Nonquilibrium and Equilibrium Stationary States of Zwitterionic

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Non-quilibrium and Equilibrium Stationary States of Zwitterionic Surfactant Dynamic Adsorption on Limestone Cores at Oil-Reservoir Conditions David Aaron Nieto-Alvarez, Adlai Marin-Leon, Erick E. Luna-Rojero, José-Manuel Martínez-Magadán, Raul Oviedo-Roa, Marissa Pérez-Alvarez, Galileo Dominguez-Zacarías, and Luis S. Zamudio-Rivera Ind. Eng. Chem. Res., Just Accepted Manuscript • DOI: 10.1021/acs.iecr.7b03610 • Publication Date (Web): 17 Jan 2018 Downloaded from http://pubs.acs.org on January 17, 2018

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Industrial & Engineering Chemistry Research

Non-quilibrium and Equilibrium Stationary States of Zwitterionic Surfactant Dynamic Adsorption on Limestone Cores at Oil-Reservoir Conditions

David A. Nieto-Alvarez*1, Adlaí Marín-León1, Erick E. Luna-Rojero1, José M. MartínezMagadan1, Raúl Oviedo-Roa1, Marissa Pérez-Alvarez2, Galileo Dominguez-Zacarías1, Luis S. Zamudio-Rivera*1

1

Instituto Mexicano del Petróleo, Eje Central Lázaro Cárdenas Norte 152, San Bartolo Atepehuacan, Ciudad de México, 07730, México. 2CONACyT Research Fellow- Instituto Mexicano del Petróleo, Gerencia Centro-Norte La Reforma Hidalgo, Carretera Pachuca a Ciudad Sahagún Km 7.5, Parque Industrial Canacinta, Mineral de la Reforma, Hidalgo, 42186, México.

Corresponding Authors Email: [email protected] and [email protected]

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ABSTRACT

Dynamic

adsorption

of

a

zwitterionic-type

surfactant

cocamidopropyl

hydroxysultaine on limestone cores at oil reservoir conditions, i.e., under 2,000 psi pressure, 130 ºC temperature, and in presence of seawater with 30,800 ppm as NaCl, has been studied through core-flood displacement tests and in the absence of oil, at an injection rate of 120 cm3.h-1 up to 60 pore volumes (PV). The amount of adsorbed surfactant has been determined from mass balance by calculating its concentration through High Performance Liquid Chromatography (HPLC). The normalized surfactant concentrations (NSC) have been used in terms of the PV, and then they are obtained the corresponding dynamic adsorption curves. Dynamic adsorption isotherm curves of the zwitterionic surfactant diluted in seawater showed a steep rise between 1 and 3 pore volumes (PV), and the saturation conditions were kept up to 60 PV. An average surfactant adsorption of 0.1138 ± 0.0126 mg⋅g-1 was determined. Quantum theoretical studies show that the electronic energy gap of (104) the limestone is electrically neutral, preferably acquiring a negative charge tendency, these results imply that the calcite surface will preferentially interact with positive ions, so that the cations present in the solution interacting in the limestone, resulting in a positive charge in the rock that implies that the surfactant cocamidopropyl hydroxysultaine interacts in the rock by the anionic group

Keywords: Dynamic adsorption, cocamidopropyl hydroxysultaine, zwitterionic surfactant, Enhanced oil recovery, Density Functional Theory.


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1.

INTRODUCTION At present, primary and secondary oil recovery processes are inadequate because

their maximum performance only reaches around 30 % of the original oil in place as a consequence of an adverse balance among in viscous and capillary-forces, which limit the drain phenomena. Consequently, over 70 % of the original oil in place1 (POES) remains trapped in the reservoir rock as residual oil in natural oil fields. Enhanced oil recovery (EOR) is generally considered as the third and last stage of the extraction-process sequence of crude oil from a reservoir, i.e., tertiary oil production. Considering that world´s oil consumption will grow to 37% by the 2040 year, EOR processes have recently increased their technical and economical viability and therefore the scientific research in the field has recaptured interest2. In a broad sense, these processes are directed to modify the quotient between viscous and capillary forces towards a larger value. The selection of thermal, gaseous or chemical oil-recovery methods depend upon reservoir characteristics and conditions. Usually, chemical methods consist on introducing a substance that modifies physicochemical properties of the crude oil in order to favour its displacement trough a porous reservoir by modifying interfacial forces at oil-water and oil-rock boundaries, as well as intermolecular forces within bulk oil3. This physicochemical alteration is manifested at macroscopic level as changes in viscosity, oil/water interfacial tension, contact angle, principally, which ultimately result in an increment of the oil recovery. There are different types of chemical agents that can be used in EOR processes. Among them, operations based on surfactant injection exhibit important potential advantages due to they generate a wide scope of phenomena such as interfacial-tension reduction, wettability alteration, emulsion formation, mainly, all these occurring at relative low concentration values4-12. 3 ACS Paragon Plus Environment


In chemical injection processes, surfactants are inevitably adsorbed on the surface of the reservoir rock due to the oil-water-rock interaction. Accordingly, the adsorption of surfactants13-20 is one of the most important factors governing economic viability and profitability of the surfactant flooding process and therefore, in order to estimate the technical performance and economics losses in EOR processes of new-surfactants injection, it is indispensable to accurately determine the amount of adsorbed surfactant per gram of rock. Surfactant adsorption on a reservoir-rock surface depends on both the solid substrate and the solution. According to some estimations, more than 60% of the world’s oil reserves are held in carbonates, but conversely, reports on surfactant adsorption at carbonate surface are rather scarce in comparison to other minerals. On another hand, amphoteric surfactants, betaine and amidobetaines in particular, have recently gained attention due to their advantages such as high-salinity tolerance, strong multivalent-cations resistance, and low critical-micelle-concentration. Recently, some researchers have used different kinds of betaines for the enhancing of the crude-oil recovery and have obtained satisfying results21-23. However, up to our best knowledge few works have discussed betaines adsorption and only two works discuss it for carbonate surfaces, but nobody discusses the dynamic-adsorption behaviour of this kind of surfactants at high temperature, high pressure and high salinity. In this regard, although it has been stablished that both static and dynamic experiments conclude the same trends, it has also been observed that the dynamic method reveals a quantitative behavior of the surfactant adsorption process within reservoirs. Thus, dynamic adsorption is a more reliable experiment to estimate the amount of surfactant loss and, therefore, the technical and economic viability of an EOR process. 4 ACS Paragon Plus Environment

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Dynamic conditions are necessary in order to obtain an accurate estimation of the surfactant-rock interaction within a reservoir, so that the studies on dynamic adsorption7, 2436

have been conducted for a number of mineral, surfactant types and different experimental

condition studies in a core holder as show in the Table 1. The present work deals with forced displacements in limestone cores with cocamidopropyl hydroxysultaine surfactant at extreme reservoir conditions37-39 such as high temperature, high pressure, and in the presence of seawater. Ref .

Core

Temp. °C

Pressure Psi

Salinity Ppm

Surfactant

Conc. ppm

7

Stevns Klint Oil fiel

50

365

12,400 NaCl 3400 CaCl2

100010,000

24

Sandstone

30-50

15,000 NaCl 5,000 CaCl2

25

Naharkotiy a oil fiel

28

3,000 Na Cl

26

Sandstone

Room temp.

27

Berea

Room temp.

Formation water

C12TAB C16TAB C12TAB Dodecyl Sulfato Calcium Lignosulfonato Sodium Lignosulfonato Nonyl phenol oxyethylene Alkil aryl sulfonic acid

28

Sandstone Kaolinite

25

30,00060,000 Na Cl

30

20,000 Na Cl

Alkil sulfonic ester Dietanolami

500010,000

Flux ml/hr

Φ

K m D

0.45

2-7

0.18

139

2000

60 120 350 15

0.19

86

1500

55

0.19

151

2000 1% NaOH 40005000

15

0.20

200

12

0.20

300

Table 1. Experimental condition for studies in dynamic adsorption. The present work is focused on the experimental determination of dynamic adsorption curves for cocamidopropyl hydroxysultaine (CAHS) within limestone cores 5 ACS Paragon Plus Environment


under non-equilibrium conditions in the absence of oil, since this determine the appropriate analytic technique, but at oil reservoir conditions, that is, 2,000 psi core pressure, 3,000 psi confining pressure, 130 °C temperature, and seawater medium with 3800 ppm as NaCl. The method aims to investigate the retention of the chemical in the rock in a real context, that is, under non-equilibrium conditions in a saline solution, and in the absence of oil and air, by using High Performance Liquid Chromatography (HPLC) which allows to detect surfactant concentration in the effluent from core-flood system. In the sake of getting validity and reproducibility, we have performed the same experiment over three limestone cores. The obtained information could be useful to design in the future enhanced-hydrocarbonrecovery processes for mature oil fields, i.e., tertiary oil production.

2. 2.1

EXPERIMENTAL SECTION Equipment HPLC measurements were carried out in an Agilent 1100 chromatograph using a

prep Nova-Pack HR C18 column. The Agilent 3D Chem-Station software for LC systems (Rev. A.10.01 [1635], 1990-2003) was used to control the chromatographic units, acquire and process the chromatographic data. Dynamic adsorption experiments were carried out in a core-flood system which diagram is shown in Figure 1. The equipment was connected to a National Instruments data acquisition system. The core-flood system has the following elements: A, Positive displacement pump, Vinci Technologies steel 31655 ht # 6 MC2, with a capacity of 30 cm3, pressure range betwen 0 to 10,000 psi. B, High Pressure transference cylinder for surfactant in brine solution, Corelab Model BPR-150-HC with 15,000 psi as limit pressure. C, Oneway valve, High Pressure. D, Two-way valve, High Pressure, Model 15-15 a F2. E, 6 ACS Paragon Plus Environment

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Manometer. F, Differential pressure indicator, Validyne Model P365D. G, Inverse Back Pressure Regulator (BPR). H, Coreholder. I, Temperature controller. J, Positive displacement pump.

Figure 1. Diagram core-flood system. 2.2

Materials Surfactant: The surfactant CAHS was provided by Stepan Co. as its Amphosol ®

CS-50 commercial product, which contains 43.5% of cocamidopropyl hydroxysultaine, 6.5% of NaCl and 50.0% of water. It molecular structure is shown in Figure 2. The thermochemical stability of the surfactant was determined to be between 125 and 250°C through Termogravimetric Analysis (TGA) by using a PerkinElmer TGA under a constant heating rate of 5 °C/min and heating from 30 to 510 °C and purging was performed with nitrogen gas for a sample of 20 mg as shown in Figure 3. Firstly, due to the commercial surfactant contains 50% of water it is observed a diminishing in the weight % up to approximately 125 °C, because of water elimination; later a plateau between 125 and 250 °C is observed, where the surfactant structure is maintained stable; and finally from 250 °C the structure starts to be degraded up to 300 °C. 7 ACS Paragon Plus Environment


O O

S

-

O

HO

N

+

O NH

Figure 2. Molecular structure of cocamidoproyl-hydroxysultaine (CAHS).

Figure 3: TGA of surfactant cocamidoproyl-hydroxysultaine CASH.

Solvents and seawater: Methanol and water, both HPLC-grade were acquired from J. T. Baker. Seawater was sampled at 8 m depth and at a distance of 10 km from the seashore in the region of Paraíso, Tabasco, México. The physicochemical characteristics of this water from stiff Davis analysis are reported in Table 2. Limestone cores: Bedford limestone cores, labeled from 1 to 3, were used as mineral substrates to reproducibly determine three times the CAHS dynamic adsorption. Petrophysical properties of seawater in are shown in Table 3. The rock cores were washed with sequential refluxes in a soxhlet system using hexane and then were dried in an oven at 100 °C, and finally allowed to dry at room temperature.


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pH

8.00

Salinity (as NaCl)

30,800.00

Cation

(mg·L-1)

Na+

10,873.00

Ca2+

455.60

Mg2+

1,302.48

Fe3+

2.02

Anions

(mg·L-1)

Cl-

19,927.00

SO42-

2,695.30

HCO3-

201.30

Table 2. Physicochemical properties of the seawater used in the evaluations. Property

Core 1

Core 2

Core 3

Diameter (cm)

3.81

3.81

3.81

Length (cm)

6.74

7.02

7.00

Volume (cm3)

76.90

80.14

79.81

Weight (g)

164.96

170.78

169.21

Pore Volume (cm3)

14.87

14.87

14.87

Pore-volume fraction, Φ

0.1934

0.1856

0.1864

Absolute Permeability, K (mD)

33.57

34.13

38.93

Table 3: Petrophysical properties of limestone cores 9 ACS Paragon Plus Environment


2.3

Theoretical methodology In order to determine the electronic properties of the rock surface, we have

calculated the frontier orbitals, i.e., Highest Occupied Molecular Orbital, HOMO, and Lowest Unoccupied Molecular Orbital, LUMO, for a (104) calcite surface through the Density Functional Theory (DFT) as implemented in CASTEP module of the Materials Study software by using the Generalized Gradient corrected functional by Perdew and Wang (GGA/PW91), the Double Numerical plus Polarization (DNP) basis set, and the Effective Core Potentials for core treatment. Coarse options settings for all remaining run parameters were used. 2.4

Determination of the Surfactant Concentration by the HPLC method. The following conditions were used in a Nova-pack HR C18 chromatographic

column: 30 °C temperature, 30 cm3·h-1 flow rate, methanol:water mobile-phase volume composition of 7:3, 15 µL injection volume and UV detection at λ=215 nm. For further details, please refer to the prevoius report18. 2.5

Calibration curves. Calibration curves were obtained by preparing different concentrations of the CAHS

in seawater (5,000; 4,500; 4,000; 3,500; 3,000; 2,500; 2,000; 1,500; 1,000 and 500 ppm), and then the CAHS was quantified through the HPLC method (Supporting Information). 2.6

Setting experimental conditions on the core-flood system. The core-flood experiments were carried out at reservoir conditions: 130 °C

temperature, 2,000 psi core pressure and 3,000 psi confining pressure. In all cases, an injection rate of 120 cm3·h-1 was used. 2.7

Saturation of limestone cores.


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Seawater was circulated through each limestone core until saturation was reached; then, a solution of 2,000 ppm of CAHS (CMC in sweater18 198.9 mg/Kg) was prepared in the seawater and injected to the system. The fluid displaced from the pore volume of each limestone core was separately collected. 2.8

Determination of CASH concentration as PV function. Each pore volume (PV) sample collected was analyzed by HPLC to determine

surfactant concentration, these values were normalized to obtain dynamic adsorption curves. 2.9

Calculation of Surfactant Adsorption. The surfactant adsorption calculation is based on the mass balance of surfactant

under dynamic conditions according to the following equation (1):

= −

(1)

Where is the adsorbed mass [mg] of chemical, is the mass introduced to the core-flood system, and is the mass of surfactant detected at the system output for PV. The total original mass [mg] at a given volume was calculated as follows equation (2):

= ∙

(2)

Where: = Is the volume of the HPLC injection equipment (1.5x10-5 L) and is the initial concentration (2,000 ppm). Moreover, to calculate the mass of the chemical in a similar volume after the nonequilibrium adsorption process, it is used the equation (3).

= ∙


(3)


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Where is the output concentration of the chemical in non-equilibrium experiment, and was obtained from calibration curves from the area under the curve obtained in the in cromatrogram (see support information). Finally, for a pore volume, PV [L], the adsorbed mass, , [mg], as shown in equation (4):

, =

(4)

The surfactant-adsorption representation in units of milligrams per gram of rock [mg/g] was used. The surfactant-adsorption was calculated according to to equation (5), considering the porosity of a representative rock:

!"#$" =

, %&

(5)

Where: Φ is the rock porosity fraction and & the rock mass [g]

3 RESULTS AND DISCUSSION 3.1

Surfactant stability Results from TGA show a weight loss due to either free or occluded water

evaporation from 30 to 150 °C. Subsequently, a slight weight loss was recorded before 194 °C, but then, at 250 °C the rate of weight loss shows an abrupt decrease, indicating the decomposition of the sample. Thus, it is defined that the decomposition temperature of this surfactant is 250 °C and, therefore, we can carry out the core-flooding experiments at the appropriate temperature of 130°C (Figure 3). 3.2

Calibration of Standard Preparation


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A retention time of 20 min was obtained under experimental conditions at a wavelength of λ=215 nm, which allows integrating the area under the curve accurately. Thus, the chromatograms (Supporting information) for each concentration were processed for a later plotting of concentration versus area (Supporting information), the coefficient of determination was R2 = 0.9983 and the linear equation, y = 0.7206 x. 3.3

Dynamic adsorption isotherms For each of the three core-flood system experiments, approximately 60 samples of

PV size were collected at the outlet of the core-flood system. These samples were analyzed through HPLC (Supporting information) following the previously mentioned procedure in order to determine the dynamic adsorption from chromatograms (Figure 4). The area under the curve of each peak was associated to a concentration value CPV, the concentration of the surfactant produced per PV. Then, the normalized surfactant concentration (NSC) was obtained (see supporting information), by dividing each CPV between the initial concentration Co as follows: - =

./0 .1

(6)

Where: along with CPV, the concentration of the surfactant produced per PV, Co is the concentration of the injected surfactant. Dynamic adsorption isotherms were obtained by plotting NSC vs injected PV at saturation conditions, as shown in Figure 5.



Figure 4. Chromatogram of the experiment 1 under dynamic adsorption conditions for volumes a) 1 PV, b) 27 PV and c) 49 PV for CASH in seawater medium.

Figure 5. Dynamic adsorption isotherm of CASH in sea water at the injection rate of 120 cm3·h-1 14 ACS Paragon Plus Environment

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From results of the core-flooding experiments of three cores, Table 4, an average surfactant adsorption of 0.1138 ± 0.0126 mg·g-1 has been determined at 120 cm3·h-1 flow rate. As we have mentioned above, to our best knowlegde this is the first report on the dynamic adsorption behavior for a surfactant at the oil-reservoir conditions, high temperature 130 °C, and high pressure 2000 psi in seawater medium. It is observed that the dynamic adsorption value at saturation is 1/16 times the value for the adsorption of the same surfactant but at static conditions18 (1.9180 mg·g-1) under atmospheric pressure and room temperature within a seawater enviroment, and 1/6 times the value18 (0.618 mg/g) when the temperature is 70 °C. Surfactant Core

Flow

PV

234 (ppm) , 5 Adsorption

(cm3·h-1)

(mg/g)

1

120

9

1,771.4

3.3992

0.1065

2

120

9

1,779.6

3.2773

0.1034

3

120

8

1,720.6

4.1546

0.1317

Table 4. Surfactant adsorption for cores 1-3 under 120 cm3·h-1 seawater flow rate.

From the dynamic adsorption isotherms (Figure 5), we can see that: 1- Initially there is a zone of fast variation between 0 to 3 ml (0 to 0.20 PV), this fact is associated to diffusive-dispersive transport phenomena of the chemical product in the porous medium (Figure 6).



Figure 6. Schemes for the step of diffusion and dispersion of surfactant in seawater within cores and graphics of CNS vs PV. 2- The output concentration Co was never reached during the experiment; this suggests that in the injected PV was not possible to thoroughly saturate the internal surface rock. 3- The slope estimated after eight PV is practically zero, it allows us assume that those experiments are far from equilibrium since NSC indefinitely keeps lower than unity. It is possible to infer that there is an adsorption-desorption linear process (implying that the difference between what enters and leaves is practically constant) (Figure 7).


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Figure 7. Core in the stage of dynamic adsorption and graphic CNS vs PV.

4- The slope of the adsorption-desorption linear process depends on the interaction between surfactant and surface of the rock, equation 7.

= 6 7 234

(7)

5- For very long times; t→∞, the surface of the rock will be saturated; ηad→0, and therefore the surfactant amount that enters the nucleus will be equal to the output minj = mout (Figure 8).



Figure 8. Graphic CNS vs PV in step of equilibrium.

In any interface, there exists an unequal distribution of electric charge between the mineral, such as limestone and the surfactant solution. Although bulk calcite is electrically neutral, it is expected that its exposed (104) surface has a polarized charge distribution since calcite is an ionic solid (Figure 9a). Thus, in principle, calcite surface can adsorbs either cationic, anionic or zwitterionic surfactants. However, carbonate oxygen atoms protrude at the calcite surface relative to calcium cations, and moreover CO32- anions occup a major volume than Ca2+ cations; then the exposed area of negative charges must be predominant on the calcite surface. Conversely, theoretical results show that the HOMO, which is electron donor, of the calcite surface, lies just on the exposed carbonate oxygen atoms (Figure 9b), whereas the LUMO, the electron acceptor, rests mainly on the exposed Ca2+ cations (Figure 9c). Both orbitals extend away above the calcite surface, and then they could interact with either 18 ACS Paragon Plus Environment

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positive or negative charges of molecules approaching the calcite surface. Additionally, the HOMO-LUMO energy gap is found to be 102.81 kcal/mol40. Consequently, LUMO would be somewhat difficult to be involved in interaction with a negative dispersion medium. These results imply that calcite surface will interact preferently with positive ions, therefore, the limestone preferentially acquires a negative charge tendency such that the cations present in the solution tend to interact over the rock and the excess of these ions gives place to the formation of an electric potential through the interface denominated “Stern double electric layer”. The physicochemical properties of seawater used in this evaluation (Table 2) show pH = 2, and have shown that the surface of limestone is positively charged41, so in seawater the presence of cations in solution interacts with the negative tendency of the limestone acquiring positive charge. The sea waters analysis present a salinity of 30,800 ppm as NaCl and the content of Na+ is 10,870 ppm and comparing salinity with connater-water18 present 200,000 ppm as NaCl and the content of Na+ is 23,000 ppm and the divalent cations (Ca2+, Mg2+) 45,000 ppm. By the same way the electrical double layer theory implies that the divalent cations like Ca2+ are located in the double layer preferably than the monovalent cations like Na+, because divalent ions have less solvation area (Ca2+ 145 Å2) than the monovalent cations (Na+ 196 Å2). In this case the exchange capacity of the cations is bigger due to the high amount of Ca2+ in solution, giving place to a higher concentration of species on the mineral18. Which implies that the surfactant cocamidopropyl hydroxysultaine interacts on the rock by among the anionic group (Figure 10) and this is stronger in connate-water that seawater



Figure 9. (a) Electrical atomic charges on the exposed (104) surface of calcite (the view is perpendicular to the surface). Side calcite surface views of the (b) HOMO and (c) LUMO states.

Figure 10. It is shown A) a mimic molecule of surfactant that possessing two charge at the same time (blue color) and B) represent an external surface positive charged of channel present in a limenston (grey color). 20 ACS Paragon Plus Environment

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4.

CONCLUSIONS Herein, to the best of our knowledge, the first literature dynamic zwitterionic

surfactant adsorption study under extreme reservoir conditions of high-temperature, pressure and salinity, has been performed through HPLC, providing highly reliable results according to the calibration setup. Dynamic adsorption isotherm of zwitterionic surfactant in sea water present an average surfactant adsorption of 0.1138 ± 0.0126 mg•g-1 was determined for an injection rate of 120 cm3•h-1. This value represents 1/16 times the value for the adsorption (1.918 mg/g) of the same surfactant but at static conditions under atmospheric pressure and ambient temperature for a seawater medium and 1/6 times the value (0.618 mg/g) when temperature is 70 °C, so the results confirm the necesity to performe dynamic adsorption experiments in order to accurately estimate the surfactant loss during EOR process implementation. Theoretical results show that, although the limestone is electrically neutral, preferentially acquires a negative charge tendency such that the cations present in the solution tend to interact over the rock and the excess of these ions gives place to the formation of an electric potential through the interface denominated “Stern double electric layer”. This implies that the cocamidopropyl hydroxysultaine surfactant interacts on the rock by ionic interaction between the anionic group. Further research will be performed in order to establish the effect of rock, flux and salinity on the dynamic adsorption behaviour of this porous systems.



SUPPORTING INFORMATION The description of the supporting information consists of the following figures and tables. Figure 1: Chromatograms of the calibration curve of cocamidopropyl hydroxysultaine (CASH) in sea water, Figure 2: Chromatograms of the 1st dynamic adsorption (120 cm3 h-1) of CASH in sea water. Figure 3: Chromatograms of the 2nd dynamic adsorption (120 cm3 h1

) of CASH in sea water. Figure 4: Chromatograms of the 3rd dynamic adsorption (120 cm3

h-1) of CASH in sea water. Figure 5: 1st Dynamic adsorption of CASH in seawater flow of 120 cm3 h-1. Figure 6: 2nd Dynamic adsorption of CASH in sea water flow of 120 cm3 h-1. Figure 7: 3rd Dynamic adsorption of CASH in sea water flow of 120 cm3 h-1. Figure 8: Standard calibration for CASH in sea water. Table 1: Results obtained in the 1st test surfactant (core 1) in sea water with 120 cm3 h-1. Table 2: Results obtained in the 2nd test surfactant (core 2) in sea water with 120 cm3 h-1. Table 3: Results obtained in the 3rd test surfactant (core 3) in sea water with 120 cm3 h-1.

ACKNOWLEDGMENTS The authors want to acknowledge to the Mexican Institute of Petroleum (IMP), Projects D.61029 “Diseño y síntesis de nuevos prototipos de productos químicos multifuncionales con propiedades dispersantes de asfaltenos, modificadoras de la mojabilidad y desemulsificantes and Y.00123 “Procesos de rm en yacimientos carbonatados fracturados de alta salinidad y temp. con base en el diseño, desarrollo y escalamiento de productos quimicos AD HOC (under the auspices of the found CONACYT- SENER-Hidrocarburos Project 146735), for financial support. Marissa PérezAlvarez thanks to Dirección de Cátedras CONACyT for its appointment.


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Diagram core-flood system.

Figure 2

Molecular structure of cocamidoproyl-hydroxysultaine CAHS.

Figure 3

TGA of surfactant cocoamidopropyl-hydroxysultaine CASH

Figure 4

Chromatogram of the experiment 1 under dynamic adsorption conditions for volumes a) 1 PV, b) 27 PV and c) 49 PV for CASH in seawater.

Figure 5

Dynamic adsorption isotherm of CASH in sea water at the injection rate of 120 cm3·h-1

Figure 6

Schemes for the step of diffusion and dispersion of surfactant in seawater within cores and graphics of CNS vs PV.

Figure 7

Core in the stage of dynamic adsorption and graphic CNS vs PV.

Figure 8

Graphic CNS vs PV in step of equilibrium.

Figure 9

(a) Electrical atomic charges on the exposed (104) surface of calcite (the view is perpendicular to the surface). Side calcite surface views of the (b) HOMO and (c) LUMO states.

Figure 10

It is shown A) a mimic molecule of surfactant that possessing two charge at

the same time (blue color) and B) represent an external surface negatively charged of channel present in a limenston (grey color).


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Tables Table 1

Experimental condition for studies in dynamic adsorption.

Table 2

Physicochemical properties of the seawater used in the evaluations.

Table 3

Petrophysical properties of limestone cores

Table 4

Surfactant adsorption for cores 1-3 under 120 cm3·h-1 seawater flow.

Abbreviation

Φ

Pore-volume fraction

K

Absolute Permeability

HPLC

High Performance Liquid Chromatography

CAHS

cocamidopropyl hydroxysultaine

TGA

Termogravimetric Analysis

VP

Pore Volume (cm3)

HOMO

Highest Occupied Molecular Orbital

LUMO

Lowest Unoccupied Molecular

DFT

Density Functional Theory



Graphic for Manuscript


Page 30 of 30

Nonquilibrium and Equilibrium Stationary States of Zwitterionic

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