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Experimental investigation into l-Arg and l-Cys eco-friendly surfactants in enhanced oil recovery by considering IFT reduction and wettability alteration

Experimental investigation into l-Arg and l-Cys eco-friendly surfactants in enhanced oil recovery... Surfactant flooding is an important technique used to improve oil recovery from mature oil reservoirs due to minimizing the interfacial tension (IFT) between oil and water and/or altering the rock wettability toward water-wet using various surfactant agents including cationic, anionic, non-ionic, and amphoteric varieties. In this study, two amino-acid based surfactants, named lauroyl arginine (l -Arg) and lauroyl cysteine (l -Cys), were synthesized and used to reduce the IFT of oil–water systems and alter the wettability of carbonate rocks, thus improving oil recovery from oil-wet carbonate reservoirs. The synthesized surfactants were characterized using Fourier transform infrared spectroscopy and nuclear magnetic resonance analyses, and the critical micelle concentration (CMC) of surfactant solutions was determined using conductivity, pH, and turbidity tech- niques. Experimental results showed that the CMCs of l -Arg and l -Cys solutions were 2000 and 4500 ppm, respectively. It was found that using l -Arg and l -Cys solutions at their CMCs, the IFT and contact angle were reduced from 34.5 to 18.0 and 15.4 mN/m, and from 144° to 78° and 75°, respectively. Thus, the l -Arg and l -Cys solutions enabled approximately 11.9% and 8.9% additional recovery of OOIP (original oil in place). It was identified that both amino-acid surfactants can be used to improve oil recovery due to their desirable effects on the EOR mechanisms at their CMC ranges. Keywords Chemical EOR · Amino-acid surfactant · IFT · Wettability · Coreflooding 1 Introduction Consumption of oil, the most common energy source, has Edited by Yan-Hua Sun been increased in the world and discovery of new oil reser- voirs has been reduced due to exploration difficulties (Ali * Ghasem Zargar et al. 2018a). Thus, the oil industry focuses more on increas- gzha.nano113@gmail.com ing the production from the currently producing reservoirs using different oil recovery methods including primary, sec- Department of Petroleum Engineering, Abadan Faculty of Petroleum Engineering, Petroleum University ondary, and tertiary recovery processes (Ali et al. 2018b). In of Technology (PUT), Abadan, Iran the primary phase, oil is usually recovered using the internal Department of Petroleum Engineering, Ahwaz Faculty energy of the reservoir, while, water and gas injections are of Petroleum Engineering, Petroleum University secondary methods used to maintain the reservoir pressure of Technology (PUT), Ahwaz, Iran and increase the recovery factor after the decline of the res- Department of Petroleum Engineering, Faculty ervoir. As is obvious, the primary and secondary recovery of Engineering, Soran University, Soran, Kurdistan Region, techniques enable the production of only about one-third of Iraq the oil from the reservoir (Kamal et al. 2017; Emadi et al. Department of Petroleum Engineering, College 2018; Ali et  al. 2019a). Hence, EOR processes, such as of Engineering, Knowledge University, Erbil, thermal recovery, chemical recovery, miscible and immis- Kurdistan Region, Iraq 5 cible flooding play a great role in extracting some of the School of Engineering, Edith Cowan University, Joondalup, remaining crude oil and improving oil recovery. Chemical WA 6027, Australia Vol.:(0123456789) 1 3 106 Petroleum Science (2020) 17:105–117 EOR techniques (cEOR) have been attracted more attention the displacement of oil at the pore scale is related to the nowadays due to having different challenges including IFT volumetric sweep (microscopic) efficiency of the recov - reduction, wettability alteration, and adsorption behavior ery process, which is controlled by the capillary forces (Ali et al. 2019b; Nowrouzi et al. 2018, 2019). Selecting and viscous forces. The capillary numbers are developed an appropriate EOR technique to be effective in reality can from a relationship between these two forces dependent be done using screening criteria and screening algorithms on the viscosity, interfacial tension (IFT), and contact (Mashayekhizadeh et al. 2014). Among all cEOR methods, angle (Wang et  al. 2010; Bera et  al. 2013). According surfactant flooding is the most effective chemical EOR to Kamal et al. (2017), increasing the capillary numbers −7 −6 −3 −2 method having the greatest potential to improve oil recovery. from 10 and 10 to about 10 and 10 will reduce During surfactant flooding, the force that lowers the interfa- the oil saturation by 90% and to zero. To reach these cial tension (IFT) and alters the wettability tends to allow the ranges, IFT between oil and water must be reduced to trapped crude oil in the pore spaces to be displaced (Howe about 20–30 mN/m, which can be achieved by injecting et al. 2015; Manshad et al. 2016; Ahmadi and Shadizadeh, the surfactant. Surfactant flooding also has an impact on 2018; Hanamertani et al. 2017; Olayiwola and Dejam 2019a, micro-emulsification, wettability alteration, and mobility b; Najimi et al. 2019). ratio (Kumar and Mandal 2018; Ahmadi and Shadizadeh In chemical EOR, many chemicals including sur- 2013; Ahmadi et al. 2015). Numerous types of surfactants factants, polymers, and alkalis are used to modify the dis- (cationic, anionic, and non-ionic) have been investigated placement efficiency and the volumetric sweep efficiency. in the laboratory and at the field scale based on the sur - The displacement (microscopic) efficiency consists of the factant structure, adsorption and cost, reservoir tempera- ability of the displacing fluid to sweep out crude oil in ture, salinity and pH, rock properties and the oil recovery the reservoir, horizontally and vertically, toward the pro- (Table  1). In this study, two newly synthesized eco- duction wells (Kamal et al. 2015). This can be achieved friendly surfactants were used to improve the oil recovery by controlling the mobility ratio between oil and injected by their IFT reduction and wettability alteration. Rostami fluid (Dejam 2018, 2019). For this purpose, polymers et al. (2017) studied the effect of lysine derivative amino- as highly viscous solutions are usually injected into oil acid surfactant on IFT reduction and wettability altera- reservoirs (Saboorian-Jooybari et al. 2015). Meanwhile, tion; wherein IFT reduced from 35 to 19.6  mN/m, and Table 1 Summary of previous works on effects of various surfactants on interfacial tension (IFT), contact angle, and oil recovery Surfactant IFT, mN/m Contact angle, degree Oil recovery, % References OOIP Without With surfactant Without With surfactant surfactant surfactant [C12mim][Cl] 15.59 0.07 – 62.1 Nabipour et al. (2017) [C18mim][Cl] 15.59 0.15 – – AN-120 15.59 0.12 – – NX-610 15.59 1.20 – – NX-1510 15.59 0.36 – – NX-2760 15.59 0.13 – – TR-880 15.59 0.11 – – CTAB 21.00 0.01 76.3 8 – Kumar and Mandal (2016) SDS 21.00 0.03 76.3 4 – TWEEN 80 21.00 0.14 76.3 10 – [C12mim][Br] 43.97 9.10 – – Nandwani et al. (2017) [C14mim][Br] 43.97 7.20 – – [C16mim][Br] 43.97 4.70 – 75.6 CTAB 43.97 7.70 – 71 Lysine derivative 35.00 19.58 160 119 53.19 Rostami et al. (2017) l -Arginine 32.47 17.76 126.3 103.7 – Takassi et al. (2017) Cedar 30.1 7.1 – 15 Daghlian et al. (2016) CTAB 30.1 Ultralow – 17 SDS 30.1 7.2 – – AOS 30.1 6.0 – 13 1 3 Petroleum Science (2020) 17:105–117 107 the wettability of the rock changed toward water-wet by 2 Experimental decreasing the contact angle from 160° to 119°, and con- sequently, the oil recovery was increased to 53.9% OOIP. The experimental work of this study was divided into three Nabipour et al. (2017) used two anionics ([C12mim][Cl] parts, as illustrated schematically in Fig. 1. These were (i) and [C18mim][Cl]) and five most common (AN-120, synthesis and characterization of eco-friendly surfactants, NX-610, NX-1510, NX-2760, and TR-880) surfactants to (ii) the preparation and CMC identification of surfactant reduce IFT and increase oil recovery. Their results showed solutions, and (iii) the IFT, contact angle, and coreflooding that the minimum IFT was 0.07 mN/m and a maximum oil tests. recovery up to 62.1% OOIP were achieved using an ani- onic surfactant with a concentration of 4000 ppm (Nabi- 2.1 Materials pour et  al. 2017). Additionally, Daghlian et  al. (2016) investigated the effect of a natural surfactant called Cedar All the salts and chemical reagents including arginine, and three common surfactants (CTAB, SDS, and AOS) cysteine, lauroyl chloride, methanol, toluene, ethanol, on IFT reduction. IFT was reduced from 30.1 to about sodium dodecyl sulfate, sodium hydroxide, and sodium chlo- 6 mN/m and ultralow values with increasing oil recovery ride with a purity of about 99% were purchased from Merck up to 17% OOIP. Kumar and Mandal (2018) synthesized Company. The chemical structures of arginine and cysteine a zwitterionic surfactant for improving oil recovery from are shown in Fig. 2. carbonate reservoirs; they identified a significant reduc- For preparing surfactant and brine solutions, distilled tion in IFT value and altered the wettability of rock from water with a density of 0.998 g/cm and pH of 7.02 was oil-wet to water-wet with additional oil recovery of 30.8% used. Brine was prepared by mixing NaCl to 10,0000 ppm OOIP. More recently, Olayiwola and Dejam (2019a, b) concentration with distilled water. The density and viscosity stated that the role of chemical processes (i.e., surfactant) of the synthetic seawater (SSW) were about 1.068 g/cm and in improving oil recovery can be improved by adding 1.42 cP, respectively. In addition, crude oil with a density of nanoparticles. 0.875 g/cm (30° API) and a viscosity of 11 cP was obtained The ultimate goal of this study is to investigate the from the Kupal oilfield and used in coreflooding tests. How - effects of two synthetic eco-friendly surfactants called ever, for IFT and contact angle measurements, kerosene with lauroyl arginine (l -Arg) and lauroyl cysteine (l -Cys) on improving oil recovery from carbonate reservoirs. The (a) NH OO (b) synthesized surfactants were examined using Fourier transform infrared spectroscopy (FT-IR) and nuclear mag- H N N OH HS OH netic resonance (NMR). The effects of l -Arg and l -Cys surfactants at different concentrations on IFT reduction, NH NH 2 2 wettability alteration, and oil recovery improvement have been experimentally investigated. Fig. 2 Molecular structures of a arginine, and b cysteine HS OH NH2 Cysteine IFT and contact angle tests CI Surfactant solution Lauroyl chloride Thermowell Coreflooding preparation NH O Characterization L-Arg & L-Cys Synthesis Pressure drop products H2N N OH NH Core Arginine Sample Pendant drop Contact angle Coreflooding IFT measurement measurement recovery measurement Synthesis & characterization CMC measurement Fig. 1 Schematic illustration of experimental procedures of synthesizing l -Arg and l -Cys surfactants and their EOR applications 1 3 108 Petroleum Science (2020) 17:105–117 a density of 0.79 g/cm and a viscosity of 1.32 cP was used formation of the target surfactant has effectively decreased instead of crude oil due to the lack of clarity in the surfactant the melting point of arginine. The product in that state was color. For the wettability measurement and coreflooding, dispatched for FT-IR and H-NMR spectra analysis tests. the core plugs and thin sections were collected from the A Bomem MB-Series 1998 spectrophotometer (Quebec, Asmari Carbonate Formation outcrop from the Baba-kuhi Canada) was used to obtain the FT-IR spectrum of the sam- Mountain in Iran. ple applying the potassium bromide (KBr) pellet approach −1 with a 4 cm resolution. A Bruker (Rheinstetten, Germany) 2.2 Synthesis of amino‑acid surfactants Avance 500 spectrometer was used to record H-NMR spec- trum of the surfactant sample at ambient temperature in deu- Two amino-acid surfactants, lauroyl arginine (l -Arg) and terated dimethyl sulfoxide (DMSO-d6) as solvent. Units of lauroyl cysteine (l -Cys), were used as eco-friendly EOR parts per million (ppm) denoted by δ were utilized to show agents in this study since they are non-toxic. the chemical shifts in this spectrum. The number of protons (N) was reported for a specific resonance by NH. Multiplici- 2.2.1 l A ‑ rg synthesis ties were also indicated as singlet (s), triplet (t), and multi- plet (m). The melting point of the sample was determined In order to synthesize l -Arg with accordance with Takassi in capillary tubes with a melting point device (Barnstead et al. (2017) and Madani et al. (2019), 5 mL of lauroyl chlo- Electrothermal 9200, Dubuque, Iowa, USA). The melting ride and 3.0 mg of arginine were mixed with 100 mL of point of l -Cys was 176–178 °C. methanol in a 250-mL beaker. After mixing thoroughly for 2 h, the solution was transferred into a dry round-bottom 2.3 Preparation and CMC measurement flask and was mixed for 24 h by magnetic stirring at the of surfactant solutions reflux temperature when a white precipitate was observed in the bottom of the flask. Afterward, the white deposit was To prepare surfactant solutions, l -Arg and l -Cys were sepa- filtered and dried at 80 °C and atmospheric pressure. The rately mixed with distilled water in a beaker using a mag- collected powder of l -Arg was recrystallized from the dis- netic stirrer (MR3001 K) for 30–60 min. The concentration tilled water–ethanol solvent. of the surfactant solutions ranged from 200 to 10,000 ppm. Then, the densities of all the prepared surfactant solutions 2.2.2 l ‑Cys synthesis were measured using a DA-640 KEN density meter at ambi- ent conditions (Table 2). In addition, the CMC values of Using the method of Ramshini (2017), lauroyl cysteine both surfactants were determined by measuring the electrical (l -Cys) was synthesized by mixing 2 mg of cysteine and conductivity, pH, and turbidity characteristics of surfactant 100 mL of methanol in a round-bottom flask containing a solutions over a wide concentration range with a JEN- magnetic stirring bar. First, the mixture was stirred for 1 h, WAY-4510 conductivity meter, a Mettler Toledo pH-meter, but no dissolution of cysteine was observed. Then, 4 mL of and a AL250T-IR turbidity meter, respectively. lauroyl chloride was poured slowly into the flask and the cysteine completely dissolved in the methanol, and then 2.4 IFT measurement the mixture was stirred for 12 h at room temperature. The produced l -Cys (a white colored precipitate) was separated The pendant drop method is a suitable simple method that by attaching a round-bottom flask to a vacuum pump on can be used to measure IFT between liquid and liquid or the magnetic stirrer rotated at 80 °C. Finally, the produced liquid and gas. The pendant drop method can measure both material was crystallized using the distilled water–ethanol static and dynamic IFT. This method measures the IFT using mixture to obtain a purified powder. an analysis of the drop shape (Bagalkot et al. 2018): 2.2.3 Characterization of amino‑acid surfactants ΔgD (1) After the purification of the produced material by crystalli- where ∆ρ is the difference in density between the two fluids, zation in a distilled water–ethanol mixture, sufficient crystal- g is the acceleration of gravity, D is the maximum diameter lized powder was extracted for melting point, nuclear mag- of the droplet, and H is the drop shape coefficient. netic resonance ( H-NMR) and Fourier transform infrared A VIT-6000 device manufactured by Fars Company (FT-IR) spectra analyses (Takassi et  al. 2017; Ramshini with a high accuracy of 99% was used to measure the value 2017; Madani et al. 2019). The melting point of the purified of IFT between liquid–liquid systems in both static and synthesized l -Arg surfactant was measured at 185–186 °C, dynamic conditions (Fig. 3). In this study, the IFTs between which is a good indicator for the synthesis process, since the 1 3 Petroleum Science (2020) 17:105–117 109 Table 2 Formulation of l -Arg and l -Cys surfactant solutions used in this study 3 3 l -Arg sample Surfactant concentra- Density, g/cm l -Cys sample Surfactant concentra- Density, g/cm tion, ppm tion, ppm l -Arg-200 200 0.9986 l -Cys-200 200 0.9985 l -Arg-400 400 0.9987 l -Cys-400 400 0.9986 l -Arg-600 600 0.9988 l -Cys-600 600 0.9987 l -Arg-800 800 0.9989 l -Cys-800 800 0.9988 l -Arg-1000 1000 0.9991 l -Cys-1000 1000 0.9989 l -Arg-2000 2000 0.9994 l -Cys-2000 2000 0.9993 l -Arg-4000 4000 0.9998 l -Cys-4000 4000 0.9998 l -Arg-6000 6000 1.0001 l -Cys-6000 6000 1.0002 l -Arg-8000 8000 1.0008 l -Cys-8000 8000 1.0011 l -Arg-10000 10,000 1.0012 l -Cys-10000 10,000 1.0017 Pump controller Surfactant solution Pump Syringe Illuminating system Camera Computer Experimental chamber Vibration-proof table Fig. 3 A schematic diagram of a VIT-6000 apparatus used to measure IFT and contact angle kerosene and surfactant solutions with different concentra- measure the contact angle at a temperature of 70–80 °C and tions (200–10,000 ppm) were measured. IFT measurements a pressure of 1200 psi (Fig. 3). For this purpose, a carbonate were simply performed as follows: (1) kerosene and sur- rock thin section with a diameter of 2 mm were trimmed from factant solutions with different concentrations were prepared; the carbonate outcrop sample and polished to become entirely (2) they were stored in the solution injection chambers; (3) smooth. The prepared rock sections were then cleaned with first, kerosene was pumped into the main chamber of the toluene and distilled water to remove all impurities, and as device; (4) the surfactant solution was then injected from the outlined by Villard et al. (1993) and Manshad et al. (2017), injection chamber into the needle device in order to provide a they were aged in kerosene at 70 °C for 12 days to become oil- drop of the surfactant solution on the end of the needle to be wet. In order to change the wettability of oil-wetted rock slices hung inside the kerosene phase; and (5) the IFT measurement under static conditions, they were submerged in enclosed between kerosene and the surfactant solution was performed. containers filled with surfactant solutions ( l -Arg and l -Cys) for 5 days. The wettability of carbonate rock sections was 2.5 Contact angle measurement qualitatively assessed by measuring the contact angle of a kerosene droplet on the surface of the prepared rock thin sec- The contact angle is one of the quantitative methods which tions, before and after the treatment with surfactant solutions. identifies the wetting of the reservoir rock in the presence of two fluids. This method is the most common wettability meas-2.6 Coreflooding test urement in the oil industry. It can be performed under differ - ent pressure and temperature conditions (Tiab and Donaldson Figure 4 illustrates a schematic diagram of the coreflooding 2016). In the current work, a VIT-6000 apparatus was used to setup. The device is mainly composed of tanks containing 1 3 110 Petroleum Science (2020) 17:105–117 Confining pressure PI Water feed Fluid accumulator PI Start Core holder Pump injection Production Oven Fig. 4 A schematic diagram of the coreflooding apparatus injection fluids, pumps, a core holder, and a produced-oil col- shows the FT-IR spectrum of the produced l -Arg revealing −1 lector. Fluids from their chambers are pumped into the core the absorption peak of the amine group at 3341 cm . The −1 plug. In this research, the core chamber can hold a core plug absorption band at 2927 cm was a characteristic peak for with a maximum length of 3.5 in and a maximum diameter aliphatic hydrogens. The carbonyl peak of the carboxylic acid −1 of 1.5 in. The coreflooding was performed at 75 °C and 1500 group appeared at 1743 cm which was overlapped by that −1 psi. Fluid accumulators containing crude oil, brine, and sur- of amide carbonyl groups. The peaks at 1589 and 1511 cm factant solutions are located along with a core holder inside were ascribed to N–H asymmetric and symmetric in-plane an oven to control the temperature of the system. The output bending of amide and amine groups, respectively. The peak −1 line of the core holder chamber is removed from the oven and at 1445 cm could be attributed to vibration of the amino the outlet fluid is stored in a special fluid collection vessel. In group which is in resonance with the attached amine group. −1 order to conduct displacement tests, carbonate core plugs with The C–O stretching band was observed at 1057 cm and −1 porosity of 9.3%–13.2% and permeability of 7.6–10.4 mD were a peak appeared at 729 cm due to the N–H out of plane selected from the Asmari outcrop in Iran. The selected plugs bending (Takassi et al. 2017; Madani et al. 2019). Addition- were cleaned with toluene using Soxhlet extraction at 80 °C ally, Fig.  6b illustrates the FT-IR spectrum of l -Cys sur- for 24 h in order to remove the presence of water, oil, and any factant, absorption of the amine group appeared at around -1 -1 other residues. Then the core samples were dried in an oven at 3433 cm . The absorption band at 2955 cm was the char- 120 °C for 24 h. Displacement tests were conducted on core acteristic peak for aliphatic hydrogens. The weak absorption -1 plugs at 75 °C. The experimental procedures are as follows: (1) peak at 2379 cm was due to the S–H stretching vibration. 1.6 pore volume (PV) of brine (100,000 ppm NaCl solution) The carbonyl peak of the amide group and carboxylic acid 3 −1 was injected into the core plug at a flow rate of 0.5 cm /min group appeared at 1637 and 1715 cm . The peaks at 1541 −1 (as a secondary recovery). Two pressure transducers were used and 1509 cm were ascribed to N–H asymmetric and sym- to record the pressure values at the injection and production metric in-plane bending of amide groups, respectively. The −1 points. (2) Afterward, 1.4 PV surfactant solution (as a tertiary C–O stretching band could be observed at 1280 cm and the −1 recovery, l -Arg-2000 or l -Cys-4500 solution) was injected into peak that appeared at 792 cm was due to the N–H out of the core plug at a flow rate of 0.3 cm /min. The oil recovery plane bending (Ramshini 2017). factors (RF) of both brine injections and l -Arg-2000 and l -Cys- Figure  7a presents the H-NMR spectrum of l -Arg, 4500 surfactant flooding were determined from the volume of wherein the carboxyl proton was observed at 12.38 ppm. the oil collected from the outlet of the coreflooding apparatus. The NH protons of amide, imine, and amine groups were observed at 8.19, 7.39, and 7.17 ppm, respectively. The peak at 4.99 ppm is related to the chiral center proton. The meth- 3 Results and discussion ylene group attached to the amine group was observed at 3.00 ppm. The peak at 2.87 ppm was due to the methylene 3.1 Spectral characterization of synthesized group attached to the amide group. Some of the peaks of the surfactants methylene protons and one of the amine groups were merged together. The resonance of these protons was observed at The mechanisms of synthesizing l -Arg and l -Cys surfactants around 1.81–1.39  ppm. The methyl group of the hydro- are shown in Fig. 5. FT-IR and 1 H-NMR spectroscopy were carbon tail was also observed as a triplet peak at 0.90 ppm used to confirm the structure of the synthesized amino-acid- (Takassi et al. 2017; Madani et al. 2019). In the H-NMR based-surfactant, as shown in Figs.  6 and 7. Figure  6a spectrum of the developed l -Cys, the carboxyl proton was 1 3 Petroleum Science (2020) 17:105–117 111 (a) NH O H2NN OH Cl Refluxing NH for 24 h/methanol Arginine Dodecanyl chloride NH HO N NH2 O NH Synthesized surfactant (Lauroy arginine) (b) O O HS OH Cl NH 2 Refluxing for 24 h/methanol Cysteine Dodecanyl chloride NH OH HS Synthesized surfactant (Lauroy cysteine) Fig. 5 Mechanisms of synthesized surfactants. a L-Arg. b L-Cys Fig. 6 FT-IR spectrum of the synthesized amino-acid surfactants. a L-Arg (Takassi et al. 2017; Madani et al. 2019). b L-Cys (Ramshini 2017) observed at 12.48 ppm. The appearance of the NH proton of center appeared in the range of 3.12–3.31 ppm. The peaks of amide group at 8.335 ppm as a peak indicated the presence the methylene protons of the dodecanoyl chain were merged of an amide group in the surfactant structure. The proton of together. The resonance of these protons was observed at the chiral center appeared as a doublet of the doublet in the around 2.01–2.28  ppm. The SH proton was observed at range of 4.79–4.81 ppm. The resonance of the diastereotopic 1.50 ppm and also the methyl group of the hydrocarbon tail hydrogens bonded to the neighboring carbon of the chiral was observed at 0.88 ppm (Ramshini 2017). 1 3 0.902 1.181 1.228 1.396 2.94 23.07 2.875 3.004 3.89 4.988 0.98 7.171 3.11 7.390 8.194 1.04 1.00 12.384 112 Petroleum Science (2020) 17:105–117 (a) (b) H O DMSO DMSO H2O a b fk NH c d g H C CH SH 3 2 NH h CH d 2 i CH2 C H C C 2 CH2 CH NH 2 O CH2 NH b-e g COOH c HC O H3C C e COOH CH2 NH 15 14 13 12 11 10 9 8 7 6 5 4 3 2 1 0 16 14 12 10 8642 0 Chemical shift, ppm Chemical shift, ppm Fig. 7 H-NMR spectrum of the synthesized amino-acid surfactants. a L-Arg (Takassi et al. 2017; Madani et al. 2019). b L-Cys (Ramshini 2017) reduce the IFT and alter the wettability of rock surfaces. For 3.2 Characterization of surfactant solutions the l -Arg surfactant, a sharp decline in the IFT curve was observed from increasing the concentration to 2000 ppm, In this part, the characteristics of the prepared surfactant wherein the IFT was reduced by about 50%, from 34.5 to solutions (200–10,000 ppm) including conductivity, pH, 18.0 mN/m (red color on Fig. 10). However, when the l - and turbidity were measured to identify the critical micelle Arg concentration increased from 2000 to 10,000  ppm, concentrations (CMC). Figure  8 illustrates the results of only a small decrease in IFT was observed, from 18.0 to conductivity, pH, and turbidity of the l -Arg solutions. As it 16.1 mN/m (about 5% compared with the initial value of can be seen, the optimum values of the CMC from conduc- IFT). tivity, pH, and turbidity were 1700, 1900, and 2200 ppm, The measured values of IFT between kerosene and l - respectively. Although there is a small difference among the Cys solutions (blue solid circles) are also shown in Fig. 10. values of CMC dependent on the three measured properties Although the CMC of l -Cys is higher compared with the of solutions, 2000 ppm was selected as an average effective l -Arg (Figs. 8, 9), its IFT curve shows a similar trend to the value of the CMC for the solution prepared from l -Arg. The l -Arg IFT curve as shown in Fig. 10. Additionally, a sharp measured properties of the l -Cys solutions at different con- reduction in the IFT value was observed from the zero to centrations of 200, 400, 600, 800, 1000, 2000, 4000, 8000, 4000 ppm of l -Cys. From the initial value 34.5 mN/m, the and 10,000 ppm were shown in Fig. 9. From the conductiv- IFT was decreased to 15.4 mN/m at the CMC concentra- ity, pH, and turbidity curves, different values of CMC were tion. Totally, both types of the surfactants demonstrated determined which were 5200, 4400, and 4500 ppm, respec- the same performance in reducing IFT. Shapes of kerosene tively. Accordingly, the concentration of 4500 ppm has been droplets within both l -Arg and l -Cys solutions are illustrated chosen as the effective CMC for the l -Cys solution. in Fig. 11. 3.3 IFT 3.4 Contact angle Figure 10 shows IFT curves of l -Arg and l -Cys solutions. The contact angle values between kerosene and the prepared Surfactant solutions were prepared using different concentra- surfactant solutions of different concentrations are shown tions of the synthesized amino-acid surfactants. The selected in Fig. 12. The measured contact angles (Fig. 12a) between concentrations were 200, 400, 600, 800, 1000, 2000, 4000, kerosene and l -Arg solutions reduced from 144° to 70°. It 8000, and 10,000 ppm. The value of IFT decreased with is also clear that a rapid drop in the value of contact angle an increase in the surfactant concentration, which is simi- occurred with increasing the l -Arg concentration up to lar to the results discussed by Pal et al. (2018) where they 2000 ppm (from 144° to 78°), and this decline continued used a synthesized sodium ethyl ester sulfonate surfactant to 1 3 Petroleum Science (2020) 17:105–117 113 (a) (a) 0 2000 4000 6000 8000 10000 0 2000 4000 6000 8000 10000 L-Arg concentration, ppm L-Cys concentration, ppm 7.0 3.5 (b) (b) 3.0 6.5 2.5 2.0 6.0 1.5 1.0 5.5 0.5 5.0 0 2000 4000 6000 8000 10000 02000 400060008000 10000 L-Cys concentration, ppm L-Arg concentration, ppm (c) (c) 0 2000 4000 6000 8000 10000 0 2000 4000 6000 8000 10000 L-Cys concentration, ppm L-Arg concentration, ppm Fig. 9 CMC determination of the l -Cys solution. a Conductivity. b Fig. 8 CMC determination of the l -Arg solution via different meth- pH. c Turbidity ods. a Conductivity. b pH. c Turbidity very smoothly to 70° at 10,000 ppm concentration. This point, the value of the contact angle changed only slightly. is quite consistent with the descriptions of Mandal et al. Generally, both used surfactants were active in reducing the (2015), wherein they used a mixed Tween 80 and SDBS contact angle and changing the wettability toward water-wet. solution to alter the wettability of quartz rocks. In addition, while using l -Cys solutions, the contact angle between 3.5 Coreflooding kerosene and surfactant solutions decreased gradually and significantly from 144° to 75° at the CMC point (4000 ppm In this study, surfactant solutions were prepared by dis- concentration), as shown in Fig. 12b. While, above the CMC persing the synthesized surfactant in water at different 1 3 Turbidity, NTU pH Conductivity, µS/cm Conductivity, µS/cm pH Turbidity, NTU 114 Petroleum Science (2020) 17:105–117 35 Flooding profiles in Fig.  13 illustrate that an oil recov- L-Arg L-Cys ery of 38.6% OOIP was achieved after injecting 1.6 PV of brine into Plug #1; and a follow-up injection of 1.4-PV l - Arg-2000 solution recovered an additional 11.9% OOIP for a total oil recovery 50.5% OOIP (green and black lines in 20 Fig. 13). However, from Plug #2, 43.7% OOIP was recov- ered by water injection, and an additional 8.9% OOIP was produced by the tertiary flooding of l -Cys-4500, as shown by red and blue lines in Fig. 13. These improvements in oil recovery could be due to the IFT reduction and wettability 010002000300040005000 6000 7000 8000 9000 10000 alteration. Generally, l -Arg-2000 surfactant (11.9% OOIP) Surfactant concentration, ppm provided a better recovery performance than l -Cys-4500 surfactant (8.9% OOIP). This may be due to higher adsorp- Fig. 10 IFT values measured between kerosene and l -Arg and l -Cys tion of the l -Cys-4500 than that of l -Arg-2000 onto the solutions at concentration of 200–10,000 ppm rock surface. concentrations (200–10000  ppm). The CMC for l -Arg and l -Cys surfactants were determined from the results of 4 Conclusions conductivity, pH, and turbidity. The minimum IFTs and contact angles of l -Arg and l -Cys were measured at their In this study, the effects of lauroyl arginine (L-Arg) and CMCs, 2000 and 4500 ppm, respectively. These l -Arg- lauroyl cysteine (L-Cys) surfactants on the IFT reduction, 2000 and l -Cys-4500 solution were selected to be injected wettability alteration and oil recovery were studied. The after water injection (Table 3). For this purpose, two core IFT and wettability were measured using the pendant drop plugs were prepared and their properties are listed in method and the contact angle method, also oil recovery Table 3. was determined by coreflooding tests. The outcomes of this study are summarized as follows: Fig. 11 Shape profiles of kerosene droplets against surfactant solutions 1 3 IFT, mN/m Petroleum Science (2020) 17:105–117 115 Fig. 12 Contact angle between kerosene and a l -Arg and b l -Cys solutions at different concentrations Table 3 Summary of secondary and tertiary flooding Core Porosity, % Perme- Pore volume S ,% Injection fluid Water flooding Surfactant flooding Total oil oi ability, (PV), cm recovery, Oil recovery, S , % Oil recovery, S , % or or mD %OOIP % OOIP % OOIP Plug #1 13.097 10.41 12.74 72.2 l -Arg-2000 38.6 44.3 11.9 35.7 50.5 Plug #2 9.314 7.68 9.08 74.3 l -Cys-4500 43.7 41.9 8.9 35.2 52.6 The contact angle of the carbonate thin section was Water flooding Surfactant flooding decreased slightly more by l -Arg than by the l -Cys sur- factant at CMCs from 144° to 70° and 77°, respectively. • l -Arg surfactant enabled the production of more addi- tional crude oil compared to the l -Cys surfactant at their CMCs. l -Arg-2000 improved oil recovery from 38.6% to Waterflooding I 50.5% OOIP (extra 11.9% OOIP), while it was increased Waterflooding II 10 from 43.7% to 52.6% OOIP (extra 8.9% OOIP) by l -Cys- L-Cys-4500 L-Arg-2000 • Despite obtaining promising results in this study through 0 0.4 0.8 1.2 1.6 2.0 2.4 2.8 getting almost the same performance of l -Arg and l -Cys Pore volume injected surfactants in reducing IFT and altering the wettability, l -Arg was more effective in improving oil recovery com- Fig. 13 Oil recovery profiles of water injection, l -Arg-2000 and l - pared with l -Cys. Cys-4500 flooding into the Asmari core plugs. The green line rep- resents the first brine injection into Plug #1, the red line shows the recovery from the second brine injection into Plug #2, the black line is for the l -Arg solution injection at 2000 ppm into Plug #1 after the Open Access This article is distributed under the terms of the Crea- first brine injection, and the blue line demonstrates the l -Cys solution tive Commons Attribution 4.0 International License (http://creat iveco injection at 4500 ppm into Plug #2 after the second water injection mmons.or g/licenses/b y/4.0/), which permits unrestricted use, distribu- tion, and reproduction in any medium, provided you give appropriate credit to the original author(s) and the source, provide a link to the Creative Commons license, and indicate if changes were made. CMCs of l -Arg and l -Cys solutions were measured to be 2000 and 4500 ppm, respectively, from electrical conductivity, pH, and turbidity measurements. 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Experimental investigation into l-Arg and l-Cys eco-friendly surfactants in enhanced oil recovery by considering IFT reduction and wettability alteration

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Springer Journals
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Copyright © The Author(s) 2019
Subject
Earth Sciences; Mineral Resources; Industrial Chemistry/Chemical Engineering; Industrial and Production Engineering; Energy Policy, Economics and Management
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1672-5107
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1995-8226
DOI
10.1007/s12182-019-0354-2
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Abstract

Surfactant flooding is an important technique used to improve oil recovery from mature oil reservoirs due to minimizing the interfacial tension (IFT) between oil and water and/or altering the rock wettability toward water-wet using various surfactant agents including cationic, anionic, non-ionic, and amphoteric varieties. In this study, two amino-acid based surfactants, named lauroyl arginine (l -Arg) and lauroyl cysteine (l -Cys), were synthesized and used to reduce the IFT of oil–water systems and alter the wettability of carbonate rocks, thus improving oil recovery from oil-wet carbonate reservoirs. The synthesized surfactants were characterized using Fourier transform infrared spectroscopy and nuclear magnetic resonance analyses, and the critical micelle concentration (CMC) of surfactant solutions was determined using conductivity, pH, and turbidity tech- niques. Experimental results showed that the CMCs of l -Arg and l -Cys solutions were 2000 and 4500 ppm, respectively. It was found that using l -Arg and l -Cys solutions at their CMCs, the IFT and contact angle were reduced from 34.5 to 18.0 and 15.4 mN/m, and from 144° to 78° and 75°, respectively. Thus, the l -Arg and l -Cys solutions enabled approximately 11.9% and 8.9% additional recovery of OOIP (original oil in place). It was identified that both amino-acid surfactants can be used to improve oil recovery due to their desirable effects on the EOR mechanisms at their CMC ranges. Keywords Chemical EOR · Amino-acid surfactant · IFT · Wettability · Coreflooding 1 Introduction Consumption of oil, the most common energy source, has Edited by Yan-Hua Sun been increased in the world and discovery of new oil reser- voirs has been reduced due to exploration difficulties (Ali * Ghasem Zargar et al. 2018a). Thus, the oil industry focuses more on increas- gzha.nano113@gmail.com ing the production from the currently producing reservoirs using different oil recovery methods including primary, sec- Department of Petroleum Engineering, Abadan Faculty of Petroleum Engineering, Petroleum University ondary, and tertiary recovery processes (Ali et al. 2018b). In of Technology (PUT), Abadan, Iran the primary phase, oil is usually recovered using the internal Department of Petroleum Engineering, Ahwaz Faculty energy of the reservoir, while, water and gas injections are of Petroleum Engineering, Petroleum University secondary methods used to maintain the reservoir pressure of Technology (PUT), Ahwaz, Iran and increase the recovery factor after the decline of the res- Department of Petroleum Engineering, Faculty ervoir. As is obvious, the primary and secondary recovery of Engineering, Soran University, Soran, Kurdistan Region, techniques enable the production of only about one-third of Iraq the oil from the reservoir (Kamal et al. 2017; Emadi et al. Department of Petroleum Engineering, College 2018; Ali et  al. 2019a). Hence, EOR processes, such as of Engineering, Knowledge University, Erbil, thermal recovery, chemical recovery, miscible and immis- Kurdistan Region, Iraq 5 cible flooding play a great role in extracting some of the School of Engineering, Edith Cowan University, Joondalup, remaining crude oil and improving oil recovery. Chemical WA 6027, Australia Vol.:(0123456789) 1 3 106 Petroleum Science (2020) 17:105–117 EOR techniques (cEOR) have been attracted more attention the displacement of oil at the pore scale is related to the nowadays due to having different challenges including IFT volumetric sweep (microscopic) efficiency of the recov - reduction, wettability alteration, and adsorption behavior ery process, which is controlled by the capillary forces (Ali et al. 2019b; Nowrouzi et al. 2018, 2019). Selecting and viscous forces. The capillary numbers are developed an appropriate EOR technique to be effective in reality can from a relationship between these two forces dependent be done using screening criteria and screening algorithms on the viscosity, interfacial tension (IFT), and contact (Mashayekhizadeh et al. 2014). Among all cEOR methods, angle (Wang et  al. 2010; Bera et  al. 2013). According surfactant flooding is the most effective chemical EOR to Kamal et al. (2017), increasing the capillary numbers −7 −6 −3 −2 method having the greatest potential to improve oil recovery. from 10 and 10 to about 10 and 10 will reduce During surfactant flooding, the force that lowers the interfa- the oil saturation by 90% and to zero. To reach these cial tension (IFT) and alters the wettability tends to allow the ranges, IFT between oil and water must be reduced to trapped crude oil in the pore spaces to be displaced (Howe about 20–30 mN/m, which can be achieved by injecting et al. 2015; Manshad et al. 2016; Ahmadi and Shadizadeh, the surfactant. Surfactant flooding also has an impact on 2018; Hanamertani et al. 2017; Olayiwola and Dejam 2019a, micro-emulsification, wettability alteration, and mobility b; Najimi et al. 2019). ratio (Kumar and Mandal 2018; Ahmadi and Shadizadeh In chemical EOR, many chemicals including sur- 2013; Ahmadi et al. 2015). Numerous types of surfactants factants, polymers, and alkalis are used to modify the dis- (cationic, anionic, and non-ionic) have been investigated placement efficiency and the volumetric sweep efficiency. in the laboratory and at the field scale based on the sur - The displacement (microscopic) efficiency consists of the factant structure, adsorption and cost, reservoir tempera- ability of the displacing fluid to sweep out crude oil in ture, salinity and pH, rock properties and the oil recovery the reservoir, horizontally and vertically, toward the pro- (Table  1). In this study, two newly synthesized eco- duction wells (Kamal et al. 2015). This can be achieved friendly surfactants were used to improve the oil recovery by controlling the mobility ratio between oil and injected by their IFT reduction and wettability alteration. Rostami fluid (Dejam 2018, 2019). For this purpose, polymers et al. (2017) studied the effect of lysine derivative amino- as highly viscous solutions are usually injected into oil acid surfactant on IFT reduction and wettability altera- reservoirs (Saboorian-Jooybari et al. 2015). Meanwhile, tion; wherein IFT reduced from 35 to 19.6  mN/m, and Table 1 Summary of previous works on effects of various surfactants on interfacial tension (IFT), contact angle, and oil recovery Surfactant IFT, mN/m Contact angle, degree Oil recovery, % References OOIP Without With surfactant Without With surfactant surfactant surfactant [C12mim][Cl] 15.59 0.07 – 62.1 Nabipour et al. (2017) [C18mim][Cl] 15.59 0.15 – – AN-120 15.59 0.12 – – NX-610 15.59 1.20 – – NX-1510 15.59 0.36 – – NX-2760 15.59 0.13 – – TR-880 15.59 0.11 – – CTAB 21.00 0.01 76.3 8 – Kumar and Mandal (2016) SDS 21.00 0.03 76.3 4 – TWEEN 80 21.00 0.14 76.3 10 – [C12mim][Br] 43.97 9.10 – – Nandwani et al. (2017) [C14mim][Br] 43.97 7.20 – – [C16mim][Br] 43.97 4.70 – 75.6 CTAB 43.97 7.70 – 71 Lysine derivative 35.00 19.58 160 119 53.19 Rostami et al. (2017) l -Arginine 32.47 17.76 126.3 103.7 – Takassi et al. (2017) Cedar 30.1 7.1 – 15 Daghlian et al. (2016) CTAB 30.1 Ultralow – 17 SDS 30.1 7.2 – – AOS 30.1 6.0 – 13 1 3 Petroleum Science (2020) 17:105–117 107 the wettability of the rock changed toward water-wet by 2 Experimental decreasing the contact angle from 160° to 119°, and con- sequently, the oil recovery was increased to 53.9% OOIP. The experimental work of this study was divided into three Nabipour et al. (2017) used two anionics ([C12mim][Cl] parts, as illustrated schematically in Fig. 1. These were (i) and [C18mim][Cl]) and five most common (AN-120, synthesis and characterization of eco-friendly surfactants, NX-610, NX-1510, NX-2760, and TR-880) surfactants to (ii) the preparation and CMC identification of surfactant reduce IFT and increase oil recovery. Their results showed solutions, and (iii) the IFT, contact angle, and coreflooding that the minimum IFT was 0.07 mN/m and a maximum oil tests. recovery up to 62.1% OOIP were achieved using an ani- onic surfactant with a concentration of 4000 ppm (Nabi- 2.1 Materials pour et  al. 2017). Additionally, Daghlian et  al. (2016) investigated the effect of a natural surfactant called Cedar All the salts and chemical reagents including arginine, and three common surfactants (CTAB, SDS, and AOS) cysteine, lauroyl chloride, methanol, toluene, ethanol, on IFT reduction. IFT was reduced from 30.1 to about sodium dodecyl sulfate, sodium hydroxide, and sodium chlo- 6 mN/m and ultralow values with increasing oil recovery ride with a purity of about 99% were purchased from Merck up to 17% OOIP. Kumar and Mandal (2018) synthesized Company. The chemical structures of arginine and cysteine a zwitterionic surfactant for improving oil recovery from are shown in Fig. 2. carbonate reservoirs; they identified a significant reduc- For preparing surfactant and brine solutions, distilled tion in IFT value and altered the wettability of rock from water with a density of 0.998 g/cm and pH of 7.02 was oil-wet to water-wet with additional oil recovery of 30.8% used. Brine was prepared by mixing NaCl to 10,0000 ppm OOIP. More recently, Olayiwola and Dejam (2019a, b) concentration with distilled water. The density and viscosity stated that the role of chemical processes (i.e., surfactant) of the synthetic seawater (SSW) were about 1.068 g/cm and in improving oil recovery can be improved by adding 1.42 cP, respectively. In addition, crude oil with a density of nanoparticles. 0.875 g/cm (30° API) and a viscosity of 11 cP was obtained The ultimate goal of this study is to investigate the from the Kupal oilfield and used in coreflooding tests. How - effects of two synthetic eco-friendly surfactants called ever, for IFT and contact angle measurements, kerosene with lauroyl arginine (l -Arg) and lauroyl cysteine (l -Cys) on improving oil recovery from carbonate reservoirs. The (a) NH OO (b) synthesized surfactants were examined using Fourier transform infrared spectroscopy (FT-IR) and nuclear mag- H N N OH HS OH netic resonance (NMR). The effects of l -Arg and l -Cys surfactants at different concentrations on IFT reduction, NH NH 2 2 wettability alteration, and oil recovery improvement have been experimentally investigated. Fig. 2 Molecular structures of a arginine, and b cysteine HS OH NH2 Cysteine IFT and contact angle tests CI Surfactant solution Lauroyl chloride Thermowell Coreflooding preparation NH O Characterization L-Arg & L-Cys Synthesis Pressure drop products H2N N OH NH Core Arginine Sample Pendant drop Contact angle Coreflooding IFT measurement measurement recovery measurement Synthesis & characterization CMC measurement Fig. 1 Schematic illustration of experimental procedures of synthesizing l -Arg and l -Cys surfactants and their EOR applications 1 3 108 Petroleum Science (2020) 17:105–117 a density of 0.79 g/cm and a viscosity of 1.32 cP was used formation of the target surfactant has effectively decreased instead of crude oil due to the lack of clarity in the surfactant the melting point of arginine. The product in that state was color. For the wettability measurement and coreflooding, dispatched for FT-IR and H-NMR spectra analysis tests. the core plugs and thin sections were collected from the A Bomem MB-Series 1998 spectrophotometer (Quebec, Asmari Carbonate Formation outcrop from the Baba-kuhi Canada) was used to obtain the FT-IR spectrum of the sam- Mountain in Iran. ple applying the potassium bromide (KBr) pellet approach −1 with a 4 cm resolution. A Bruker (Rheinstetten, Germany) 2.2 Synthesis of amino‑acid surfactants Avance 500 spectrometer was used to record H-NMR spec- trum of the surfactant sample at ambient temperature in deu- Two amino-acid surfactants, lauroyl arginine (l -Arg) and terated dimethyl sulfoxide (DMSO-d6) as solvent. Units of lauroyl cysteine (l -Cys), were used as eco-friendly EOR parts per million (ppm) denoted by δ were utilized to show agents in this study since they are non-toxic. the chemical shifts in this spectrum. The number of protons (N) was reported for a specific resonance by NH. Multiplici- 2.2.1 l A ‑ rg synthesis ties were also indicated as singlet (s), triplet (t), and multi- plet (m). The melting point of the sample was determined In order to synthesize l -Arg with accordance with Takassi in capillary tubes with a melting point device (Barnstead et al. (2017) and Madani et al. (2019), 5 mL of lauroyl chlo- Electrothermal 9200, Dubuque, Iowa, USA). The melting ride and 3.0 mg of arginine were mixed with 100 mL of point of l -Cys was 176–178 °C. methanol in a 250-mL beaker. After mixing thoroughly for 2 h, the solution was transferred into a dry round-bottom 2.3 Preparation and CMC measurement flask and was mixed for 24 h by magnetic stirring at the of surfactant solutions reflux temperature when a white precipitate was observed in the bottom of the flask. Afterward, the white deposit was To prepare surfactant solutions, l -Arg and l -Cys were sepa- filtered and dried at 80 °C and atmospheric pressure. The rately mixed with distilled water in a beaker using a mag- collected powder of l -Arg was recrystallized from the dis- netic stirrer (MR3001 K) for 30–60 min. The concentration tilled water–ethanol solvent. of the surfactant solutions ranged from 200 to 10,000 ppm. Then, the densities of all the prepared surfactant solutions 2.2.2 l ‑Cys synthesis were measured using a DA-640 KEN density meter at ambi- ent conditions (Table 2). In addition, the CMC values of Using the method of Ramshini (2017), lauroyl cysteine both surfactants were determined by measuring the electrical (l -Cys) was synthesized by mixing 2 mg of cysteine and conductivity, pH, and turbidity characteristics of surfactant 100 mL of methanol in a round-bottom flask containing a solutions over a wide concentration range with a JEN- magnetic stirring bar. First, the mixture was stirred for 1 h, WAY-4510 conductivity meter, a Mettler Toledo pH-meter, but no dissolution of cysteine was observed. Then, 4 mL of and a AL250T-IR turbidity meter, respectively. lauroyl chloride was poured slowly into the flask and the cysteine completely dissolved in the methanol, and then 2.4 IFT measurement the mixture was stirred for 12 h at room temperature. The produced l -Cys (a white colored precipitate) was separated The pendant drop method is a suitable simple method that by attaching a round-bottom flask to a vacuum pump on can be used to measure IFT between liquid and liquid or the magnetic stirrer rotated at 80 °C. Finally, the produced liquid and gas. The pendant drop method can measure both material was crystallized using the distilled water–ethanol static and dynamic IFT. This method measures the IFT using mixture to obtain a purified powder. an analysis of the drop shape (Bagalkot et al. 2018): 2.2.3 Characterization of amino‑acid surfactants ΔgD (1) After the purification of the produced material by crystalli- where ∆ρ is the difference in density between the two fluids, zation in a distilled water–ethanol mixture, sufficient crystal- g is the acceleration of gravity, D is the maximum diameter lized powder was extracted for melting point, nuclear mag- of the droplet, and H is the drop shape coefficient. netic resonance ( H-NMR) and Fourier transform infrared A VIT-6000 device manufactured by Fars Company (FT-IR) spectra analyses (Takassi et  al. 2017; Ramshini with a high accuracy of 99% was used to measure the value 2017; Madani et al. 2019). The melting point of the purified of IFT between liquid–liquid systems in both static and synthesized l -Arg surfactant was measured at 185–186 °C, dynamic conditions (Fig. 3). In this study, the IFTs between which is a good indicator for the synthesis process, since the 1 3 Petroleum Science (2020) 17:105–117 109 Table 2 Formulation of l -Arg and l -Cys surfactant solutions used in this study 3 3 l -Arg sample Surfactant concentra- Density, g/cm l -Cys sample Surfactant concentra- Density, g/cm tion, ppm tion, ppm l -Arg-200 200 0.9986 l -Cys-200 200 0.9985 l -Arg-400 400 0.9987 l -Cys-400 400 0.9986 l -Arg-600 600 0.9988 l -Cys-600 600 0.9987 l -Arg-800 800 0.9989 l -Cys-800 800 0.9988 l -Arg-1000 1000 0.9991 l -Cys-1000 1000 0.9989 l -Arg-2000 2000 0.9994 l -Cys-2000 2000 0.9993 l -Arg-4000 4000 0.9998 l -Cys-4000 4000 0.9998 l -Arg-6000 6000 1.0001 l -Cys-6000 6000 1.0002 l -Arg-8000 8000 1.0008 l -Cys-8000 8000 1.0011 l -Arg-10000 10,000 1.0012 l -Cys-10000 10,000 1.0017 Pump controller Surfactant solution Pump Syringe Illuminating system Camera Computer Experimental chamber Vibration-proof table Fig. 3 A schematic diagram of a VIT-6000 apparatus used to measure IFT and contact angle kerosene and surfactant solutions with different concentra- measure the contact angle at a temperature of 70–80 °C and tions (200–10,000 ppm) were measured. IFT measurements a pressure of 1200 psi (Fig. 3). For this purpose, a carbonate were simply performed as follows: (1) kerosene and sur- rock thin section with a diameter of 2 mm were trimmed from factant solutions with different concentrations were prepared; the carbonate outcrop sample and polished to become entirely (2) they were stored in the solution injection chambers; (3) smooth. The prepared rock sections were then cleaned with first, kerosene was pumped into the main chamber of the toluene and distilled water to remove all impurities, and as device; (4) the surfactant solution was then injected from the outlined by Villard et al. (1993) and Manshad et al. (2017), injection chamber into the needle device in order to provide a they were aged in kerosene at 70 °C for 12 days to become oil- drop of the surfactant solution on the end of the needle to be wet. In order to change the wettability of oil-wetted rock slices hung inside the kerosene phase; and (5) the IFT measurement under static conditions, they were submerged in enclosed between kerosene and the surfactant solution was performed. containers filled with surfactant solutions ( l -Arg and l -Cys) for 5 days. The wettability of carbonate rock sections was 2.5 Contact angle measurement qualitatively assessed by measuring the contact angle of a kerosene droplet on the surface of the prepared rock thin sec- The contact angle is one of the quantitative methods which tions, before and after the treatment with surfactant solutions. identifies the wetting of the reservoir rock in the presence of two fluids. This method is the most common wettability meas-2.6 Coreflooding test urement in the oil industry. It can be performed under differ - ent pressure and temperature conditions (Tiab and Donaldson Figure 4 illustrates a schematic diagram of the coreflooding 2016). In the current work, a VIT-6000 apparatus was used to setup. The device is mainly composed of tanks containing 1 3 110 Petroleum Science (2020) 17:105–117 Confining pressure PI Water feed Fluid accumulator PI Start Core holder Pump injection Production Oven Fig. 4 A schematic diagram of the coreflooding apparatus injection fluids, pumps, a core holder, and a produced-oil col- shows the FT-IR spectrum of the produced l -Arg revealing −1 lector. Fluids from their chambers are pumped into the core the absorption peak of the amine group at 3341 cm . The −1 plug. In this research, the core chamber can hold a core plug absorption band at 2927 cm was a characteristic peak for with a maximum length of 3.5 in and a maximum diameter aliphatic hydrogens. The carbonyl peak of the carboxylic acid −1 of 1.5 in. The coreflooding was performed at 75 °C and 1500 group appeared at 1743 cm which was overlapped by that −1 psi. Fluid accumulators containing crude oil, brine, and sur- of amide carbonyl groups. The peaks at 1589 and 1511 cm factant solutions are located along with a core holder inside were ascribed to N–H asymmetric and symmetric in-plane an oven to control the temperature of the system. The output bending of amide and amine groups, respectively. The peak −1 line of the core holder chamber is removed from the oven and at 1445 cm could be attributed to vibration of the amino the outlet fluid is stored in a special fluid collection vessel. In group which is in resonance with the attached amine group. −1 order to conduct displacement tests, carbonate core plugs with The C–O stretching band was observed at 1057 cm and −1 porosity of 9.3%–13.2% and permeability of 7.6–10.4 mD were a peak appeared at 729 cm due to the N–H out of plane selected from the Asmari outcrop in Iran. The selected plugs bending (Takassi et al. 2017; Madani et al. 2019). Addition- were cleaned with toluene using Soxhlet extraction at 80 °C ally, Fig.  6b illustrates the FT-IR spectrum of l -Cys sur- for 24 h in order to remove the presence of water, oil, and any factant, absorption of the amine group appeared at around -1 -1 other residues. Then the core samples were dried in an oven at 3433 cm . The absorption band at 2955 cm was the char- 120 °C for 24 h. Displacement tests were conducted on core acteristic peak for aliphatic hydrogens. The weak absorption -1 plugs at 75 °C. The experimental procedures are as follows: (1) peak at 2379 cm was due to the S–H stretching vibration. 1.6 pore volume (PV) of brine (100,000 ppm NaCl solution) The carbonyl peak of the amide group and carboxylic acid 3 −1 was injected into the core plug at a flow rate of 0.5 cm /min group appeared at 1637 and 1715 cm . The peaks at 1541 −1 (as a secondary recovery). Two pressure transducers were used and 1509 cm were ascribed to N–H asymmetric and sym- to record the pressure values at the injection and production metric in-plane bending of amide groups, respectively. The −1 points. (2) Afterward, 1.4 PV surfactant solution (as a tertiary C–O stretching band could be observed at 1280 cm and the −1 recovery, l -Arg-2000 or l -Cys-4500 solution) was injected into peak that appeared at 792 cm was due to the N–H out of the core plug at a flow rate of 0.3 cm /min. The oil recovery plane bending (Ramshini 2017). factors (RF) of both brine injections and l -Arg-2000 and l -Cys- Figure  7a presents the H-NMR spectrum of l -Arg, 4500 surfactant flooding were determined from the volume of wherein the carboxyl proton was observed at 12.38 ppm. the oil collected from the outlet of the coreflooding apparatus. The NH protons of amide, imine, and amine groups were observed at 8.19, 7.39, and 7.17 ppm, respectively. The peak at 4.99 ppm is related to the chiral center proton. The meth- 3 Results and discussion ylene group attached to the amine group was observed at 3.00 ppm. The peak at 2.87 ppm was due to the methylene 3.1 Spectral characterization of synthesized group attached to the amide group. Some of the peaks of the surfactants methylene protons and one of the amine groups were merged together. The resonance of these protons was observed at The mechanisms of synthesizing l -Arg and l -Cys surfactants around 1.81–1.39  ppm. The methyl group of the hydro- are shown in Fig. 5. FT-IR and 1 H-NMR spectroscopy were carbon tail was also observed as a triplet peak at 0.90 ppm used to confirm the structure of the synthesized amino-acid- (Takassi et al. 2017; Madani et al. 2019). In the H-NMR based-surfactant, as shown in Figs.  6 and 7. Figure  6a spectrum of the developed l -Cys, the carboxyl proton was 1 3 Petroleum Science (2020) 17:105–117 111 (a) NH O H2NN OH Cl Refluxing NH for 24 h/methanol Arginine Dodecanyl chloride NH HO N NH2 O NH Synthesized surfactant (Lauroy arginine) (b) O O HS OH Cl NH 2 Refluxing for 24 h/methanol Cysteine Dodecanyl chloride NH OH HS Synthesized surfactant (Lauroy cysteine) Fig. 5 Mechanisms of synthesized surfactants. a L-Arg. b L-Cys Fig. 6 FT-IR spectrum of the synthesized amino-acid surfactants. a L-Arg (Takassi et al. 2017; Madani et al. 2019). b L-Cys (Ramshini 2017) observed at 12.48 ppm. The appearance of the NH proton of center appeared in the range of 3.12–3.31 ppm. The peaks of amide group at 8.335 ppm as a peak indicated the presence the methylene protons of the dodecanoyl chain were merged of an amide group in the surfactant structure. The proton of together. The resonance of these protons was observed at the chiral center appeared as a doublet of the doublet in the around 2.01–2.28  ppm. The SH proton was observed at range of 4.79–4.81 ppm. The resonance of the diastereotopic 1.50 ppm and also the methyl group of the hydrocarbon tail hydrogens bonded to the neighboring carbon of the chiral was observed at 0.88 ppm (Ramshini 2017). 1 3 0.902 1.181 1.228 1.396 2.94 23.07 2.875 3.004 3.89 4.988 0.98 7.171 3.11 7.390 8.194 1.04 1.00 12.384 112 Petroleum Science (2020) 17:105–117 (a) (b) H O DMSO DMSO H2O a b fk NH c d g H C CH SH 3 2 NH h CH d 2 i CH2 C H C C 2 CH2 CH NH 2 O CH2 NH b-e g COOH c HC O H3C C e COOH CH2 NH 15 14 13 12 11 10 9 8 7 6 5 4 3 2 1 0 16 14 12 10 8642 0 Chemical shift, ppm Chemical shift, ppm Fig. 7 H-NMR spectrum of the synthesized amino-acid surfactants. a L-Arg (Takassi et al. 2017; Madani et al. 2019). b L-Cys (Ramshini 2017) reduce the IFT and alter the wettability of rock surfaces. For 3.2 Characterization of surfactant solutions the l -Arg surfactant, a sharp decline in the IFT curve was observed from increasing the concentration to 2000 ppm, In this part, the characteristics of the prepared surfactant wherein the IFT was reduced by about 50%, from 34.5 to solutions (200–10,000 ppm) including conductivity, pH, 18.0 mN/m (red color on Fig. 10). However, when the l - and turbidity were measured to identify the critical micelle Arg concentration increased from 2000 to 10,000  ppm, concentrations (CMC). Figure  8 illustrates the results of only a small decrease in IFT was observed, from 18.0 to conductivity, pH, and turbidity of the l -Arg solutions. As it 16.1 mN/m (about 5% compared with the initial value of can be seen, the optimum values of the CMC from conduc- IFT). tivity, pH, and turbidity were 1700, 1900, and 2200 ppm, The measured values of IFT between kerosene and l - respectively. Although there is a small difference among the Cys solutions (blue solid circles) are also shown in Fig. 10. values of CMC dependent on the three measured properties Although the CMC of l -Cys is higher compared with the of solutions, 2000 ppm was selected as an average effective l -Arg (Figs. 8, 9), its IFT curve shows a similar trend to the value of the CMC for the solution prepared from l -Arg. The l -Arg IFT curve as shown in Fig. 10. Additionally, a sharp measured properties of the l -Cys solutions at different con- reduction in the IFT value was observed from the zero to centrations of 200, 400, 600, 800, 1000, 2000, 4000, 8000, 4000 ppm of l -Cys. From the initial value 34.5 mN/m, the and 10,000 ppm were shown in Fig. 9. From the conductiv- IFT was decreased to 15.4 mN/m at the CMC concentra- ity, pH, and turbidity curves, different values of CMC were tion. Totally, both types of the surfactants demonstrated determined which were 5200, 4400, and 4500 ppm, respec- the same performance in reducing IFT. Shapes of kerosene tively. Accordingly, the concentration of 4500 ppm has been droplets within both l -Arg and l -Cys solutions are illustrated chosen as the effective CMC for the l -Cys solution. in Fig. 11. 3.3 IFT 3.4 Contact angle Figure 10 shows IFT curves of l -Arg and l -Cys solutions. The contact angle values between kerosene and the prepared Surfactant solutions were prepared using different concentra- surfactant solutions of different concentrations are shown tions of the synthesized amino-acid surfactants. The selected in Fig. 12. The measured contact angles (Fig. 12a) between concentrations were 200, 400, 600, 800, 1000, 2000, 4000, kerosene and l -Arg solutions reduced from 144° to 70°. It 8000, and 10,000 ppm. The value of IFT decreased with is also clear that a rapid drop in the value of contact angle an increase in the surfactant concentration, which is simi- occurred with increasing the l -Arg concentration up to lar to the results discussed by Pal et al. (2018) where they 2000 ppm (from 144° to 78°), and this decline continued used a synthesized sodium ethyl ester sulfonate surfactant to 1 3 Petroleum Science (2020) 17:105–117 113 (a) (a) 0 2000 4000 6000 8000 10000 0 2000 4000 6000 8000 10000 L-Arg concentration, ppm L-Cys concentration, ppm 7.0 3.5 (b) (b) 3.0 6.5 2.5 2.0 6.0 1.5 1.0 5.5 0.5 5.0 0 2000 4000 6000 8000 10000 02000 400060008000 10000 L-Cys concentration, ppm L-Arg concentration, ppm (c) (c) 0 2000 4000 6000 8000 10000 0 2000 4000 6000 8000 10000 L-Cys concentration, ppm L-Arg concentration, ppm Fig. 9 CMC determination of the l -Cys solution. a Conductivity. b Fig. 8 CMC determination of the l -Arg solution via different meth- pH. c Turbidity ods. a Conductivity. b pH. c Turbidity very smoothly to 70° at 10,000 ppm concentration. This point, the value of the contact angle changed only slightly. is quite consistent with the descriptions of Mandal et al. Generally, both used surfactants were active in reducing the (2015), wherein they used a mixed Tween 80 and SDBS contact angle and changing the wettability toward water-wet. solution to alter the wettability of quartz rocks. In addition, while using l -Cys solutions, the contact angle between 3.5 Coreflooding kerosene and surfactant solutions decreased gradually and significantly from 144° to 75° at the CMC point (4000 ppm In this study, surfactant solutions were prepared by dis- concentration), as shown in Fig. 12b. While, above the CMC persing the synthesized surfactant in water at different 1 3 Turbidity, NTU pH Conductivity, µS/cm Conductivity, µS/cm pH Turbidity, NTU 114 Petroleum Science (2020) 17:105–117 35 Flooding profiles in Fig.  13 illustrate that an oil recov- L-Arg L-Cys ery of 38.6% OOIP was achieved after injecting 1.6 PV of brine into Plug #1; and a follow-up injection of 1.4-PV l - Arg-2000 solution recovered an additional 11.9% OOIP for a total oil recovery 50.5% OOIP (green and black lines in 20 Fig. 13). However, from Plug #2, 43.7% OOIP was recov- ered by water injection, and an additional 8.9% OOIP was produced by the tertiary flooding of l -Cys-4500, as shown by red and blue lines in Fig. 13. These improvements in oil recovery could be due to the IFT reduction and wettability 010002000300040005000 6000 7000 8000 9000 10000 alteration. Generally, l -Arg-2000 surfactant (11.9% OOIP) Surfactant concentration, ppm provided a better recovery performance than l -Cys-4500 surfactant (8.9% OOIP). This may be due to higher adsorp- Fig. 10 IFT values measured between kerosene and l -Arg and l -Cys tion of the l -Cys-4500 than that of l -Arg-2000 onto the solutions at concentration of 200–10,000 ppm rock surface. concentrations (200–10000  ppm). The CMC for l -Arg and l -Cys surfactants were determined from the results of 4 Conclusions conductivity, pH, and turbidity. The minimum IFTs and contact angles of l -Arg and l -Cys were measured at their In this study, the effects of lauroyl arginine (L-Arg) and CMCs, 2000 and 4500 ppm, respectively. These l -Arg- lauroyl cysteine (L-Cys) surfactants on the IFT reduction, 2000 and l -Cys-4500 solution were selected to be injected wettability alteration and oil recovery were studied. The after water injection (Table 3). For this purpose, two core IFT and wettability were measured using the pendant drop plugs were prepared and their properties are listed in method and the contact angle method, also oil recovery Table 3. was determined by coreflooding tests. The outcomes of this study are summarized as follows: Fig. 11 Shape profiles of kerosene droplets against surfactant solutions 1 3 IFT, mN/m Petroleum Science (2020) 17:105–117 115 Fig. 12 Contact angle between kerosene and a l -Arg and b l -Cys solutions at different concentrations Table 3 Summary of secondary and tertiary flooding Core Porosity, % Perme- Pore volume S ,% Injection fluid Water flooding Surfactant flooding Total oil oi ability, (PV), cm recovery, Oil recovery, S , % Oil recovery, S , % or or mD %OOIP % OOIP % OOIP Plug #1 13.097 10.41 12.74 72.2 l -Arg-2000 38.6 44.3 11.9 35.7 50.5 Plug #2 9.314 7.68 9.08 74.3 l -Cys-4500 43.7 41.9 8.9 35.2 52.6 The contact angle of the carbonate thin section was Water flooding Surfactant flooding decreased slightly more by l -Arg than by the l -Cys sur- factant at CMCs from 144° to 70° and 77°, respectively. • l -Arg surfactant enabled the production of more addi- tional crude oil compared to the l -Cys surfactant at their CMCs. l -Arg-2000 improved oil recovery from 38.6% to Waterflooding I 50.5% OOIP (extra 11.9% OOIP), while it was increased Waterflooding II 10 from 43.7% to 52.6% OOIP (extra 8.9% OOIP) by l -Cys- L-Cys-4500 L-Arg-2000 • Despite obtaining promising results in this study through 0 0.4 0.8 1.2 1.6 2.0 2.4 2.8 getting almost the same performance of l -Arg and l -Cys Pore volume injected surfactants in reducing IFT and altering the wettability, l -Arg was more effective in improving oil recovery com- Fig. 13 Oil recovery profiles of water injection, l -Arg-2000 and l - pared with l -Cys. Cys-4500 flooding into the Asmari core plugs. The green line rep- resents the first brine injection into Plug #1, the red line shows the recovery from the second brine injection into Plug #2, the black line is for the l -Arg solution injection at 2000 ppm into Plug #1 after the Open Access This article is distributed under the terms of the Crea- first brine injection, and the blue line demonstrates the l -Cys solution tive Commons Attribution 4.0 International License (http://creat iveco injection at 4500 ppm into Plug #2 after the second water injection mmons.or g/licenses/b y/4.0/), which permits unrestricted use, distribu- tion, and reproduction in any medium, provided you give appropriate credit to the original author(s) and the source, provide a link to the Creative Commons license, and indicate if changes were made. CMCs of l -Arg and l -Cys solutions were measured to be 2000 and 4500 ppm, respectively, from electrical conductivity, pH, and turbidity measurements. 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Published: Feb 26, 2020

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