MICROEMULSION SYSTEMS FOR EXTRACTION AND DISPLACEMENT OF OIL IN SANDSTONE ROCKS

Abstract

The present invention provides for obtaining microemulsion formulations without the presence of an oil phase for the removal of oil from solid surfaces, specifically in sandstone rocks. Oil impregnation on solid surfaces is a major challenge due to the need to purify environments affected by environmental disasters and accidents related to the oil and gas industry. Thus, the study and development of technologies capable of preventing or remedying the effects that oil contamination on solid surfaces can cause is justified, Several technologies present themselves as promising candidates for the remediation of contaminated surfaces, but many of them can have high execution costs, as in the case of classic microemulsions, or generation of secondary residues. The process of the present invention does not present these disadvantages, consisting of obtaining microemulsion systems containing nonionic surfactants of different degrees of ethoxylation (lauryl alcohol with 10, 8 and 6 ethoxylation bonds), short-chain alcohol (1-butanol) and distilled water for the extraction of heavy crude oil impregnated in sandstone rocks. The formulations presented are capable of using low active matter compositions, unlike classical microemulsions which, in most cases, require a high amount of surfactant.

Claims

1-8. (Canceled).

9. A microemulsion formulation comprising a non-ionic surfactant lauryl alcohol ethoxylate in a concentration ranging from 0.01% to 5%, a short-chain alcohol in a concentration ranging from 0.01% to 5%, and water in a concentration ranging from 90% to 99.98%.

10. The microemulsion formulation of claim 9, wherein the non-ionic surfactant lauryl alcohol ethoxylate contains from four to twelve ethoxylated bonds.

11. The microemulsion formulation of claim 9, wherein the short-chain alcohol is ethanol, propanol, or butanol.

12. A method of making the microemulsion formulation of claim 9, wherein the formulation is mechanical stirred at a speed of up to 1,000 rpm, until a single clear phase is formed.

13. The method of claim 12, wherein the ethoxylated lauryl has from four to twelve ethoxylated bonds.

14. The method of claim 12, wherein the short-chain alcohol is ethanol, propanol, or butanol.

15. A method of extracting and displacing oil from sandstone rocks, wherein the sandstone rocks are exposed to the microemulsion formulation of claim 9 in a volume/weight ratio of 20 to 40 mL of the microemulsion formulation per gram of the sandstone rocks, at a temperature ranging from 40° C. to 60° C., and for a period of 3 to 4 hours.

16. The method of claim 15, wherein the non-ionic surfactant lauryl alcohol ethoxylate contains from eight to twelve ethoxylated bonds.

17. A method of extracting and displacing oil from sandstone rocks, wherein the sandstone rocks are exposed to the microemulsion formulation of claim 9 in a volume/weight ratio of 5 to 20 mL of the microemulsion formulation per gram of the sandstone rocks, at a temperature ranging from 20° C. to 40° C., and for a period of 1 to 2 hours.

18. The method of claim 17, wherein the non-ionic surfactant lauryl alcohol ethoxylate contains from four to six ethoxylated bonds.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

[0009] FIG. 1 shows the ternary diagram obtained from the combination of different mass compositions of the three components of the systems (surfactants, alcohol and water) and the phases found.

[0010] FIG. 2 shows the calibration curve obtained to quantify the oil extracted and present in the microemulsion with the aid of ultraviolet spectroscopy (UV-Vis).

[0011] FIG. 3 shows the physical appearance of microemulsions after oil extraction, with an increase in color with each extraction, which shows the continuous removal of oil.

DESCRIPTION OF THE INVENTION

[0012] As a preferred way of carrying out the invention, among the various possible compositions of constituents for the microemulsion without oil phase, it is established, for this patent, that the following proportions of the system components are used: from 0.01% to 5% of lauryl alcohol, preferably from four to twelve ethoxylated bonds; from 0.01% to 5% of a short-chain alcohol, preferably ethanol, propanol and butanol; and from 90% to 99.98% aqueous phase, preferably water.

[0013] The order of reagents in the preparation of formulations can be done randomly. The mixture of constituents to obtain these systems should be carried out by mechanical agitation at a maximum speed of 1,000 rpm over time until a single clear phase is ensured.

[0014] For application of the system, in the case of microemulsions containing the surfactant lauryl alcohol with twelve to five ethoxylated bonds, it is preferable that the extraction system be placed under high temperatures (between 40° C. and 60° C.), long contact time (3 h to 4 h) and 20 mL to 40 mL. of microemulsion to be applied to every 1 g of contaminated rock.

[0015] For application of the system, in the case of microemulsions containing the lauryl alcohol surfactant from six to four ethoxylated bonds, it is preferable that the extraction system be placed at low temperatures (between 20° C. to 40° C.), low contact time (1 h 2 h) and 5 mL to 20 mL of microemulsion to be applied to every 1 g of contaminated rock.

RESULTS OBTAINED

[0016] Three microemulsion systems were obtained using distilled water as aqueous phase, 1-butanol as amphisolvent (co-surfactant) and ethoxylated lauric alcohol with ten, eight and six ethoxylated groups (LA 10EO, LA 8EO and LA 6EO, respectively) as surfactants. A conventional oily phase was not used because 1-butanol could perform a role similar to that of an oily phase as it is a predominantly non-polar molecule.

[0017] A composition of the single-phase region of each microemulsion system was chosen to be the extraction solvent. To delimit the area of that region, a volumetric titration analysis was used to determine the Winsor regions in pseudoternary diagrams. For this, nine mixtures of different compositions of surfactants and aqueous phase (X.sub.T+X.sub.FA=2 g, 10% to 90% by weight of surfactant) were titrated dropwise with alcohol until the transition from clear to cloudy appearance was achieved in a test tube. The same procedure was carried out with nine mixtures of different compositions of surfactant and co-surfactant (X.sub.T+X.sub.C=2 g, 10% to 90% by weight of surfactant) and titration with aqueous phase.

[0018] FIG. 1 shows the three ternary diagrams obtained and condensed into a single diagram. When observing the diagram, two biphasic regions are perceived, one of which is characterized by the solubilization of the three constituents (water, butanol and surfactant) with an excess of surfactant (1ϕ+US), since this molecule has a solubility limit in aqueous media , with the exception of LA 6EO, which requires little water molecule for its complete hydration due to the smaller amount of ethoxylated groups; while the other region is characterized by the insufficient amount of surfactants to form micelles, causing the separation of water and butanol solvents (2ϕ). The single-phase region (1ϕ) represents the largest area of the diagram. We made the option for the formulation of a single-phase chemical system rich in water and, consequently, with a low percentage of alcohol and surfactant. The formulation contains 90% water, 5% butanol and 5% surfactant. This composition is illustrated in FIG. 1.

[0019] The micellar diameter (±0.3 standard deviation) was 12 nm to 14 nm for the formulation containing LA 10EO, 20 nm to 25 nm for the formulation containing LA 8EO and 40 nm to 45 nm for the formulation containing LA 6EO. Micellar diameter increases as the degree of ethoxylation of surfactants decreases. This was expected because the more predominantly non-polar the surfactant, the more alcohol will be encapsulated in the micellar nucleus, which increases the size of the aggregate. All value ranges are as expected for microemulsion systems according to the literature.

[0020] The surface tension values of the microernulsion formulations were: 29.12 mN.m.sup.−1 to 30 mN.m.sup.−1 for the formulation containing LA 10EO; 28.32 mN.m.sup.−1 to 29 mN.m.sup.−1 for the formulation containing LA 8EO and 27.68 mN.m.sup.−1 to 27.90 mN.m.sup.−1 for the formulation containing LA 6EO. This slight decrease in surface tension values with the decrease in the degree of ethoxylation was expected, as the lower the degree of ethoxylation, the greater the migration of surfactant molecules to the liquid-gas interface, significantly decreasing the surface tension, as already reported in literature,

[0021] As a way to test the present invention, Botucatu sandstone rocks (RN/Brazil) were broken and their particles separated in granulometric sieves from 100 mesh to 150 mesh to obtain grains of uniform size.

[0022] The contamination of the rocks consisted of the addition of heavy oil to the dry sandstone rocks in the proportion of 1:10 by weight. The mixture was stirred in the presence of an ultrasonic bath, in order to obtain a good homogenization between the oil and the rocks, as well as to avoid oil impregnation on the container walls. Next, the mixture was spread on a tray and covered with aluminum foil, with small openings made to allow ventilation. Finally, the mixture was placed in an oven at a temperature of 40° C. to 50° C. for 4 h to 5 h, for better oil impregnation. The entire process was controlled via mass balance with minimal oil losses during heating (0.12% to 0.15%), which was neglected in the final calculations.

[0023] Between 1 g and 1.2 g of oil-contaminated sandstone was added to a 250 mL Erlenmeyer flask. Then, an amount of microemulsion was added, in volume, according to the experimental design. The samples were placed in a thermostatic bath under constant stirring of 50 rpm. After reaching the desired contact time, a filtration (14 μm, ϕ=11 cm) was performed to separate the treated rock grains from the solvent carrying the extracted oil.

[0024] The quantification of the oil content in the microemulsion was performed with the aid of UV-Vis spectroscopy. A spectrum scan was performed and the wavelength with the highest absorbance (A) was between 190 nm and 210 nm. The absorbance values were converted into the concentration of oil present in the microemulsion by means of a previously obtained calibration curve, which was constructed from the addition of a fixed amount of oil to different volumes of microemulsions, and these mixtures were analyzed by absorbance. FIG. 2 shows the calibration curve representing the amount of petroleum solubilized in the microemulsion as a function of absorbance values. The calibration equation (Equation 1) presented a coefficient of determination R.sup.2=0.984, thus showing a good adjustment of the experimental data.

C=0,0035.(Abs)−0,0003   (Eq. 1)

[0025] It is known that, depending on the external or operating conditions of the system, surfactants can change their hydrophilic-lipophilic (HLB) nature, becoming more polar, which reduces the interaction with oil, or extremely non-polar, which can cause adsorption of the surfactants in the rock and, by affinity, remove the oil through its encapsulation inside the micelle. To study the efficiency of the solid-liquid extraction process, the following variables were selected: volume of the microemulsion system used (V.sub.MES mL), bath temperature (T, °C.) and solvent-to-feed contact time (t, h). The density of all microemulsion systems was 1 g/mL. To investigate the effects of these variables and optimize the process, an experimental 2.sup.3 factorial design was carried out with three repetitions at the central point. The response variable was the oil extraction efficiency (% EE) from the rock (Equation 2). All tests were performed in duplicate. Table 1 shows the levels of each factor.

[00001]$\begin{array}{cc}\mathrm{EE}\left(\%\right)=\frac{{\left(m_0\right)}_F-{\left(m_f\right)}_R}{{\left(m_0\right)}_F}& \left(\mathrm{Eq}.2\right)\end{array}$

TABLE-US-00001 TABLE 1 Levels assumed by the influence parameters in the solid-liquid extraction process. Levels Variables −1 0 1 V.sub.MES (g) 20 30 40 Temperature (° C.) 27 43.5 60 Contact time (h) 1 2.5 4

[0026] Table 2 presents the values of extraction efficiency (% EE) of oil, showing percentages between 3.680±0.933% and 99.8±0.266%, proving that the variables (V.sub.MES, T et) directly interfere with the extraction process. However, it is clear that the decrease in the degree of ethoxylation is decisive to increase the extraction efficiency. This is due to the predominance of the non-polar tail in relation to the head, which reduces its structure, making the LA 6EO more suitable for interacting with the non-polar solute.

TABLE-US-00002 TABLE 2 Results of planning experiments for oil extraction efficiency (% EE). Variables V.sub.MES T t EE (%) Assays (g) (° C.) (h) LA EO10 LA EO8 LA EO6 1 20 27 1 4.220 ± 0.631 14.318 ± 0.206 99.800 ± 0.266 2 40 27 1 4.154 ± 0.015 14.413 ± 0.604 87.440 ± 0.212 3 20 60 1 9.057 ± 0.280  9.789 ± 0.491 75.240 ± 0.207 4 40 60 1 10.916 ± 0.870  18.253 ± 0.179 57.505 ± 0.112 5 20 27 4 3.680 ± 0.933 13.523 ± 0.169 59.283 ± 0.267 6 40 27 4 3.913 ± 0.331 10.347 ± 0.120 20.973 ± 0.220 7 20 60 4 10.756 ± 0.098  21.571 ± 0.104 77.688 ± 0.132 8 40 60 4 15.065 ± 0.114  26.678 ± 0.334 34.745 ± 0.388 9 30 43.5 2.5 7.719 ± 0.342 16.851 ± 0.781 64.748 ± 0.783 10 30 43.5 2.5 7.792 ± 0.319 16.224 ± 0.354 64.504 ± 0.715 11 30 43.5 2.5 7.156 ± 0.334 16.772 ± 0.334 64.129 ± 0.132

[0027] It is possible to notice that the surfactants LA 10EO and LA 8EO had higher oil extraction values when they were in larder volumes of microemulsion, higher temperature and longer contact time. The percentage of oil extraction is increased with the increase in the volume of the microemulsion, since more micelles are found in the medium, which allows the encapsulation of larger amounts of oil in the micellar nuclei.

[0028] Also for LA 10EO and LA 8EO, the percentage of oil extraction increases with increasing temperature. The increase in temperature makes the surfactants more non-polar, which provides greater contact between the micelles and the oil adsorbed with the rock and, therefore, more oil is removed. Furthermore, the increase in temperature causes greater collisions of micelles with the rock, which increases oil capture. Another important phenomenon is the decrease in the surface tension of the microemulsion, which reduces the interfacial tension between this system and the oil, and thus facilitates the encapsulation of oil in the micelle. All these phenomena make the surfactants LA 10EO and LA 8EO improve their percentages in oil removal.

[0029] For LA 6EO, the best extractions occur in smaller microemulsion volume, lower temperature and shorter contact time. In this case, the increase in the volume of the microemulsion caused a reduction in the percentage of oil removal, which shows the interference of another phenomenon. Among the surfactants, LA 6EO is the one with the greatest affinity to oil and, therefore, should have the highest percentage of extraction. However, this surfactant is also more easily adsorbed by the rock, which allows the oil to return to the rock because it is solubilized inside the micelle. Consequently, for larger volumes of microemulsion, the microemulsion/rock ratio is increased, which increases the possibility of more micelles being adsorbed by the rock. Thus, the extraction efficiency ends up being higher when there is a smaller volume of microemulsion. This phenomenon of adsorption of non-ionic surfactants due to HLB was identified by several studies in the literature, which corroborates the results obtained here,

[0030] Also for the LA 6EO, the increase in temperature further decreased the percentage of extraction, as the increase in temperature decreases the solubility of the surfactant in the medium, contributing to its migration and adsorption into the rock surface. This adsorption phenomenon due to the increase in temperature is more evident when there is a greater volume of microemulsion, because in this case the amount of adsorbed surfactant increases even more, which justifies the decrease in the percentage of oil extraction.

[0031] The percentage of oil extraction increases with increasing stirring time. The longer the stirring time, the greater the possibility of the micelles colliding with the rock, which facilitates the incorporation of oil into the micelle core and, thus, increases the efficiency of the surfactants LA 10EO and LA 8EO. For LA 6EO, the increase in stirring decreases the percentage of oil extraction, as the surfactant is adsorbed into the rock right after the oil is removed, as already mentioned. Thus, the longer the stirring time, the longer the micelles contact with the rock, favoring the return of oil to the rock.

[0032] After obtaining the results of the statistical analysis of the experimental design, the best operational conditions (microemulsion volume, temperature and contact time) for oil extraction for each formulation, containing the surfactants used, were grouped into an operational condition called the optimal point, which were chosen for each system to continue the study in order to assess the efficiency of a cross-current process using the microemulsion as feed (carrying capacity of the microemulsion in relation to oil).

[0033] Table 3 shows the results of the load capacity of microemulsions and the surface tension values of each filtrate, as a way to monitor the stability of the microemulsions. All systems were efficient in removing oil until the third extraction. From the fourth attempt on, the microemulsion was broken, generating two phases (microemulsion and co-surfactant), which made it impossible to quantify the oil removed.

TABLE-US-00003 TABLE 3 Carrying capacity of petroleum extraction by microemulsions in three stages. LA 10EO LA 8EO LA 6EO Surface Surface Surface tension tension tension Assay EE (%) (mN/m) EE (%) (mN/m) EE (%) (mN/m) 1 15.065 ± 0.114 29.12 26.678 ± 0.334 28.32 99.98 ± 0.266 27.68 2 12.959 ± 0.938 29.92 15.065 ± 0.398 29.92 48.237 ± 0.874  28.39 3  8.317 ± 0.182 31.36 10.608 ± 0.182 31.49 4.825 ± 0.945 29.24

[0034] However, it should be noted that even after its imbalance, the microemulsion still continued to extract oil from the rock, which no longer occupies the micelle nucleus (since it is already saturated), but rather as an excess phase of the microemulsion. This behavior was already expected, as the authors had already demonstrated in previous studies.

[0035] After each reuse, the microemulsions had their surface tension values increased, indicating that the surfactants are not migrating to the liquid-gas interface, but to the liquid-liquid interface (oil and continuous phase of the microemulsion), which justifies the packaging of oil by micelles. In addition, an increase in the color of the microemulsion was noted after its reuse, which indicates a greater amount of extracted oil, as seen in FIG. 3.

EXAMPLES OF EMBODIMENTS OF THE INVENTION

[0036] To evaluate the oil extraction efficiency by microemulsions, the systems were compared to micellar solutions widely used in the literature and containing the same percentage of surfactant. Table 4 illustrates the extraction efficiency values for microemulsions and surfactant solutions. For all analyzed situations, the microemulsion showed a higher percentage of oil removal efficiency than the surfactant solutions. The presence of butanol makes the microernulsion a more non-polar formulation, which facilitates the action of the surfactant in oil removal and, thus, justifies the greater extraction action by microemulsions. The evaluation of surfactant solutions elucidates how decisive the surfactant structure is for the oil extraction process, making it clear that the smaller the amount of ethoxylate group, the greater its affinity for nonpolar fluids, resulting in greater extraction.

TABLE-US-00004 TABLE 4 Results of petroleum extraction using micellar solution and microemulsion. EE (%) Surfactant Micellar solution Microemulsion LA EO10 6.387 ± 0.087 15.065 ± 0.114 LA EO8 8.522 ± 0.279 26.678 ± 0.334 LA EO6 78.754 ± 0.129  99.800 ± 0.266