Application of henna extract in minimizing surfactant adsorption on quartz sand in saline condition: A sacrificial agent approach
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This study examined the adsorption ability of henna extract as an environment-friendly and accessible sacrificial agent. In this study, the Fourier transform infrared-attenuated total reflectance (FTIR-ATR) was used to characterized henna extract and quartz sand. The adsorption of the henna extract on quartz sand was executed using the ultraviolet–visible spectroscopy (UV–Vis). The current study also assesses the effects of salinity on the henna extract adsorption on quartz sand, and the mechanisms of the adsorption process were interpreted. Apart from that, the ability of henna extract in reducing the adsorption of surfactant in the presence of salts were recorded. The outcome demonstrated that henna extract adsorption on quartz sand increased with the increase of salinity concentrations. Note that the adsorption value increased from 3.14 to 8.11 mg/g in 0 and 50,000 mg/L of salinity, respectively. The main mechanisms involved in the adsorption process were hydrogen bond, hydrophobic interactions, and electrostatic attractions. A reduction of 46% of surfactant adsorption was observed. This was a profound decrease in the adsorption of surfactant in the presence of henna extract, suggesting a possibility to be utilized as a sacrificial agent in reducing surfactant adsorption.
KeywordsHenna extract Surfactant Quartz sand Adsorption Salinity
Surfactant flooding has been a vital part in enhanced oil recovery (EOR). This method is used to reduce the interfacial tension (IFT) of oil and water to improve the displacement efficiency through oil recovery . Nevertheless, the surfactant adsorption on reservoir rock may impact the deprivation of the concentration of the surfactant, which may yield them less productive and competent .
The issues of the adsorption phenomenon of surfactants spark interests in lessening the adsorption of surfactant on reservoir rocks. Investigations on the implementation of similarly charged surfactant on the same surface charge of rock demonstrated that the anionic surfactant adsorption decreased on sandstone. The studies also concluded that the adsorption of cationic surfactant decreased on carbonate because of the repulsion of electrostatic between the adsorbent and the type of surfactants used [3, 4]. However, because of the heterogeneity of the reservoir especially with the diversity of minerals including carbonate, aluminates, silicates, and various clays, it is hard to determine either anionic or cationic surfactants to be used.
Besides that, alkali as additives has been used to lower the adsorption of surfactants  and the mechanism of which was considered as changing the surface charge on the rock surface. However, the usage of alkali induces such problems such as severe scaling in the near wellbore and production systems .
Following the research, the application of a sacrificial agent (SA) is deemed to be a promising method in reducing surfactant adsorption. The SA is a material that is injected to significantly inhibit or conceal all probable adsorption sites of the rock within the hydrocarbon formation. Weston et al.  have found that the formation of admicelles on the solid surface by the molecules of surfactant is the primary reason for adsorption to occur. The SA is strategically implemented to inhibit the development of these admicelles. ShamsiJazeyi et al.  in their work announced that polyelectrolyte had been proved to lessen adsorption of anionic surfactant on carbonates and clays minerals. In addition, surfactant adsorption was successfully reduced after the addition of the SA.
However, the materials used in reducing surfactant adsorption were chemicals which may be hazardous to living creatures and environment. Thus, materials that are eco-friendly, fewer impurities and simply accessible and are found from natural products, for instance, plant extracts that can act as an SA or inhibitor are being researched.
In this research, henna, a natural plant-based material was investigated as a potential SA. Henna is also known as Lawsonia inermis L. This substance has been implemented as a corrosion inhibitor [9, 10] and Moslemizadeh et al.  revealed that henna extract can reduce the swelling of sodium bentonite better than exposing sodium bentonite to polyamine and potassium chloride due to its inhibitive capability. Apart from that, several researchers conducted inclusive studies on the effect of various parameters on the adsorption of surfactant, especially regarding the influence of added salts. Bera et al.  observed that the adsorption of surfactant magnifies with the increased of NaCl concentration while, ShamsiJazeyi et al.  found that by increasing the salinity of Na+ ions, the adsorption of surfactant will simultaneously increase too. As indicated by Yekeen et al. , the degree of the adsorption of surfactant on reservoir rocks relies mostly on the electrolytes and the mineralogical composition of the rocks. Nevertheless, there is an absence of detailed knowledge on the application of henna extract as a SA in reducing surfactant adsorption in the vicinity of salts. Furthermore, the mechanisms of adsorption of the henna extract on quartz sand are still not well-understood by scholars.
This study was driven by the desire to comprehend the adsorption behavior of the henna extract on quartz sand and its ability in reducing surfactant adsorption with the influence of salinity. To reach this aim, the mechanisms of the adsorption process were analyzed. This study aimed to validate the notion that henna extract could be used as a SA in minimalizing surfactant adsorption.
2 Materials and methods
Fresh henna leaves were gathered from henna trees in Johor, Malaysia. Methanol of 99.9% (Acros Organics (USA)) was used as the solvent in methanolic extraction. The anionic surfactant, sodium dodecyl sulfate (SDS) of 98% purity weighing 288.38 g/mol of molecular weight and manufactured by Fisher Chemical (UK) was used for the surfactant adsorption. Sodium chloride, NaCl (99.8% pure) provided by Vchem was used to study the effect of salinity, and quartz sand used in the experiment was collected in Desaru, Johor, Malaysia. Deionized water (DIW) was used for all experiments. All substances used in this study were of scientific quality and were used as acquired; in other words, devoid of added purifications.
2.2 Preparation of henna powder
The fresh leaves of henna were dried at room temperature and then grounded into powder using an electric blender. The henna powder was carefully packed in an airtight, BPA-free container and stored in room temperature until further used.
2.3 Characterization of henna extract and quartz sand
2.3.1 FTIR-ATR analysis
The FTIR-ATR was conducted using the Perkin Elmer FTIR Spectrometer (USA). Meanwhile, the functional groups of henna extract and quartz sand were identified using the spectrometer by observing the vibrational motion of bonds in the molecules. The spectra were measured in the range of 650–4000 cm−1 with a scan resolution of 2 cm−1. The FTIR data were documented in the transmittance mode. Then, the pattern of the spectrum was examined and compared to the IR absorption table to determine the functional groups encompassed in the samples.
2.3.2 XRD analysis
The quartz sand sample was further characterized by using the X-ray diffraction (XRD) in the continuous scanning mode on SmartLab X-Ray Diffractometer (Rigaku, Japan) operated at 40 kV and a current of 30 mA with Cu–Kβ filter and Cu–Kα radiation source (λ = 0.154056 nm). Particle size ought to be fine to attain a tolerable statistical representation of the components and their numerous diffracting crystal planes and to evade diffraction-related artifacts . All the patterns were collected at room temperature with steps of 0.02° in the 2θ range of 3°–100°. The measurements were taken at room temperature with a scan rate of 8.2551° per minute.
2.4 Preparation of henna extract and surfactant solutions
The solutions of henna extract were prepared in standard 250 ml Erlenmeyer flasks. The henna extract was weighed and transferred into the flasks, and the DIW water was added to the required volume. Henna extract concentrations were prepared in the range of 3000–8000 mg/L. It should be noted that the surfactant solutions were prepared similarly as henna extract solutions. Different concentrations of surfactant were prepared in the range of 1000–5000 mg/L. The influence of salinity on henna extract adsorption was determined by preparing different henna extract solutions using NaCl at concentrations 10,000, 30,000, and 50,000 mg/L.
2.5 Ultraviolet–visible spectroscopy (UV–Vis)
UV–Vis measurement was performed to determine the maximum absorption wavelength of henna extract and surfactant. Besides that, it is also used to compute the concentration of henna extract and surfactant before and after adsorption using Shimadzu UV-1800 Spectrophotometer (Japan). The absorbance–wavelength between 200 and 800 nm was recorded. Quartz cuvettes were used as the vessel.
2.6 Adsorption experiments
3 Results and discussion
3.1 Characterization of henna extract and quartz sand
3.1.1 FTIR analysis
3.1.2 XRD analysis
3.2 Ultraviolet–visible spectroscopy (UV–Vis)
The wavelength of henna extract and surfactant were determined at 673 nm and 238 nm respectively, which corresponds to the maximum absorbance peak. Standard calibration curves were established by plotting absorbance against henna extract and surfactant concentrations to determine the final adsorption concentrations.
3.3 Adsorption experiments
3.3.1 FTIR-ATR analysis on the adsorption of henna extract on quartz sand
3.3.2 Effect of salinity on the adsorption of henna extract on quartz sand
From the figures, it can be noted that the increasing salinity from 10,000 to 30,000, and 50,000 mg/L, improved the adsorption of henna extract on quartz sand. Adsorption of henna extract on quartz sand increased from 4.48 to 6.65, and to 8.11 mg/g in the presence of 10,000, 30,000, and 50,000 mg/L of NaCl, respectively. Comparable results were attained by Yekeen et al. , who also mentioned that the adsorption increased with the increase of the concentration of salt, in the presence of NaCl salts.
In addition, the effect of salinity on henna extract adsorption on quartz sand can be attributed to the positive cations (Na+). These cations were attracted to the permanently negative- charged sites (silanol sites, Si–O) on quartz sand surfaces . Therefore, an increase in the adsorption of henna extract with increasing salinity implies that increasing salinity reduces the negatively-charged sites on the quartz sand surface, increasing henna extract adsorption . Then, the negatively-charged groups from henna extract molecules can bind more to these positively charged surface on quartz sand due to the electrostatic forces.
3.3.3 Influence of salinity on the adsorption of surfactant on quartz sand without the presence of henna extract
As displayed in Fig. 11, surfactant adsorption on quartz sand increased from 1.57 to 5.16 mg/g from DIW to saline solutions. These remarks are due to cation being adsorbed on the negatively-charged quartz sand surface, producing additional positive sites for the anionic surfactant to adsorb . Furthermore, the added salt in the solutions made the EDL and zeta potential of the quartz sand surface to compress, allowing more surfactant to be adsorbed [39, 40].
3.3.4 Influence of salinity on the adsorption of surfactant on quartz sand with the presence of henna extract
It is shown that the adsorption of surfactant on pre-treated quartz sand was reduced in the presence of NaCl from 5.16 mg/g to 2.77 mg/g. The reduction of surfactant adsorption was about 46%. The reduced surfactant adsorption on the pre-treated quartz sand with henna extract can be attributed to the presence of cation (Na+). Based on the mechanism discussed above, the cation allows the henna extract molecules to adsorb more, providing less binding option for surfactant molecules to bind to the surface of quartz sand and henna extract molecules. This made the surfactant molecules free to move, reducing surfactant adsorption.
The existence of the functional groups in henna extract, hydroxyls, carbonyls, phenolics, aromatic benzene ring, and aliphatic carbon-hydrogen groups allow for the adsorption process. Quartz sand was characterized and used as an adsorbent to investigate the effect of salinity on henna extract adsorption on quartz sand and to evaluate the performances of henna extract as a SA in reducing surfactant adsorption. The presence of salt improved the adsorption of henna extract on quartz sand, and increasing the salinity further improved the adsorption. Meanwhile, the electrostatic interactions played a substantial role as perceived from the role of a cation such as sodium (Na+). The study of surfactant adsorption was done to determine the efficiency of the henna extract adsorption. This was determined by analyzing the results of before-and-after adsorption values of surfactant adsorption on quartz sand. The salinity demonstrated that the surfactant adsorption exhibited identical traits of adsorption with the henna extract adsorption process. This follows that the adsorption of surfactant on quartz sand increased in the existence of salts rather than in the absence of salts. Moreover, the adsorption of surfactant on pre-treated quartz sand with henna extract in the presence of salts managed to be reduced. It was observed that there was a 46% reduction, caused by the electrostatic attractions between henna extract and quartz sand. The surface of quartz sand was covered with henna extract molecules, inhibiting the surfactant molecules from being adsorbed. Hydrogen bond, electrostatic attraction, and hydrophobic interactions played a significant role in the mechanism of adsorption between henna extract and quartz sand. This study proved that henna extract has the potential to be a SA in reducing surfactant adsorption in the presence of salts.
The authors wish to thank the Ministry of Higher Education (MOHE), Malaysia, and Universiti Teknologi Malaysia for assisting this research through Fundamental Research Grant Scheme (R.J130000.7846.4F931) and Research University Grant (12429).
Compliance with ethical standards
Conflict of interest
On behalf of all authors, the corresponding author states that there is no conflict of interest.
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