Adsorption of Zwitterionic Surfactant on Limestone Measured with

Article pubs.acs.org/Langmuir

Adsorption of Zwitterionic Surfactant on Limestone Measured with High-Performance Liquid Chromatography: Micelle−Vesicle Influence David Aaron Nieto-Alvarez,*,†,‡ Luis S. Zamudio-Rivera,*,†,§ Erick E. Luna-Rojero,∥ Dinora I. Rodríguez-Otamendi,‡ Adlaí Marín-León,‡ Raúl Hernández-Altamirano,⊥ Violeta Y. Mena-Cervantes,⊥ and Tomás Eduardo Chávez-Miyauchi# †

Grupo de Química Aplicada a la Industria Petrolera, ‡Dirección Regional Marina, §Programa de Ingeniería Molecular, and ∥Programa de Recuperación de Hidrocarburos, Instituto Mexicano del Petróleo, Eje Central Lázaro Cárdenas 152, Colonia San Bartolo Atepehuacan, Mexico City 07730, Mexico ⊥ Centro Mexicano para la Producción más Limpia, Instituto Politécnico Nacional, Avenida Acueducto s/n, Colonia La Laguna Ticomán, Mexico City 07340, Mexico # Facultad de Ciencias Químicas, Universidad La Salle México, Benjamin Franklin 47, Colonia Hipódromo Condesa, Mexico City 06140, Mexico S Supporting Information *

ABSTRACT: Herein is presented a new methodology to determine the static adsorption of a zwitterionic surfactant on limestone in three different aqueous media [high-performance liquid chromatography (HPLC) water, seawater, and connate water] with the use of HPLC at room temperature and 70 °C. The results showed that, in both HPLC water and seawater, the surfactant adsorption followed a monolayer Langmuir tendency. In contrast, for connate water, the surfactant presented a new adsorption profile, characterized by two regions: (i) At surfactant concentrations below 1500 mg L−1, an increase of adsorption is observed as the amount of divalent cations increases in the aqueous media. (ii) At surfactant concentrations above 1500 mg L−1, the adsorption decreases because the equilibrium, monomer ⇆ micelle ⇆ vesicle, is shifted to the formation of vesicles, giving as a result a decrease in the concentration of monomers, thus reducing the interaction between the surfactant and the rock, and therefore, lower adsorption values were obtained. The behavior of the surfactant adsorption under different concentrations of divalent cations was well-described by the use of a new modified Langmuir model: (dΓ/dt)ads = kadsc(Γ∞ − Γ) − kcmc(c − ccmc)nΓH(c − ccmc). It was also observed that, as the temperature increases, the adsorption is reduced because of the exothermic nature of the adsorption processes.

1. INTRODUCTION

less than 30% and 50% of the known reservoirs are carbonatetype. Carbonate reservoirs are often characterized as highly fractured and with very low relative permeability, and it is also known that 90% of these reservoirs are considered neutral to preferably wet to oil. As mentioned, the EOR purpose is to modify the physicochemical properties of the reservoir to increase the oil recovery factor, specifically the interaction between the rock and the reservoir fluids.4−6 In this sense, one of the most promising processes for achieving this purpose is the injection of chemical compounds that modify the wettability of the rock, promoting the spontaneous imbibition of the oil from the matrix. It is important to notice that, for the application of these

Oil recovery is carried out in three phases. Primary recovery: Oil is pushed out to the surface because of the pressure gradient between the reservoir and the wellhead. Secondary recovery: When the wellbore pressure decreases, pressurized gas or water is injected into the reservoir to maintain the pressure gradient and drive the residual oil. After primary and secondary phases, the reservoir still contains 60−80% of the oil. When the reservoir pressure decreases during the secondary phase, it is necessary for the implementation of the tertiary extraction, also known as enhanced oil recovery (EOR), which is the generic name for processes and techniques applied to increase the hydrocarbon recovery factor by modifying the original physicochemical properties of the reservoir. EOR1−3 has received particular attention in recent years because of its potential application in carbonate reservoirs, because global hydrocarbon recovery has been estimated much © 2014 American Chemical Society

Received: May 22, 2014 Revised: September 24, 2014 Published: September 25, 2014 12243

dx.doi.org/10.1021/la501945t | Langmuir 2014, 30, 12243−12249

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chemical compounds, a cost−benefit analysis is essential to assess the feasibility of its application in the future. By this way, a relevant aspect that must be studied is the adsorption capability of the chemical compound and its interfacial properties. Surfactants have been implemented in the oil industry to increase the recovery of oil remaining in porous media,5−13 and recently, these compounds have been used in the form of foams in naturally fractured reservoirs to prevent channeling of gas or water and improve the sweeping of the remaining oil.14−17 Mexican oil reservoirs are mostly mature naturally fractured carbonate reservoirs, with the presence of high salinity and temperature. For these reservoirs to be considered nowadays as productive assets, the implementation of EOR techniques is required; in that way, new chemical products capable of resisting extreme conditions (ultrahigh salinity, high temperature, etc.) have been developed to increase the oil recovery factor.18−22 To improve the design of new chemical compounds capable of increasing the oil recovery factor and in the knowledge that the chemical compounds interact with the rock, the analysis of the adsorption phenomena of the chemical compounds with the mineral provides reliable data that can be used for further design or other areas, such as reservoir simulation or estimating the chemical product loss by adsorption at an industrial scale, evaluating by this way its effectiveness and the implied costs. In this work, a new methodology was implemented for evaluating with more accuracy the adsorption phenomena at different temperatures and in the presence of mono- and divalent ions, considering reservoirs presenting ultrahigh salinity and temperature. To our best knowledge, this constitutes the first report of such analytic determination and study of adsorption behavior under conditions of ultrahigh salinity typical of many reservoirs around the world.

Figure 1. Molecular structure of cocamidoproyl hydroxysultaine.

Table 1. Physicochemical Properties of the Types of Water Used in the Evaluations sample pH salinity in NaCl (mg L−1) cations (mg L−1) Na+ Ca2+ Mg2+ Fe3+ Ba2+ Sr2+ anions (mg L−1) Cl− SO42− HCO3−

seawater

connate water

8.00 30800.00

6.01 203252.15

10873.00 455.60 1302.48 2.02

23142.62 40360.00 3900.85 1.90 91.32 1600.00

19927.00 2695.30 201.30

123300.00 50.00 109.80

2.3. Rock Treatment. Bedford limestone was used as a mineral substrate. The rock was passed through a mesh sieve number 60, to obtain particles with a mean surface area of 1.0 m2/g. The rock was then washed with sequential refluxes in a Soxhlet system using hexane, toluene, chloroform, and methanol, then dried at 30 °C in an oven, and finally allowed to dry at room temperature for 48 h. 2.4. Determination of cmc. A plot of the surface tension as a function of the surfactant concentration was constructed, and cmc was determined as the point where the resulting curve changes its slope. The concentration range used was from 0.15 to 15 mmol L−1. 2.5. Determination of the Concentration of the Surfactant (Cocamidopropyl Hydroxysultaine) by HPLC. To determine the concentration of the surfactant by HPLC, the following conditions were used: column, Nova-Park HR C18; column temperature, 30 °C; flow, 0.5 mL/min; mobile phase, methanol/water (7:3, v/v); injection, 15 μL; and detector, ultraviolet (UV) (λ, 215, 210, and 200 nm). 2.5.1. Preparation of Calibration Standards. Dilutions of the surfactant within the range of 40−4000 mg L−1 were prepared from a stock solution of 5000 mg L−1 in the different aqueous media and then were analyzed by HPLC using the above-specified conditions to obtain calibration curves from which it was possible to calculate chromatogram areas as a linear function of the surfactant concentration. For further details, see the Supporting Information. 2.6. Static Adsorption of the Surfactant. Adsorption isotherms were determined by batch equilibrium adsorption procedures. Samples of 4.00 g of limestone previously treated were placed in beakers of 100 mL. To each sample, 20 mL of surfactant dilutions was added. Surfactant solutions were prepared at different concentrations with three different aqueous media. The samples were stirred for 13 h at ambient temperature and then left to repose for 2 h. Each sample was passed through HPLC filters. The solutions were analyzed in HPLC by determining the surfactant concentration according to eq 1

2. EXPERIMENTAL SECTION 2.1. Equipment. Critical micelle concentration (cmc) measurements were performed in a Data Physic DCAT11EC tensiometer at 25 °C using the method of the sessile drop. High-performance liquid chromatography (HPLC) measurements were performed in an Agilent 1100 chromatograph using a Nova-Park HR C18 column; 3D Chem Station for liquid chromatography (LC), revision A.10.01, Agilent Technologies software was used for processing the chromatograms. The morphology and dispersion of the particles were analyzed in a transmission electron microscope JEM-2200FS, which operates at 200 kV, equipped with a Schottky field-emission electron gun, an ultrahighresolution configuration [spherical aberration (Cs), 0.5 mm; chromatic aberration (Cc), 1.1 mm; and point−point resolution, 0.19 nm], and Omega in-column energy filter. The microscope operates with an aberration-corrected CEOS device in STEM mode. Punctual chemical analysis in the particles was performed by energy-dispersive X-ray spectroscopy (EDXS) using a NORAN spectroscope attached to the microscope. 2.2. Materials. Surfactant: Amphosol CS-50 was provided by Stepan Co. and used without further treatment. The product contains 43.5% cocamidopropyl hydroxysultaine, whose structure can be observed in Figure 1, 6.5% NaCl, and 50.0% water. Methanol and water were purchased from J.T.Baker (at HPLC grade). Three types of water were used for the evaluations: HPLC water, seawater, sampled at 8 m depth and 10 km from the seashore in ́ Tabasco, Mexico, and connate water formulated the region of Paraiso, with similar characteristics to brine obtained from a reservoir located in the southeast of Tabasco, Mexico. The physicochemical characteristics of these waters can be observed in Table 1.

adsorption =

(c0 − ceq)V m

(1)

where “adsorption” is milligrams of surfactant per gram of limestone (mg/g), “c0” is the initial surfactant concentration, “ceq” is the concentration of the surfactant after the adsorption, “V” is the volume 12244


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Figure 2. Efect of the aqueous medium (a, HPLC water; b, seawater; and c, connate water) on the retention time with the same concentration of surfactant cocamidopropyl hidroxysultaine. of the surfactant solution added to the sample (mL), and “m” is the mass of limestone (g). 2.7. Obtaining Transmission Electron Microscope Images. Sample preparation: A 3500 mg L−1 surfactant solution was dropped onto a 3 mm diameter copper grid covered with a polymeric film, then dried in a vacuum desiccator for 3 h, and directly imaged.

connate water), it was observed that the retention times varied because of the presence of mono- and divalent ions (Figure 2). As a result of the different tests, the best conditions for measuring the concentration of the surfactant by HPLC were Nova-Park HR C18 column, temperature of 30 °C, flow rate of 0.5 mL/min, methanol/water (7:3, v/v) as the mobile phase, injection volume of 15 μL, and UV (λ, 215, 210, and 200 nm) detector. 3.2. cmc. The obtained values for cmc are presented in Table 2; it was observed that, as salinity increased, cmc of

3. RESULTS AND DISCUSSION 3.1. Development of a HPLC Analytical Method. 3.1.1. UV Detection. For the development of the analytical method, the maximum UV absorption values of the surfactant at different concentrations were studied. The maximum UV absorption values were observed at 215, 210, and 200 nm, obtaining the best linear correlation in the first case. Thus, quantitative determinations were based on 215 nm values. 3.1.2. Method Optimization. For the development of the analytical methodology, different tests were performed, modifying the variables involved: column type, column temperature, flow, mobile phase, and injection volume. As a result of the process, the best chromatographic conditions were obtained to analyze the surfactant used in this work. 3.1.2.1. Mobile Phase. Different relationships between methanol and water were tested. For relationships of 10:0, 9:1, and 8:2, the retention times of the surfactant and the solvent front were very similar as the signals overlapped. It was found that, when a relationship of methanol/water (7:3) was used, the retention times allowed the signals to be perfectly distinguished. 3.1.2.2. Flow Velocity. It was observed that, when the flow was greater than 1 mL/min, the retention time of the surfactant was also reduced, causing the signal to overlap for the surfactant and the solvent front. Derived from this analysis, it was found that the optimum flow velocity was 0.5 mL/min. 3.1.2.3. Effect of the Aqueous Medium. As a result of the analysis of the surfactant at the same concentration (2000 mg L−1) in the three aqueous media (HPLC water, seawater, and

Table 2. Values Obtained from Langmuir and Modified Langmuir Models in Connate Water, Seawater, and HPLC Water HPLC water correlation coefficient (R2) xm k correlation coefficient (R2) k km Γ∞ ccmc n

seawater

Langmuir Model [x = xmc/(c + 1/k)] 0.7540 0.819

connate water 0.684

0.00276 0.00952 0.0069 0.02255 Modified Langmuir Model (eq 4) 0.814 0.848

0.890

8.31421 × 10−4 4.61179 × 10−7 0.00466 279.34 2

0.01816 5.87767 × 10−6 0.09892 185.90 2

0.0053 1.01581 × 10−6 0.0169 200.89 2

0.08736 0.31024

cocamidopropyl hydroxysultaine decreased. This information was later used as an entry parameter for the calculation of adsorption models. All of the obtained curves were included in the Supporting Information. 3.3. Effect of the Aqueous Media to the Adsorption of Cocoamidopropyl Hydroxysultaine. The behavior of the 12245


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adsorption isotherms of the surfactant with the three different aqueous media is presented in Figure 3; the results show that,

Figure 4. Schematic of the electrical double layer (double-sided arrors indicate repulsion).

exchange capacity of the cations is bigger because of the high amount of Ca2+ in solution, giving place to a higher concentration of species on the mineral. Thereby, the surfactant adsorption depended upon the predominant cations in the aqueous medium, and for the three systems evaluated, the adsorption magnitude tendency was as follows: surfactant in connate water > surfactant in seawater > surfactant in HPLC water 3.4. Behavior of the Adsorption Isotherm. The behavior of the adsorption isotherms for the surfactant with HPLC water and seawater can be explained by the model of “four regions” proposed by Somasundaran and Fuerstenau.23,24 The model implies that, for carrying out the adsorption, electrostatic and hydrophobic interactions are involved as well as micellar systems. In the case of the adsorption isotherm of the surfactant in connate water (Figure 3), a high adsorption region was characterized within the concentration range from 100 to 1500 mg L−1, reaching an adsorption maximum of 4.609 mgsurfactant/ grock (1.3852 × 10−5 mol/m2) at the initial surfactant concentration (c0) of 1500 mg L−1; above this concentration, the adsorption decreased, as shown in Figure 3 (for further detail, see the Supporting Information). This behavior was not explained by the “four regions” postulate, and it is proposed to be explained as follows: The presence of high salinity in an aqueous medium has been reported to promote the transition from micelles to vesicles.27−29 In the case of connate water, particles acquired positive charge, which promoted a significant and rapid increment in surfactant adsorption onto the limestone surface with a maximum at 1500 mg L−1. In this region, a first stage was characterized below the cmc point, where adsorbed species are surfactant monomers, and a second stage was characterized above the cmc point, in this case, 185.90 mg L−1, where the predominant species both on the liquid phase and at the limestone surface are surfactant micelles; as mentioned before, this region ends at the point of maximum adsorption. A second region was identified starting from the point of maximum adsorption characterized for a sustained decrease in adsorption values. This significant decrease was attributed to vesicle formation because of the fact that it has been reported that salts in solution promoted the formation of higher ordered selfassemblies, i.e., vesicles. Thus, the equilibrium monomer ⇆ micelle ⇆ vesicle is shifted to the formation of vesicles. These vesicles presented lower adsorption toward the limestone particle surface fundamentally because of steric hindrance. Therefore, as the initial concentration of surfactant (c0) in

Figure 3. Experimental adsorption isotherms obtained for cocamidopropyl hydroxysultaine in different aqueous media at room temperature and comparison of the models of adsorption isotherms in different aqueous media (HPLC water, seawater, and connate water).

for HPLC water and seawater, the behavior follows a monolayer Langmuir tendency, characteristic of limestone.23,24 To ensure a monolayer adsorption in the case of HPLC and seawater systems, the cross-section molecular area at the solid/ water and air/water interfaces were calculated and compared, obtaining 0.2738 and 0.3880 nm2, respectively, for the HPLC system and 0.2002 and 0.2770 nm2, respectively, for the seawater system, and thus, a ratio of approximately 1 in both HPLC and seawater cases was obtained, which confirms the adsorption of a monolayer. On the other hand, it was observed that, for the case of the connate water system, the adsorption value is almost 2 times the obtained value for HPLC and seawater systems. The effect of the increase of adsorption values in connate water can be attributed to the dielectric layer phenomena. In any interface, there exists an unequal distribution of electric charges, in this case, in the interface between the mineral (limestone) and the surfactant. The limestone acquires a negative charge such that the cations present in the solution tend to neutralize the charge of the rock, and the excess in these ions gives place to the formation of an electric potential through the interface denominated “Stern double electric layer”24 (Figure 4). In HPLC water and seawater, the absence or very low concentration of divalent cations in solution causes the adsorption of the surfactant on the rock to take place by ionic interactions among the ammonium group of the surfactant and the surface with a negative charge tendency. For the connate water, the presence of the electrolytes (Ca2+ and Mg2+) causes the mineral surface to have a positive charge tendency; therefore, the interaction with the surfactant takes place by the sulfonium group.25,26 By the same way, the electrical double layer theory implies that the divalent cations, such as Ca2+, are located in the double layer preferably than the monovalent cations, such as Na+, because divalent ions have less solvation area (Ca2+, 145 Å2) than the monovalent cations (Na+, 196 Å2). In this case, the 12246


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term on the right side of eq 2. On the other hand, the adsorption process is inhibited by the micelles and vesicles once they appear; such behavior is modeled by the second term in the same equation, where it is supposed to be proportional to a power function of the difference between the concentration (c) and the critical micelle concentration (ccmc)

connate water is increased, vesicle formation is favored, and because vesicles presented a lower adsorption at the solid surface, consequently, a minimum in adsorption is reached at the highest initial concentration surfactant of 3500 mg L−1. It is important to point out that, although this phenomenon is somehow similar to the salting-out effect, the fact that no phase segregation is observed makes one important difference. Actually, vesicle formation was initially detected because the turbidity of surfactant solutions increased, and then this postulate was experimentally confirmed through transmission electron microscopy (TEM) analysis, as shown in Figure 5.

⎛ dΓ ⎞ ⎜ ⎟ = kadsc(Γ∞ − Γ) − kcmc(c − ccmc)n ΓH(c − ccmc) ⎝ dt ⎠ads (2)

where c is the surfactant concentration, Γ∞ is the maximum number of sites available, Γ is the effective number of occupied sites, kads and kcmc are constants, H(c − ccmc) is the Heaviside function, which activates the last term in eq 2 only for c > ccmc and n > 1, and n is a adjust parameter obtained during the adjustment for the model. For desorption, the rate of change is proportional to the number of absorbed species as in the Langmuir model. ⎛ dΓ ⎞ ⎜ ⎟ = kdes Γ ⎝ dt ⎠des

(3)

Here, kdes is a constant. At equilibrium, eqs 2 and 3 must be equal, and when both of them are combined, the following equation is obtained: Γ=

kc Γ∞ 1 + kc + k m(c − ccmc)n H(c − ccmc)

(4)

In the last equation, k = kads/kdes is the Langmuir equilibrium adsorption constant and km = kcmc/kdes is a new constant. Notice that, when km = 0, the Langmuir model is recovered. This four-parameter model was adjusted to the experimental results using a Levenberg−Marquardt method. From the results of Figure 3 and Table 2, it can be observed that a better correlation with experimental curves is achieved by the new model compared to classic Langmuir, especially as the salt concentration is increased in different aqueous media. These results confirmed that the equilibrium monomer ⇆ micelle ⇆ vesicle is shifted to the vesicle formation, thus resulting in lower adsorption values. 3.5. Effect of the Temperature on the Adsorption Process. Because of the importance of the temperature in EOR, the influence of such a parameter was evaluated in the process of adsorption of surfactant cocoamidopropyl hydroxysultaine at 2000 mg L−1 on limestone at different salinity conditions and 70 °C. After the adsorption process was concluded, the equilibrium concentration and the corresponding adsorption value were obtained for each sample. To analyze the effect of the temperature on the adsorption process, the results obtained at room temperature and 70 °C were compared (Table 3).

Figure 5. TEM images of vesicles in the system with connate water.

Hence, a vesicle dispersion was identified for the connate water system contrary to a well-separated phase that is observed to derive from a salting-out phenomenon. To describe the experimental behavior observed in connate water, where there is a huge amount of divalent ions, a latticetype model similar to Langmuir30 was used. The assumptions were as follows: (1) Every adsorption site on the lattice was equivalent. (2) The adsorption probability at a given site was independent of the neighborhoods. (3) Interactions between monomers in the lattice were not considered. (4) Once the micelles and vesicles appeared, these start to interact with the monomers in the solution, resulting in the capture of monomers by these structures and, as a consequence, the inhibition on the adsorption on the surface. The first three assumptions come from the Langmuir model, and the last one is proposed to explain the experimental behavior. As in the Langmuir model, the rate of change of surface coverage because of adsorption is proportional to both the concentration of the surfactant in solution and the amount of vacant sites on the lattice, which is represented by the first

Table 3. Adsorption of Surfactant on Limestone at Room Temperature and 70 °C at 2000 mg L−1 type of water

temperature (°C)

ceq (mg L−1)

adsorption (mg/g)

HPLC water

25 70 25 70 25 70

1557.220 1908.115 1616.284 1863.713 1263.344 1694.757

2.214 0.459 1.918 0.681 3.683 1.526

seawater connate water

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It can be observed that, at room temperature, the adsorption process is favored by the presence of cations in solution, having greater affinity for the divalent ions. On the other hand, it can be seen that there exists an inverse relationship between the temperature and adsorption, which was endorsed by the work of Chorro et al.,31 which indicates that, because of the exothermic nature of most of the interactions of this type, the adsorption decreases as the temperature is increased.

follows a monolayer behavior and the studied reservoirs present high temperatures (>70 °C).

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ASSOCIATED CONTENT

S Supporting Information *

HPLC method, preparation of calibration standards, and cmc. This material is available free of charge via the Internet at http://pubs.acs.org.

■

4. CONCLUSION The analytical parameters of linearity, accuracy, and precision of the HPLC method allowed us to quantify in an efficient way the adsorption of the surfactant (cocamidopropyl hydroxysultaine) on limestone in three different aqueous media (HPLC water, seawater, and connate water). To our knowledge, this constituted the first report of adsorption curves for a surfactant in an ultrahigh-salinity environment. From the adsorption data, it could be appreciated that the presence of divalent cations favors the adsorption process and that, at high temperature, the adsorption process of the surfactant on the rock is disadvantaged. According to the behavior observed for the adsorption process of the system, a modification to the Langmuir model was proposed. The experimental results (adsorption in HPLC water, seawater, and connate water) fit well with the modified equation, and it was observed that the adsorption is monomolecular and increases as the amount of divalent cations increases in the medium. The adsorption mechanism is proposed to be explained by the following: In the case of HPLC water and seawater, because of the low amount of divalent cations, the adsorption between the surfactant and the rock takes place mainly by electrostatic interactions of the ammonium group in the surfactant and the mineral surface that presents a negative charge tendency. On the other hand, in connate water, the presence of divalent cations promotes the adsorption of the surfactant with the rock by electrostatic interactions through the sulfonium group; in this case, the surface presents a positive charge tendency because of the interaction of the divalent cations with the surface explained by the Stern double electrical layer theory. Because the surfactant molecule does not bend when the interaction takes place by the sulfonium group, the steric factor is lower than in the case of the ammonium interaction, allowing by this way that more molecules can adsorb over the surface. In this manner, at the saturation concentrations, the adsorption process depends upon the amount of cations present in the aqueous media, in this case, as follows: surfactant in connate water > surfactant in seawater > surfactant in HPLC water. At higher concentrations, the amount of divalent cations promotes the transition from micelles to vesicles; as the surfactant concentration increases, the equilibrium monomer ⇄ micelle ⇄ vesicle is shifted to the vesicle formation, reducing by this way the amount of monomers, thus decreasing the amount of surfactant adsorbed on the rock. The presence of vesicles could be confirmed by the use of TEM. The present study will allow us to know the amount of losses by adsorption that can take place in an industrial application of an EOR process. It was also observed that, at 70 °C, the adsorption is inhibited; therefore, in the same tenor, it can be concluded that, for the case of cocamidopropyl hydroxysultaine, the losses by adsorption are negligible because the adsorption

AUTHOR INFORMATION

Corresponding Authors

*Telephone: 01-5591758134. E-mail: [email protected]. *E-mail: [email protected]. Notes

The authors declare no competing financial interest.

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ACKNOWLEDGMENTS The authors want to acknowledge the Mexican Institute of Petroleum (IMP), Project Y.00123 “Procesos de RM en yacimientos carbonatados fracturados de alta salinidad y temperatura con base en el diseño, desarrollo y escalamiento de productos quimicos ad hoc”, under the financial support of the SENER-CONACYT/Hidrocarburos Fund, Project 146735.

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Adsorption of Zwitterionic Surfactant on Limestone Measured with

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