SPE-145039-PP Sustainable Surfactants in Enhanced Oil Recovery

Monika Santa, Cognis GmbH, Gabriela Alvarez-Jürgenson, BASF SE, Stefan Busch, Cognis GmbH, Paul Birnbrich, Cognis GmbH, Christian Spindler, BASF SE, Gregor Brodt, BASF SE
Copyright 2011, Society of Petroleum Engineers This paper was prepared for presentation at the SPE Enhanced Oil Recovery Conference held in Kuala Lumpur, Malaysia, 19–21 July 2011. This paper was selected for presentation by an SPE program committee following review of information contained in an abstract submitted by the author(s). Contents of the paper have not been reviewed by the Society of Petroleum Engineers and are subject to correction by the author(s). The material does not necessarily reflect any position of the Society of Petroleum Engineers, its officers, or members. Electronic reproduction, distribution, or storage of any part of this paper without the written consent of the Society of Petroleum Engineers is prohibited. Permission to reproduce in print is restricted to an abstract of not more than 300 words; illustrations may not be copied. The abstract must contain conspicuous acknowledgment of SPE copyright.

Abstract Alkyl polyglucosides (APGs) are recognised as sustainable surfactants based on natural raw materials. They exhibit a low ecotoxicity profile and are therefore already used in different oil field applications. In this paper it is shown that APGs have superior solubility properties in high salinity environments. The interfacial tension of crude/brine systems can be significantly lowered even in high salinity brines. The performance of APGs can be improved by optimising the hydrophobic as well as the hydrophilic part of the surfactant. In contrast to standard surfactants used in EOR applications the performance of APGs is not reduced under elevated temperature or high salinity conditions. Their performance is not influenced by typical salinity and temperature gradients as can occur in the reservoir. Moreover, microemulsions can be formed even under high salinity and elevated temperature if APGs are used together with co-solvents. Introduction Enhanced Oil Recovery With Surfactants Oil recovery is divided in three phases: primary, secondary and tertiary oil recovery. During the primary recovery the crude is driven from the rock into the production well by natural reservoir pressure. Throughout the secondary oil recovery phase water is injected into the reservoir. The injected water prevents the reservoir pressure from dropping; the crude is driven by the water flood to the producer well. At the end of the secondary oil recovery phase capillary and viscous forces keep the residual crude trapped in the reservoir rock. The ratio between these forces is described by the capillary number Nc:

Nc =

µw ⋅ v IFTo / w

where µw is the viscosity of the displacing phase (water), ν is its velocity and IFTo/w the interfacial tension between the crude oil and water. It was shown by several researchers that an increase of the capillary number improves the mobilisation of additional oil (Foster 1973; Lefevre du Prey 1973; Ehrlich et al. 1974; Melrose and Brandner 1974; Abrams 1975; MacDonald et al. 1979; Oh and Slattery 1979). If the capillary number is modified by adding additional substances to the waterflood one refers to tertiary or enhanced oil recovery (EOR). The capillary number can be enlarged in the most efficient way by reducing the interfacial tension IFTo/w to ultra-low values. This is achieved by adding a tailor made surfactant system adapted to the injection water, the nature of the crude oil and the reservoir conditions. At ultra-low IFT values microemulsions containing water and oil are formed in the reservoir rock. Due to the ultra-low IFT spheric Ooil drops that are trapped in rock pores are become deformabled by the flood pressure. After being elongated they pass and can be pushed by the water flood through the pore throats ininto to the producer well. During the last years research activities on surfactant-based EOR methods have increased significantly. Several surfactant floods have already been applied in combination with alkaline and polymer in mature oil fields (Manrique, 2010). While the use of surfactants in tertiary oil recovery is getting more and more accepted, environmental compatibility becomes an important topic. Regulatory authorities increasingly demand that EOR chemicals are environmentally sound. Sustainable

2009) and for reducing interfacial tension in surfactant-induced tertiary oil recovery processes (Balzer and Lueders 1988. (1995) measured IFT values between water and three different model oils in the presence of APG surfactants. 1997). 1995). They are applied in environmentally safe drilling fluids (Walker et al. 1997). Iglauer et al. ultimate degradation screening tests. in well cleaning agents (Forgiarini et al. They are already widely used in the oil industry. (2009) and Kahlweit et al. (2009) showed that in comparison to other nonionic or anionic surfactants currently used in EOR processes. Evaluations utilising methods like eco-efficiency analysis. They identified surfactant formulations allowing to reach ultra-low interfacial tensions in brine/alkane or brine/xylene systems. 1). APGs are tolerant to elevated salinities or high temperatures. Kutschmann et al. latest developments show that “greenness”environmental friendlyness does not mean to compromise on superior product properties. In the present study. . 1997). as foamers in heavy oil recovery (Wael et al. life-cycle assessment and carbon footprint prove the high sustainability potential of their use in EOR and other applications (Hill et al. We will demonstrate in this paper that sustainable EOR surfactant systems based on alkyl polyglucosides can be applied in conditions of high salinity and elevated temperatures where conventional surfactants often cannot be used anymore. Kahlweit et al. 2009). All data show that APGs are easily biodegradable and not harmful to aqueous organisms. 1: Chemical structure of C8-APGs Alkyl polyglucosides (APGs) are nonionic surfactants which are composed of an alcohol and a glucose based moiety (Fig. we evaluate whether the studied APGs are promising candidates for surfactant flooding processes.2 SPE SPE-145039-PP surfactants based on renewable raw materials. Alkyl Polyglucosides (APGs) Fig. Some exemplary ecotoxicity results for a C 8/10 modified APG are given in table 1 and table 2. superior EOR surfactant systems must be able to lower the IFT between the crude and connate water to ultra-low values. life-cycle inventory. 1995). Table 2: Ecotoxicity of C8/10 APG (Hill et al. (1995) determined the IFT in combination with linear alcohols as co-solvents. Table 1: Biodegradation data for C8/10 APG (Hill et al. showing good biodegradability under aerobic conditions have therefore become interesting candidates for EOR operations. Iglauer et al. Indeed. By carrying out experiments with crude oil. we compare the properties of APGs with different alkyl chain lengths and different hydrophilic moieties (table 3) using IFT measurements and phase studies. Developing sustainable surfactants without compromising on surfactant performance has become a key driver for the chemical industry. Furthermore. As already pointed out. APGs have a superior ecotoxicity profile.

A hydrophilic surfactant is described by a high HLB value. loosing loss of performance induced by precipitation of the surfactant in the payzone during the flood or even plugging of the formation. and 8. The formation of microemulsion was studied by visual observation of Windsor type III microemulsion phases at 20°C.100 ppm Mg2+ were performed for several APG compounds at 80°C. A surfactant concentration of 0. composed by dissolution of 133g/l NaCl. 1957). brines with 1050. In addition to the 180. Germany). An average IFT value was taken as result. Equilibration and measurements were performed at 20°C. The samples were mixed. Unfortunately standard EOR surfactants have often limited solubility in high salinity conditions. resulting in an overall surfactant/co-solvent concentration of 3. Decane and crude oil (25° API) were used as oil phases.5 weight-% of 1-octanol were put into the 20 ml oil/brine system. stable solutions.5 weight-% solution. However. 13. Solubility Precipitation during flooding has to be avoided in order to guarantee the performance of the process. C10 or C12/14 respectively. 50°C and 70°C. Interfacial Tension. Determination of Interfacial Tension (IFT) IFT measurements were performed using a Dataphysics SVT20 spinning-drop tensiometer (Filderstadt. All solubility tests were performed in high salinity brines and at elevated temperatures to simulate challenging reservoir conditions. Surfactants having passed successfully the solubility tests were evaluated for their IFT reduction potential. EOR surfactant formulations have to be soluble through the whole EOR process. In contrast to many standard surfactants APGs having alkyl chain lengths of 14 or less carbon atoms formed clear.000 ppm were prepared by dilution. 37.000 ppm TDS containing beside Na+. Therefore. A cloud point for APGs is therefore not observable at surfactant concentration applied in EOR.600 ppm Ca2+ and 2. Their good solubility in brines is caused by the exceptionally strong hydration of the hydrophilic glucose moieties in the molecule. The solubility of surfactants in brine was determined with a total dissolved salinity of 180. These APGs are insoluble as long as co-surfactants or co-solvents are not added to the surfactant system.000 ppm brine described above. Otherwise the operator would risk loss of injectivity issues. Therefore phase behaviour studies were performed to assess the potential of APGs as EOR surfactants at different salinities and temperatures.SPE SPE-145039-PP 3 Experimental Materials The APGs used in this study consist of a more hydrophilic (I) or a less hydrophilic (II) glucose moiety and alcohols with chain lengths of C8/10. Afterwards 2.000 ppm TDS brine described above forming a 2. Decane and a light crude oil (API° 25) were used as oil phase. Phase Behaviour Studies Microemulsion formation is a good indication whether a surfactant formulation can be used to mobilise additional oil effectively. IFT values were measured during 10 minutes. In the phase behaviour studies discussed in this paper 1-octanol was applied as a co-solvent. They are categorised based on their HLB value (Griffin. Therefore all further experiments were performed with soluble APGs having C12/14 or smaller alkylchains (table 3).2 % was chosen as it . If no precipitate was formed within three days of storage at room temperature and 80°C. Table 3: HLB values of substances tested (calculated according to Davies. for APGs with alkyl chains lengths exceeding 14 carbon atoms the hydrophobic interactions between the surfactant molecules dominate. 50°C and 80°C.000 ppm. the surfactants were used for further investigation.2 weight-%. 10 ml of oil were added to 10 ml of the surfactant solution. especially if fresh water is not available. All concentrations are given in weight-percentages (%) or parts per million (ppm). The surfactants were added to the brines in a concentration of 0.3 g/l MgCl2 in water. The APGs were dissolved in the 180. Results and Discussion APG Properties Under High Salinity Conditions Solubility. More and more high salinity brines have to be used for injection. 1949) which describes the surfactant’s hydrophilicity/lipophilicity balance. The brines were brought in contact with the oil phase and equilibrated for 20 minutes.3 g/l CaCl2. solubility tests in brine with 180.7 weight-%.000 ppm and 50100. Therefore good solubility of the surfactants at reservoir temperatures and salinities is essential.

This can be explained by the complex composition of crude that contains other compounds beside parrafins. Usually a minimum IFT value is found. At least an HLB of 11 is needed to obtain optimum performance (0. the IFT values are displayed as a function of the HLB value. 3). the oil phase and the water phase are taken into account. So. Surfactants with lower or higher HLB values did not perform as well. In order to better understand the good performance of APG B and its deviation from the overall tendency for the crude. For the investigated crude the lowest interfacial tension of 0. 2.15 mN/m). the effect of decreasing alkyl chain length on IFT is significantly smaller: here the IFT is reduced by 40% only. With decane.7 (APG B). In these circumstances the surfactants are packed most densely on the interface. The general tendency that the use of a smaller hydrophobe results in higher IFT values can be understood if the interactions between the surfactant. . the IFT is changing drastically with the alkyl chain length. Changing the nature of the hydrophobic alkylchain or the hydrophilic head group of the surfactant influences the performance of the surfactants. IFT values are plotted against alkyl chain length taking the nature of the different glucose head groups into consideration (Fig. Reducing the HLB from 11 to even lower values does not result in a further decrease of IFT.01 mN/m was found at an HLB value of 11. If the C 12/14 alkyl chain is replaced with the significantly smaller hydrophobe C8/10 the hydrophilic interactions between the aqueous phase and the surfactant dominate and the IFT increases significantly. We assume that this is the case for APG B if the investigated crude is used. in contrast to decane the best performance was not achieved by the most hydrophobic surfactants. if the interactions between the surfactant alkyl chains and the oil phase are balanced by the interactions of the head group and the water phase. For surfactants A and B which contain both the stronger hydrophilic glucose moiety I.4 SPE SPE-145039-PP is a common dosage in EOR applications. 2: Interfacial tension vs. Fig. the lowest IFT values were found with the more hydrophobic surfactants (lower HLB). A change from C12/14 to C8/10 results in an IFT increase by two orders of magnitude. As with any EOR surfactants the performance of APGs is dependent on the nature of the oil. In Fig. For APG D and C which include the less hydrophilic headgroup II. It is shown that low IFT values can be obtained by using APGs under high salinity conditions without any further additives. value of hydrophilic/lipophilic balance.

Compared to alkylalkoxylates the interaction between water molecules and APGs is significantly stronger due to the chemical structure of the glucose surfactant headgroup. currently used in EOR processes. A similar behaviour is found if the alkyl chain is kept unchanged but the more hydrophilic head group I in APG B is substituted by the glucose moiety II (APG D). In this case the surfactant becomes overall more hydrophobic. The IFT increases. The surfactant exhibits a lower tendency to migrate to the oil/water interface. As soon as these interactions become too weak. alkylalkoxylates or petroleum sulfonates. This is exactly the behaviour observed with APG B.SPE SPE-145039-PP 5 Fig. alkyl chain length. With decreasing solubility the interfacial performance of the surfactants is drastically reduced.g. 4 and 5 respectively. 3: Interfacial tension vs. Therefore the IFT of the water/oil/surfactant system remains low as soon as a certain threshold value is exceeded. . The solubility of alkylalkoxylates decreases often with increasing temperature. Both effects make clear that not only changes in the alkyl chain but also variations of the head group structure play an important role in optimising the performance of APG surfactants. the surfactant becomes insoluble. While between 20°C and 50°C the IFT decreases by approximately 50 %. In regard to temperature changes the behaviour of APGs differs significantly from other common surfactants like e. between 50°C and 70°C the IFT remains nearly unchanged. This is due to reduced intermolecular forces between the surfactant and the surrounding water molecules. The hydration of the glucose stays nearly unchanged with increasing temperature. Influence of Salinity and Temperature Changes The influence of changes in brine salinity and temperature on the IFT performance of the APG B system is shown in Figs.

If the brine salinity is further increased to 180.6 SPE SPE-145039-PP Fig. Under these high salinity conditions common surfactants like e. alkylbenzene sulfonates or soaps are even not even soluble.000 ppm. From these measurements we conclude that the performance of APG B will not be strongly influenced by fluctuations over a broad temperature and salinity range in the reservoir.000 ppm TDS.g. These differences can be explained by changes in surfactant hydration with increasing salinity and by the chelating shielding effects caused byof divalent ions being present in the connate water in the reservoir.000 ppm salinity. 70°C. In the investigated salinity range the IFT remains nearly unchanged when the brine salinity is increased from 50.000 ppm to 100. Fig. 100. 4: Interfacial tensions of APG B at 180. 5: Interfacial tensions of APG B at 50. This is an ideal behaviour for a surfactant in EOR applications where salinity gradients are commonly encountered.000 ppm TDS.000 ppm and 180. 50. The IFT was also determined at different salinities (Fig.000 ppm salinity and 20. Microemulsion Formation With APGs . 5). 5). the IFT is reduced by a half (Fig.

Again it is observed that due to the differences in hydrophobicity and chemistry of decane and crude oil. Both. 6: Observed microemulsion phase formed with APG B/1-octanol and crude oil at 80°C. Fig. One microemulsion phase is exemplarily shown in Fig. Furthermore it was shown that the performance of APGs is not strongly influenced by salinity or temperature variations as they can occur in typical oil reservoirs. Acknowledgement The authors would like to thank BASF SE for permission to publish this paper. 6. As APG B has shown the best performance in regard to IFT reduction. Abbreviations APG alkyl polyglucoside BOD biological oxygen demand COD Chemical oxygen demand DOC dissolved organic carbon EC effective concentration HLB hydrophilic lipophilic balance IFT interfacial tension LC letal concentration NOEC no observed effect concentration OECD Organization for Economic Cooperation and Development TDS total dissolved salt TOC total organic carbon . Normally microemulsions can be created if APGs are used together with a co-solvent. An indication for reaching ultralow IFT is the formation of microemulsions. For crude this effect is much more pronounced. 50°C. different microemulsion volumes are determined with APG and 1-octanol (table 4).000 ppm. The microemulsion volume is increasing by 100 % even under the chosen brine salinity of 180.SPE SPE-145039-PP 7 Best results in regard to additional oil are obtained if ultra-low IFT values can be reached. They exhibit a superior ecotoxicity profile. Together with co-solvents APGs can be used to form stable microemulsions even in extremely high salinity brines (180. For the following investigations 1-octanol was chosen as an additional compound for creating suitable surfactant systems. With decane the microemulsion volume is increasing by 20 % if the temperature is raised from 50°C to 80°C. the potential of APG B to form microemulsions was investigated more in detail. 80°C: volume of microemulsion (ml) formed from a 20 ml sample. Table 4: Microemulsion formation for APG B with 1-octanol as co-solvent for water/decane and water/crude oil at 20°C.000 ppm TDS) and at elevated temperatures (80°C). Conclusion In the industry APGs are recognised as sustainable surfactants. decane and crude could be microemulsified at 50°C and 80°C with the chosen surfactant/co-solvent ratio. At relatively low surfactant concentrations APGs are capable to decrease the IFT of crude oil/water systems significantly even under high salinity conditions and elevated temperature.

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