Journal of Petroleum Science and Engineering 66 (2009) 117120

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Journal of Petroleum Science and Engineering

j o u r n a l h o m e p a g e : w w w. e l s ev i e r. c o m / l o c a t e / p e t r o l

Microemulsion ooding for enhanced oil recovery

V.C. Santanna a,, F.D.S. Curbelo b, T.N. Castro Dantas c, A.A. Dantas Neto c, H.S. Albuquerque c, A.I.C. Garnica b
a b c

Departamento de Cincia e Tecnologia dos Materiais, Universidade Federal da Bahia, Rua Aristides Novis, 2, Federao, Salvador, CEP 40210-630, BA, Brazil Departamento de Tecnologia Qumica e de Alimentos, Universidade Federal da Paraba, Cidade Universitria, Campus I, Joo Pessoa, PB, Brazil Departamento de Engenharia Qumica, Universidade Federal do Rio Grande do Norte, Campus Universitrio, CEP 59072-970, Natal, RN, Brazil

a r t i c l e

i n f o

a b s t r a c t
Petroleum recovery methods basically consist of uid injection aiming to displace the oil out of the rock pores. Among the methods used in enhanced oil recovery, chemical methods, which may involve microemulsion ooding, are cited. In this work, injection assays have been carried out with two types of microemulsion: one was prepared with a commercial surfactant (MCS) and another contained a surfactant synthesized in laboratory (MLS). The experiments basically consisted of the injection of uids into cylindrical plug samples from the Assu Formation (RN, Brazil). During the microemulsion ooding, samples were collected as a function of time and the mass of oil recovered by the microemulsion was determined. From the results obtained, one could conclude that the use of microemulsion prepared with the commercial MCS allowed for recovery indices as high as 87.5%, whilst the use of the MLS microemulsion permitted recovery indices as high as 78.7%. This was mainly due to the difference in viscosity between the two microemulsions used. Published by Elsevier B.V.

Article history: Received 3 September 2007 Accepted 25 January 2009 Keywords: enhanced oil recovery microemulsion ooding

1. Introduction As far as conventional oil recovery processes are concerned, it is estimated that around 30% of all oil already discovered could have been recovered. The application of enhanced recovery methods (tertiary oil displacement process) has been investigated with the purpose of responding to the requirements of energy supply when reserves of oil extracted through conventional techniques (secondary oil displacement process) start to become unproductive. As a result, enhanced oil recovery processes mainly focus on the segment that corresponds to 70% of the original oil detected, which is the mean percent volume remaining in the reservoirs after conventional extraction. Petroleum recovery methods basically consist on the injection of uid with the objective of displacing oil out of the rock pores where it is impregnated. The injected uid may be known as displacing uid and pushes the oil, called as displaced uid, out of the rock and at the same time occupies the empty space left as the displaced uid is expelled. Enhanced oil recovery methods are classied in one of three categories: thermal methods, miscible methods and chemical methods. This categorization is not singular and there may be processes that could be included in one or other class. In the present investigation, we have aimed to focus on the chemical method, which comprises microemulsion systems as templates. With chemical methods, one assumes that the processes occur with a certain
Corresponding author. Tel.: +55 71 3283 9839. E-mail addresses: vanessac@ufba.br (V.C. Santanna), fabioladias@yahoo.com (F.D.S. Curbelo), tereza@eq.ufrn.br (T.N. Castro Dantas). 0920-4105/$ see front matter. Published by Elsevier B.V. doi:10.1016/j.petrol.2009.01.009

degree of chemical interaction between the injected uid and the reservoir uid. This may be achieved by injecting polymer solutions, surfactant solutions, microemulsions or alkaline solutions. Surfactant solutions ooding is carried out with the purpose of reducing interfacial tensions between oil and water, thus increasing the displacement efciency (Kwok et al., 1995). However, this procedure usually presents low efciencies due to the low viscosity of the surfactant solutions as compared to that of the oil. In view of this, microemulsion ooding has been suggested as an alternative method, taking advantage of the unique properties of the microemulsion systems, which feature higher viscosity and induces low interfacial tension, increasing the oil extraction efciency. Nevertheless, surfactants ooding at low concentration is not a satisfactory process. This may occur if the molecules are adsorbed onto the reservoir rock (Kessel, 1989). A feasible alternative is the surfactants ooding at high concentration. The interfacial tension behavior in this type of process is better described by examining the phase behavior of microemulsion systems. Important concepts and details on the phase behavior of such systems has been presented by Winsor (Friberg and Bothorel, 1987). According to Austad and Strand (1996), very low interfacial tensions may be reached with microemulsion systems. Under such circumstances, microemulsions ow more easily through the porous medium, which enhances the oil extraction performance. Microemulsion systems formed with an anionic surfactant, alcohol, brine and crude oil reduce the interfacial tension between the brine and the oil found in excess in the reservoir rock (Wellington and Richardson, 1997). In order to promote reasonable oil recovery efciency, the surfactant must be chemically stable, reduce the interfacial tension between brine and crude oil and displace the oil

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without signicant concentration loss, which may occur by adsorption onto the reservoir rock. Surfactant retention in the reservoir rock is the most restrictive factor that affects the efciency of the oil recovery process by microemulsion ooding (Glover et al., 1979). Salinity and surfactant concentration also inuence the surfactant adsorption on the reservoir rock. Upon microemulsion ooding, a high surfactant concentration must be used so as to form micelles that can solubilize or dissolve the reservoir oil. This process takes place via incorporation of small oil droplets in the micelle core, effectively causing miscibility in the system (Shindy et al., 1997). According to Babadagli (2005), the way by which the uid is injected when the chemical method is employed is an important parameter for its optimization. Continuous injection of a chemical solution may increase operation costs and/or reduce the amount of treated material. In view of this, injection of chemical solution considering the porous volume number (PV) is required in any efcient process. Thomas and coworkers (in: Babadagli, 2005) injected porous volumes of microemulsion in sandstone plugs containing 35% of residual oil and could observe a linear relationship between the values of injected PV and the oil recovery, typically reaching 45% of residual oil recovery by injecting 10 PV of microemulsion. In this work, injection assays were carried out with two different kinds of microemulsion systems: one prepared with a commercial surfactant and another containing a surfactant that was synthesized in laboratory. 2. Materials and methods 2.1. Chemicals The chemicals used to prepare the microemulsion systems were: commercial anionic surfactant (soapsodium salt) derived from fatty acids (20 wt.% to 30 wt.% of vegetable oil and 70 wt.% to 80 wt.% of animal oil); anionic surfactant (soapsodium salt) synthesized in laboratory, derived from fatty acids (100 wt.% of vegetable oil containing 12 carbon atoms); iso-amyl alcohol (C5H11OHMerck), which acts as a cosurfactant; pine oil (organic phase, used without further purication; and distilled water. Petroleum samples assayed were provided by the treatment station of Guamar (Petrobras/RN, Brazil). 2.2. Microemulsion Microemulsion regions were determined in phase diagrams, constructed at room temperature (26 C) using pseudoternary systems comprising distilled water, vegetable oil and a xed cosurfactant/ surfactant ratio of 0.5, only varying the type of surfactant. The diagram regions were described according to Winsor's classication (Friberg and Bothorel, 1987). Winsor proposed a classication based on the nature of the phases involved. This classication establishes four types of systems: Winsor I (WI)a typical oil-in-water microemulsion phase is in equilibrium with an organic phase in excess; Winsor II (WII) a typical water-in-oil microemulsion phase is in equilibrium with an aqueous phase in excess; Winsor III (WIII)a typically bicontinuous microemulsion phase is in equilibrium with both aqueous and organic phases (three-phase system); and Winsor IV (WIV)it is a one-phase system, on a macroscopic scale, constituted only by a microemulsion. It is common practice to depict four-component microemulsion systems in pseudotenary diagrams. In order to determine the Winsor's regions in a pseudoternary diagram, the oil phase was mixed with the cosurfactant/surfactant phase and the mixture was titrated with water so as to observe any changes in the Winsor's regions. The volume of water used was determined for each region change. The pseudoternary phase diagrams were built by plotting the amounts of water, oil, and cosurfactant/surfactant phases used in each experiment.

After constructing the pseudoternary phase diagrams featuring the microemulsion regions of interest, one point with specic composition was chosen inside each microemulsion region in the diagrams. The microemulsion systems were then prepared under mechanical stirring, all chemicals were added at the same time and remained under agitation for about 30 min. 2.3. Microemulsion ooding assays Injection assays were performed with an apparatus that basically promoted the injection of uids in sandstone plugs from the Assu Formation (RN, Brazil), as schematically shown in Fig. 1. This apparatus was used with success in surfactant ooding experiments (Curbelo et al., 2007). The cylindrical plugs were insulated with resin and had the following dimensions: 3.8 cm diameter and 8.7 cm length. The brine used consisted of a 2 wt.% KCl aqueous solution. All plugs had been calcined at 700 C for 18 h prior to the treatment with resin, in order to let all the plugs in the same conditions (in terms of humidity, organic material content, porosity). This treatment reduces humidity and enhances permeability for all the samples. The following steps were observed during the injection assays: - 1st step: in order to determine the initial permeability and the porosity of the plug, the brine was injected at constant ow rate through the plug and 30 psi of pressure. Two porous volumes of brine were injected for approximately 2 h; - 2nd step: once the plug was saturated with brine, oil with 2.9 cP viscosity was injected at constant ow rate and at 30 psi of pressure. Two porous volumes of oil were injected for approximately 6 h; - 3rd step: brine is once again injected at 30 psi aiming to verify the recovery of oil by the conventional method (secondary oil displacement process) after plug saturation; - 4th step: with the purpose of determining the oil recovery, that is, the percentage of oil displaced from the plug pores, microemulsion was injected into the plug (tertiary oil displacement process) at constant ow rate and 30 psi. Samples were collected that initially presented oil, and the collection proceeded until they were clear. The oil content in the samples was determined by color readings, with a Tintometer PFX950. Microemulsion samples were collected at specic time intervals under pressure application.

Fig. 1. Microemulsion ooding experimental apparatus.

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The permeability of the plugs was assessed with the Darcy equation, Eq. (1), used with uid ow in porous materials. For a horizontal linear system, this relationship is (Ahmed, 2006): q= KA dP dx 1

where q is the volumetric ow rate in cubic centimeters per second and A is total cross-sectional area of the rock in square centimeters. The uid viscosity, , is expressed in centipoise units, and the pressure gradient, dP/dx, is in atmospheres per centimeter, taken in the same direction as q. The proportionality constant, K, is the permeability of the rock expressed in Darcy units. 2.4. Recovery factor The recovery factor was calculated by two methods, either using a secondary oil displacement procedure or by means of a tertiary oil displacement technique, overall comprising two steps: - The rst step, corresponding to the secondary recovery method, involves the injection of brine into the plug, as described in the third step of the injection assay above. At this point, a certain amount of oil is recovered and another remains in the plug. The brine only pushes away the oil found in the plug, under high interfacial tensions and lacking any chemical interaction. The amount recovered is calculated via a mass balance, according to Eq. (2). Volumeoil remaining in the plug = Volumeoil injected Volumeoil expelled 2

Fig. 3. MLS system: distilled water, synthesized surfactant (S), pine oil, iso-amyl alcohol (C), and C/S ratio = 0.5 (26 C).

The recovery factor is veried by summing up the amounts of oil recovered in each step (secondary and tertiary oil displacement processes) and is expressed in percentage (%), as shown in Eq. (3): RFTOTAL = RFSM + RFTM = MRSM + MRTM = MTOTAL INJECTED 3

- The second step is performed with the objective of recovering any amount of oil still stored in the plug, which corresponds to the implementation of a tertiary recovery method, whereby microemulsion is injected in the fourth step of the injection assay. This solution works by reducing interfacial tensions between the contacting uids and, as a result, the volume of recovered oil increases. The determination of the amount of oil recovered by microemulsion is described as follows. During microemulsion ooding, samples are collected at regular time intervals and the mass of oil is quantied via color analyses with a Lovibond PFX 950 tintometer. A calibration curve was initially constructed by plotting color versus concentration, using different oil amounts.

where: RFTOTAL is the total recovery factor (%); RFSM is the recovery factor obtained with the secondary method (%); RFTM is the recovery factor obtained with the tertiary method (%); MRSM is the mass of oil recovered by the secondary method (g); MRTM is the mass of oil recovered by the tertiary method (g); MTOTAL INJECTED is the total mass of oil injected (g). 3. Results and discussion 3.1. Phase diagrams Pseudoternary phase diagrams were constructed in order to determine the microemulsion regions, as shown in Figs. 2 and 3, where very well dened microemulsion regions (WIV) are shown. The gel region shown in Fig. 2 was used in others experiments applied in petroleum industry (Castro Dantas et al., 2006). Two points were chosen inside the microemulsion regions, one for each pseudoternary diagram. Their compositions, in wt.%, were as follows: (1) MCS13.3% surfactant, 6.7% cosurfactant, 50% organic phase, 30% aqueous phase; and (2) MLS16.7% surfactant, 8.3% cosurfactant, 45% organic phase, 30% aqueous phase. 3.2. Recovery factor (total and partial) Table 1 presents the properties of the plugs used in the recovery assays for each microemulsion studied. The total recovery factor for petroleum is established as a function of the recovery effected with brine (secondary methodSM) and the recovery promoted by microemulsion (tertiary methodTM). The partial and total recovery factors for each microemulsion studied are presented below.

Table 1 Plugs properties. Plug 1 (MCS) 2 (MLS) Porosity (%) Fig. 2. MCS system: distilled water, commercial surfactant (S), pine oil, iso-amyl alcohol (C), and C/S ratio= 0.5 (26 C). 27 21 Porous volume (cm3) 26.28 20.44 Absolute permeability (mD) 0.8 1.4

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Fig. 4. Recovery factor for MCS microemulsion.

Fig. 5. Recovery factor for MLS microemulsion.

When working with the MCS microemulsion, 8 mL brine were rstly injected (1st step) into the plug, which became saturated. As oil is passed through (2nd step), 5.4 mL of oil remained in the plug. In the 3rd step, as more brine is pumped through, 3.4 mL of the oil were extracted, thus allowing for 2 mL of oil to remain in the plug and be recovered by the MCS microemulsion. After these saturation steps, the MCS microemulsion was injected (4th step). As a result an oil recovery factor as high as 87.5% could be reached, considering the summation of both secondary and tertiary methods. These data can be observed in Fig. 4. If only the tertiary recovery method (MCS microemulsion) is taken into account, it could be inferred that, from the 2 mL of oil remaining in the plug (the secondary method could recover 3.4 mL from the 5.4 mL injected), 1.33 mL were recovered. Therefore, the recovery factor related only to the MCS microemulsion ooding can be calculated as shown in Eq. (4) and Table 2:
RFTM = volume of oil recoveredTM = volume of oil remaining in the plug

These results allowed to conclude that the MCS microemulsion is more efcient in oil recovery, in that it provides recovery factors as high as 87.5%, when compared to the MLS microemulsion (78.7%). This is mainly due to the viscosity of the microemulsion systems, the MCS microemulsion having higher viscosity (32 cP) than the MLS microemulsion (27 cP), which allows more oil to be recovered from the rock and increases the extraction efciency. The experimental errors involved in viscosity measurements (microemulsions and oil) were around 3%. 4. Conclusions Based on the fact that the main objective of this work was to evaluate petroleum recovery factors using microemulsion systems with ionic surfactants, some conclusions could be summarized: 1) The use of microemulsions in enhanced petroleum recovery is an efcient tool, for they provide high levels of extraction. When the commercial surfactant-based MCS microemulsion is used, a recovery factor as high as 87.5% was obtained, whilst the use of the synthesized surfactant-based MLS microemulsion was efcient in recovering 78.7% of oil. This was due to the difference in microemulsion viscosities, corroborated by the fact that the MCS microemulsion (32 cP viscosity) could recover more oil than the MLS microemulsion (27 cP viscosity). 2) Both microemulsion systems were efcient in the oil extraction process, in that they possessed higher viscosities than the oil itself. Acknowledgement The authors acknowledge the nancial support from CNPq (Conselho Nacional de Desenvolvimento Cientco e Tecnolgico, Brazil). References
Ahmed, T., 2006. Reservoir Engineering Handbook. Gulf Professional Publishing. 1376 pp. Austad, T., Strand, S., 1996. Chemical ooding of oil reservoirs4. Effects of temperature and pressure on the middle phase solubilization parameters close to optimum ood conditions. Colloids Surf., A Physicochem. Eng. Asp. 108, 243252. Babadagli, T., 2005. Mature eld developmenta review. SPE 93,884, 120. Castro Dantas, T.N., Santanna, V.C., Dantas Neto, A.A., Curbelo, F.D.S., Garnica, A.I.C., 2006. Methodology to break test for surfactant-based fracturing gel. J. Pet. Sci. Eng. 50, 293298. Curbelo, F.D.S., Santanna, V.C., Barros Neto, E.L., Dutra Jnior, T.V., Castro Dantas, T.N., Dantas Neto, A.A., Garnica, A.I.C., 2007. Adsorption of nonionic surfactants in sandstones. Colloids Surf., A Physicochem. Eng. Asp. 293, 14. Friberg, S.E., Bothorel, P., 1987. Microemulsions: Structure and Dynamics. CRC Press, Boca Raton. 219 pp. Glover, C.J., Puerto, M.C., Maerker, J.M., Sandvik, E.L., 1979. Surfactant phase behavior and retention in porous media. SPE 7053, 183193. Kessel, D.G., 1989. Chemical oodingstatus report. J. Pet. Sci. Eng. 2, 81101. Kwok, W., Hayes, R.E., Nasr-El-Din, H.A., 1995. Modelling dynamic adsorption of an anionic surfactant on berea sandstone with radial ow. Chem. Eng. Sci. 50 (5), 769783. Shindy, A.M., Darwich, T.D., Sayyouh, M.H., Abdel-Aziz Osman, 1997. Development of an expert system for EOR method selection. SPE 37,708, 291298. Wellington, S.L., Richardson, A.E., 1997. Low surfactant concentration enhanced waterooding. SPE 2 (30,748), 389405.

4 By summing up all steps (secondary and tertiary methods), one has the total recovery factor (Eq. (5) and Table 2): RFTOTAL = volume of oil recovered = volume of oil injected 5

When investigating the MLS microemulsion, the saturation of the plug in the 1st step was effected with 23 mL brine. This higher saturation level is due to the enhanced permeability of the plug used (Table 1). As oil was passed through (2nd step), 16 mL of oil remained in the plug. In the 3rd step, as more brine is pumped through, 8 mL of the oil were extracted, thus allowing for 8 mL of oil to remain in the plug and be recovered by the MLS microemulsion. After these saturation steps, the MLS microemulsion was injected (4th step). From the data gathered, the recovery factor for oil was, in this case, as high as 78.7%, combining both secondary and tertiary method. These results are better observed in Fig. 5. When only the tertiary recovery method (MLS microemulsion ooding) is assessed, it could be seen that, from the 8 mL of oil still remaining in the plug (the secondary method could recover 8 mL from the 16 mL injected), 4.59 mL were recovered. Thus, the recovery factor regarding only MLS microemulsion ooding can be calculated using the Eq. (4), as shown in Table 2. By summing up all steps (secondary and tertiary methods), one has the total recovery factor given by Eq. (5), as shown in Table 2:
Table 2 Recovery factors of microemulsions. Microemulsion MCS MLS RFTM (%) 66.5 57.4 RFTOTAL (%) 87.5 78.7