efficiency in porous media. The pure surfactants (i.e., sodium dodecyl sulfate and various alkyl alcohols) were selected to correlate the molecular and surface properties of foaming solutions with viscosity, and the recovery of oil. Oil-displacement efficiency was measured by water, surfactant-solution and foam-flooding processes, which included 2 types of foams (i.e., air foam and steam foam). A significant increase in heavy-oil recovery was observed by steam foam flooding compared with that by air foam flooding, whereas for light oils, the steam foam and air foam produced about the same oil recovery. An attempt was made to correlate the chain-length compatibility with the surface properties of the foaming agents and oil-recovery efficiency in porous media. For mixed foaming systems (C₁₂ SO₄ Na + C_n H_2n+1 OH), a minimum in surface tension, a maximum in surface viscosity, a minimum in bubble size and a maximum in oil recovery were observed when both components of the foaming system had the same chain length. These results were explained on the basis of thermal motions (i.e., vibrational, rotational and oscillational) and the molecular packing of surfactants at the gas-liquid interface. The effects of chain-length compatibility and the surface properties of mixed surfactants are relevant to the design of surfactant formulations for oil recovery under given reservoir conditions.     

Viscoelastic Surfactants with High Salt Tolerance,Fast‐Dissolving Property,and Ultralow Interfacial Tension for Chemical Flooding in Offshore Oilfields

Injected chemical flooding systems with high salinity tolerance and fast‐dissolving performance are specially required for enhancing oil recovery in offshore oilfields. In this work, a new type of viscoelastic‐surfactant (VES) solution, which meets these criteria, was prepared by simply mixing the zwitterionic surfactant N‐hexadecyl‐N,N‐dimethyl‐3‐ammonio‐1‐propane sulfonate (HDPS) or N‐octyldecyl‐N,N‐dimethyl‐3‐ammonio‐1‐propane sulfonate (ODPS) with anionic surfactants such as sodium dodecyl sulfate (SDS). Various properties of the surfactant system, including viscoelasticity, dissolution properties, reduction of oil/water interfacial tension (IFT), and oil‐displacement efficiency of the mixed surfactant system, have been studied systematically. A rheology study proves that at high salinity, 0.73 wt.% HDPS/SDS‐ and 0.39 wt.% ODPS/SDS‐mixed surfactant systems formed worm‐like micelles with viscosity reaching 42.3 and 23.8 mPa s at a shear rate of 6 s^?1, respectively. Additionally, the HDPS/SDS and ODPS/SDS surfactant mixtures also exhibit a fast‐dissolving property (dissolution time <25 min) in brine. More importantly, those surfactant mixtures can significantly reduce the IFT of oil–water interfaces. As an example, the minimum of dynamic‐IFT (IFT_min) could reach 1.17 × 10^?2 mN m^?1 between the Bohai Oilfield crude oil and 0.39 wt.% ODPS/SDS solution. Another interesting finding is that polyelectrolytes such as sodium of polyepoxysuccinic acid can be used as a regulator for adjusting IFT_min to an ultralow level (<10^?2 mN m^?1). Taking advantage of the mobility control and reducing the oil/water IFT of those surfactant mixtures, the VES flooding demonstrates excellent oil‐displacement efficiency, which is close to that of polymer/surfactant flooding or polymer/surfactant/alkali flooding. Our work provides a new type of VES flooding system with excellent performances for chemical flooding in offshore oilfields.     

木质素基PF泡沫的发泡工艺与性能

利用低廉的木质素部分取代苯酚制备木质素基酚醛树脂(PF)泡沫,采用正交试验对木质素基PF发泡工艺进行了研究,研究了表面活性剂(吐温–80)用量、发泡剂(正戊烷)用量、发泡温度三个因素对木质素基PF泡沫性能的影响,从而优化发泡工艺。实验结果表明,对木质素基PF泡沫的极限氧指数(LOI)和导热系数影响最大的是发泡温度,而对于压缩强度影响最大的是表面活性剂用量。木质素基PF泡沫的最佳发泡工艺为:表面活性剂(吐温–80)用量为8%、发泡剂(正戊烷)用量为12%,发泡温度为90℃,所得泡沫具有较好的热稳定性,其LOI为39%,压缩强度为0.32 MPa,导热系数为0.025 W/(m·K)。     

Separation of oil contaminants by surfactant-aided foam fractionation

The separation of oily contaminants out of aqueous/non-aqueous phases using foam fractionation with a surfactant was investigated. In the separation of the light oil (hexadecane), the eluted amount of oil and the o/w (oil/water) ratio increased with the weight percentage of SDS (sodium dodecyl sulfate); and the ratio actually remained the same above the CMC (critical micelle concentration) point (0.23 wt% of SDS). Most of the oil was eluted even at 49:1 initial o/w ratio with the surfactant. For the heavy oil (carbon tetrachloride), the eluted o/w ratio and the oil recovery had maxima at 0.05 and 0.1 wt% of SDS solution, respectively, even though the overall recovery of 20–30 % was much lower than that of 80–100 % in the light oil. It was speculated that emulsion formation might affect oil entrapment in the foams. Higher gas flow rates, in general, increased the oil recovery, but did not increase the o/w ratio in the effluents.     

Synthesis,Characterization, and Surface-Active Properties of Carboxylbetaine and Sulfobetaine Surfactants based on Vegetable Oil

A novel series of carboxylbetaine-type and sulfobetaine-type zwitterionic surfactants (castor oil amidoethyl betaine, castor oil amidoethyl sulfobetaine [CAAS], cottonseed oil amidoethyl betaine, and cottonseed oil amidoethyl sulfobetaine [COAS]) were synthesized via the reactions of nonedible vegetable oils (castor oil and cottonseed oil) with dimethylaminoethylamine, followed by the reaction with sodium chloroacetate and sodium 2-hydroxy-3-chloropropane sulfonate, respectively. Their chemical structures were confirmed using the electrospray ionization mass spectrum (ESI-MS) and infrared (IR) spectra. The surface activities of the prepared compounds were measured by surface tension. It was noticed that the sulfobetaine-type surfactants in aqueous solution performed slightly better at reducing surface tension than the carboxylbetaine-type surfactants. Meanwhile, the synthesized surfactants possess a broad range of isoelectric points, superior foam properties, and exhibit some antibacterial activity on Gram-positive and Gram-negative bacteria.     

Protocol for Studying Aqueous Foams Stabilized by Surfactant Mixtures

Even though foams have been the subject of intensive investigations over the last decades, many important questions related to their properties remain open. This concerns in particular foams which are stabilized by mixtures of surfactants. The present study deals with the fundamental question: which are the important parameters one needs to consider if one wants to characterize foams properly? We give an answer to this question by providing a measuring protocol which we apply to well‐known surfactant systems. The surfactants of choice are the two non‐ionic surfactants n‐dodecyl‐β‐d ‐maltoside (β‐C₁₂G₂) and hexaethyleneglycol monododecyl ether (C₁₂E₆) as well as their 1:1 mixture. Following the suggested protocol, we generated data which allow discussion of the influence of the surfactant structure and of the composition on the time evolution of the foam volume, the liquid fraction, the bubble size and the bubble size distribution. This paper shows that different foam properties can be assigned to different surfactant structures, which is the crucial point if one wants to tailor‐make surfactants for specific applications.     

Batch foaming of SAN/clay nanocomposites with scCO2: A very tunable way of controlling the cellular morphology

This paper aims at elucidating some important parameters affecting the cellular morphology of poly(styrene-co-acrylonitrile) (SAN)/clay nanocomposite foams prepared with the supercritical CO₂ technology. Prior to foaming experiments, the SAN/CO₂ system has first been studied. The effect of nanoclay on CO₂ sorption/desorption rate into/from SAN is assessed with a gravimetric method. Ideal saturation conditions are then deduced in view of the foaming process. Nanocomposites foaming has first been performed with the one-step foaming process, also called depressurization foaming. Foams with different cellular morphology have been obtained depending on nanoclay dispersion level and foaming conditions. While foaming at low temperature (40 °C) leads to foams with the highest cell density (∼10¹²-10¹⁴ cells/cm³), the foam expansion is restricted (d∼0.7-0.8 g/cm³). This drawback has been overcome with the use of the two-step foaming process, also called solid-state foaming, where foam expansion occurs during sample dipping in a hot oil bath (d∼0.1-0.5 g/cm³). Different foaming parameters have been varied, and some schemes have been drawn to summarize the characteristics of the foams prepared - cell size, cell density, foam density - depending on both the foaming conditions and nanoclay addition. This result thus illustrates the huge flexibility of the supercritical CO₂ batch foaming process for tuning the foam cellular morphology.     

Effect of Temperature on Foaming Ability and Foam Stability of Typical Surfactants Used for Foaming Agent

Foam has extensive applications in a wide range of industrial fields. Some surfactants are used as foaming agents in the preparation of foam. The performance of the foaming agent directly affects the application of the foam. In this paper, experiments were designed and conducted to reveal the influence of temperature on foaming performance of 10 typical anionic, cationic, nonionic, and amphiprotic surfactants. They were exposed to different temperature conditions to measure the foaming capacity (FC), foaming expansion (FE), and foam’s half-life. FC and FE represent foaming ability (FA), and half-life represents foam stability (FS). The results show that the FC increased at elevated foaming temperature, while FS decreased with rising temperature. Anionic surfactants are less affected by temperature and have better FA and longer FS. It seems that 20–30 °C is an ideal foaming temperature. This study lays an important foundation for the efficient preparation and utilization of foam in industrial fields.     

Enhanced Wettability Alteration by Surfactants with Multiple Hydrophilic Moieties

The main production mechanism during water flooding of naturally fractured oil reservoirs is the spontaneous imbibition of water into matrix blocks and resultant displacement of oil into the fracture system. This is an efficient recovery process when the matrix is strongly water-wet. However, in mixed- to oil-wet reservoirs, secondary recovery from water flooding is often poor. Oil production can be improved by dissolving low concentrations of surfactants in the injected water. The surfactant alters the wettability of the reservoir rock, enhancing the spontaneous imbibition process. Our previous study revealed that the two main mechanisms responsible for the wettability alteration are ion-pair formation and adsorption of surfactant molecules through interactions with the adsorbed crude oil components on the rock surface. Based on the superior performance of surfactin, an anionic biosurfactant with two charged groups on the hydrophilic head, it was hypothesized that the wettability alteration process might be further improved through the use of dimeric or gemini surfactants, which have two hydrophilic head groups and two hydrophobic tails. We believe that when ion-pair formation is the dominant wettability alteration mechanism, wettability alteration in oil-wet cores can be improved by increasing the charge density on the head group(s) of the surfactant molecule since the ion-pair formation is driven by electrostatic interactions. At a concentration of 1.0 mmol L⁻¹ a representative anionic gemini surfactant showed oil recoveries of up to 49% original oil-in-place (OOIP) from oil-wet sandstone cores, compared to 6 and 27% for sodium laureth sulfate and surfactin, respectively. These observations are consistent with our hypothesis.