Petroleum Science and Technology ISSN: 1091-6466 (Print) 1532-2459 (Online) Journal homepage: http://www.tandfonline.com/loi/lpet20 Experimental investigation the effect of nanoparticles on micellization behavior of a surfactant: Application to EOR Mohammad-Ali Ahmadi, Zainal Ahmad, Le Thi Kim Phung, Tomoaki Kashiwao & Alireza Bahadori To cite this article: Mohammad-Ali Ahmadi, Zainal Ahmad, Le Thi Kim Phung, Tomoaki Kashiwao & Alireza Bahadori (2016) Experimental investigation the effect of nanoparticles on micellization behavior of a surfactant: Application to EOR, Petroleum Science and Technology, 34:11-12, 1055-1061, DOI: 10.1080/10916466.2016.1148051 To link to this article: http://dx.doi.org/10.1080/10916466.2016.1148051 Published online: 12 Jul 2016 Submit your article to this journal Article views: 19 View related articles View Crossmark data Full Terms & Conditions of access and use can be found at http://www.tandfonline.com/action/journalInformation?journalCode=lpet20 Download by: [University of Exeter] Date: 21 July 2016, At: 11:59 PETROLEUM SCIENCE AND TECHNOLOGY , VOL , NOS –, – http://dx.doi.org/./.. Experimental investigation on the effect of nanoparticles on micellization behavior of a surfactant: Application to EOR Mohammad-Ali Ahmadia , Zainal Ahmadb , Le Thi Kim Phungc , Tomoaki Kashiwaod , and Alireza Bahadorie a Downloaded by [University of Exeter] at 11:59 21 July 2016 Department of Petroleum Engineering, Ahwaz Faculty of Petroleum Engineering, Petroleum University of Technology, Ahwaz, Iran; b School of Chemical Engineering, Engineering Campus, Universiti Sains Malaysia, Seri Ampangan, Nibong Tebal, Penang, Malaysia; c Department of Chemical process and Equipment, Faculty of Chemical Engineering, Hochiminh City University of Technology, Hochiminh City, Vietnam; d Department of Electronics and Control Engineering, National Institute of Technology, Niihama College, Yagumo-cho, Niihama, Ehime, Japan; e School of Environmental Science and Engineering, Southern Cross University, Lismore, Australia ABSTRACT KEYWORDS Chemical stimulation such as surfactant flooding in petroleum reservoirs makes efforts to produce remained oil and improve sweep efficiency by means of different phenomena such as lowering interfacial tension and wettability alteration of reservoir rock Implementing concentration of surfactant through surfactant flooding is one of the big challenges while interfacial tension between surfactant solution and oil after certain concentration involves little changes such as critical micelle concentration (CMC) This article highlights the effect of nanosilica on CMC of Zyziphus Spina Christi, as sugar-based surfactant, in aqueous solutions for enhanced oil recovery and reservoir stimulation purposes A conductivity approach was selected to assess the CMC of the introduced surfactant in aqueous solution at 25°C The influence of nanosilica concentrations on CMC variation of introduced surfactant is considered It is found that CMC of introduced surfactant decreased while the concentration of the nanosilica increased Results from this study can aim in optimum condition selection of surfactant flooding as an enhanced oil recovery ends Critical micelle concentration; enhanced oil recovery; hydrophobic; nanosilia; sugar based surfactant Introduction Surfactant flooding, which is normally classified as a subset of chemical enhanced oil recovery (EOR) methods, has been taken as a solution to enhance the oil displacement sweep efficiency through decreasing the interfacial tension between oil and water (McAuliffe, 1973; Dranchuk et al., 1974; Johnson, 1976; Kalfoglou, 1977; Farouq Ali et al., 1979; Mannhardt et al., 1990; Tsau et al., 2000; Grigg and Svec, 2003; Liu et al., 2007) Dependency of critical micelle concentration (CMC) of Zyziphus Spina Christi (ZSC) to nanosilica is not yet reported in the literature This article focuses on micellization behavior of ZSC in aqueous solutions contain nanosilica CMC measurement of the surfactant was determined via employing a conductivity method for aqueous phase Results from this research are demonstrated and explained in detail in subsequent sections CONTACT Alireza Bahadori alireza.bahadori@scu.edu.au School of Environmental Science and Engineering, Southern Cross University, Lismore,Australia Color versions of one or more of the figures in the article can be found online at www.tandfonline.com/lpet © Taylor & Francis Group, LLC M.-A AHMADI ET AL Downloaded by [University of Exeter] at 11:59 21 July 2016 1056 Figure (a) The image of ZSC observed under TEM (b) The image of nanosilica under TEM PETROLEUM SCIENCE AND TECHNOLOGY 1057 Table Physical properties of nanoparticles Behavior with respect to water Appearance BET-surface area, m /g Average primary particle size, nm Tapped density, g/L SiO , wt% Al O , wt% Fe O , wt% TiO , wt% HCl, wt% AEROSIL AEROSIL R Hydrophilic Fluffy white powder ± ࣙ. ࣘ. ࣘ. ࣘ. ࣘ. Hydrophobic Fluffy white powder ± ࣙ. ࣘ. ࣘ. ࣘ. ࣘ. Downloaded by [University of Exeter] at 11:59 21 July 2016 Reprinted with permission from Mohammad Ali Ahmadi and Seyed Reza Shadizadeh, Adsorption of novel nonionic surfactant and particles mixture in carbonates: Enhanced oil recovery implication, Energy & Fuels, :– Copyright American Chemical Society Experimental 2.1 Surfactant One of the most popular trees in southern of Iran is ZSC According to open literature ZSC contain high concentration of saponins (Kjellim and Johansson, 2010) It should be mentioned here that saponins are natural surface-active substances (surfactants) present in more than 500 plant species and the same as other surfactant have hydrophilic and hydrophobic parts such as triterpenoid or steroid backbone and saccharide residues (Hostettmann and Marston, 1995; Guglu-Ustundag and Mazza, 2007; Stanimirova et al., 2011) Through our research, we implemented extracted brown powder from leaves of ZSC, which contains cyclopeptide alkaloids, as well as, saponin glycosides, and several flavonoids (Hostettmann and Marston, 1995; Guglu-Ustundag and Mazza, 2007; Stanimirova et al., 2011) To achieve main goal of current work, the sugar-based surfactant was extracted from the leaves by spray dryer method while implemented leaves of ZSC were collected from south of Iran (Khuzestan State) and the total extracted powder contains Saponin and Flavonoids In addition, Image under TEM for extracted powder from ZSC leaves are shown in Figure 1a Figure Conductivity versus surfactant concentration Reprinted from Fuel, , M A Ahmadi and S R Shadizadeh, Experimental investigation of adsorption of a new nonionic surfactant on carbonate minerals, –, Copyright , with permission from Elsevier Downloaded by [University of Exeter] at 11:59 21 July 2016 1058 M.-A AHMADI ET AL Figure Effect of PPM of nanosilica on CMC of surfactant 2.2 Nanoparticles To obtain high precise results through this study, ultrapure nanosilica particles in different states were implemented According to wettability of the surface of the silica nanoparticles, they can be classified into two types: hydrophilic silica nanoparticle (NSHI) and hydrophobic silica nanoparticle (NSHO) To assess the referred purpose of this research, AEROSIL R 816 and AEROSIL 200 were carried out as partially hydrophobic and hydrophilic nanoparticles which they were purchase from Degussa Physical properties of AEROSIL R816 and AEROSIL 200 are demonstrated in Table In addition, Image under TEM for hydrophobic nanosilica is illustrated in Figure 1b 2.3 Preparation of Surfactant and Nanoparticle Solution The stock solution of ZSC with concentrations of between 1000 and 80000 mg/L were prepared by dissolving 0.10–8 g of ZSC in 1000 mL deionized water in a volumetric flask These solutions were then diluted to obtain standard solutions containing 1000–80000 mg/L of the ZSC Figure Effect of PPM of nanosilica on CMC of surfactant Downloaded by [University of Exeter] at 11:59 21 July 2016 PETROLEUM SCIENCE AND TECHNOLOGY 1059 Figure Effect of PPM of nanosilica on CMC of surfactant Thickening and thixotropic effects of nanosilica at a given concentration depend to a great extent on the intensity of the dispersing Therefore the dispersion method is of crucial importance As recommended by the producing companies, good results are achieved with ultrasonic homogenizer An ultrasonic homogenizer (UT-1200) has been implemented in this study to disperse the nanosilica particles in the aqueous media The silica powder was weighed, wetted by the dispersing media (i.e., water) and then dispersed using the ultrasonic homogenizer for more than 5–6 h .. CMC Measurement Various routs were carried out to figure out CMC of surfactant in aqueous solution based on different intrinsic characteristic of surface active agent such as surface tension, interfacial tension, thermal conductivity, and electrical conductivity Through this research based on high electrical conductance behavior of introduced surfactant in aqueous solution, electrical conductivity measurement was selected as robust and precise method to determine micellization behavior of introduced surfactant with/without nanoparticles in aqueous solutions To achieve end of this research, various concentration of introduced surfactant was considered in range of 1000–80000 ppm and plots of electrical conductance versus surfactant concentrations for each nanoparticle concentrations were generated It should be noted that a conductivity detector from the Crison Company (EC-GLP 31+ ) was carried out through this research work Electrical conductivity trend for surfactant solution in various concentrations without nanoparticles is illustrated in Figure This critical point should be mentioned here this is necessary to immerse Figure Effect of nanosilica on CMC value of surfactant 1060 M.-A AHMADI ET AL probe of the conductivity meter in solution to guarantee the accuracy and precision of solutions electrical conductance Downloaded by [University of Exeter] at 11:59 21 July 2016 Results and Discussion As known by chemical EOR experts, the value of CMC in surfactant flooding affects the performance of the surfactant flooding in oil reservoirs because as a rule of thumb the amount of required surfactant concentration for injection is two or three times of CMC value Consequently, if CMC of the surfactant is high and cost of surfactant is high, then the performance of surfactant flooding from both an economical and technical point of views is questionable Moreover, the value of CMC also affects the adsorption behavior of surfactant This is another restriction parameter in surfactant flooding because if the adsorption value of surfactant is high the applicability of surfactant is questionable again The changes in CMC with increasing the concentration of hydrophobic nanosilica are shown in Figures 3, 4, and As mentioned previously, turning point in plot of electrical conductivity against surfactant concentration represent CMC of surfactant Here we highlight micellization behavior of ZSC in presence of different nanosilica such as hydrophilic nanosilica and partially hydrophobic nanosilica Conductivity measurements revealed that at constant surfactant concentration, nanosilica presence, either hydrophilic or slightly hydrophobic, had a very small effect on solution conductivity as shown in Figure for ZSC-AEROSIL 200/AEROSIL R816 systems However, it seems that both nanoparticles influence the surfactant micellization properties particularly its CMC As can be seen in Figure 6, coexistence of ZSC and AEROSIL 200 nanosilica in a solution leaded to a CMC value lower that the one for sole ZSC system Figure represents the CMCs of different systems considered in this study, it can be seen that the presence of both nanoparticles have resulted in surfactant molecules to aggregate into micelles at lower concentrations This phenomenon is more severe for higher nanoparticle concentrations The observed phenomenon may be related to surfactant-nanoparticle interactions Ignoring the little amount of surfactant adsorption on nanoparticle surface, the similar negative electrical charge on the surfactant hydroxyl groups and nanoparticle surface results in an electrostatic repulsion between surfactant molecules toward each other and prompts the micellization process Moreover, the hydrophilic nanoparticles make the bulk solution unfavorable for hydrophobic surfactant tails and increase their affinity to form micelles Obviously, in such a situation, micelle aggregates form in lower concentration and CMC is reduced, when nanoparticle concentration increase, the repulsion forces become stronger (due to larger number of nanoparticles) Also, the bulk solution becomes more hydrophilic As a result, micellization occurs even at lower concentrations Another important point that may be inferred from Figure is that the dramatic reduction of CMC is more considerable for hydrophilic AEROSIL 200 nanoparticles As mentioned previously, the presence of these nanoparticles intensifies the hydrophilic characteristics of the solvent As general rule, in aqueous medium, the greater the dissimilarity between the surfactant hydrophobic chain and solvent, the grater the aggregation number Consequently, sharper decrease in CMC value is observed respect to AEROSIL R816 slightly hydrophobic nanoparticles Conclusions Through this research, effects of the addition of different nanosilica particles on the micellization and the micellar growth of ZSC in aqueous solution have been systematically investigated From the results obtained from this work the following conclusion can be drawn: ignoring the little amount of surfactant adsorption on nanoparticle surface, the similar negative electrical charge on the surfactant hydroxyl groups and nanoparticle surface results in an electrostatic repulsion between surfactant molecules toward each other and prompts the micellization process In aqueous medium, the greater the dissimilarity between the surfactant hydrophobic chain and solvent, the grater the aggregation number Consequently, sharper decrease in CMC value is observed respect to AEROSIL R816 slightly hydrophobic nanoparticles PETROLEUM SCIENCE AND TECHNOLOGY 1061 Downloaded by [University of Exeter] at 11:59 21 July 2016 References Ahmadi, M A., and Shadizadeh, S R (2012a) Adsorption of novel nonionic surfactant and particles mixture in carbonates: Enhanced oil recovery implication Energy Fuels 26:4655–4663 Ahmadi, M A., and Shadizadeh, S R (2013) Experimental investigation of adsorption of a new nonionic surfactant on carbonate minerals Fuel 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surfactant: Application to EOR Mohammad-Ali Ahmadia , Zainal Ahmadb , Le Thi Kim Phungc , Tomoaki Kashiwaod , and Alireza Bahadorie a Downloaded by [University of Exeter] at 11:59 21 July 2016 Department... implication Energy Fuels 26:4655–4663 Ahmadi, M A. , and Shadizadeh, S R (2013) Experimental investigation of adsorption of a new nonionic surfactant on carbonate minerals Fuel 104:462–467 Dranchuk,... questionable Moreover, the value of CMC also affects the adsorption behavior of surfactant This is another restriction parameter in surfactant flooding because if the adsorption value of surfactant