• International Journal of Technology (IJTech)
  • Vol 13, No 2 (2022)

Surfactant Production of Methyl Ester Sulfonate from Virgin Coconut Oil using Aluminum Oxide with Microwave Assistance

Surfactant Production of Methyl Ester Sulfonate from Virgin Coconut Oil using Aluminum Oxide with Microwave Assistance

Title: Surfactant Production of Methyl Ester Sulfonate from Virgin Coconut Oil using Aluminum Oxide with Microwave Assistance
Lailatul Qadariyah, Sahiba Sahila, Christiyani Sirait, Christopher P.E. Purba, Donny Satria Bhuana, Mahfud Mahfud

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Cite this article as:
Qadariyah, L., Sahila, S., Sirait, C., Purba, C.P.E., Bhuana, D.S., Mahfud, M., 2022. Surfactant Production of Methyl Ester Sulfonate from Virgin Coconut Oil using Aluminum Oxide with Microwave Assistance. International Journal of Technology. Volume 13(2), pp. 378-388

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Lailatul Qadariyah Chemical Engineering Department, Industrial Technology and Systems Engineering Faculty, Institut Teknologi Sepuluh Nopember, Jl. Teknik Kimia, Keputih, Sukolilo District, Surabaya, 60111, East Java, I
Sahiba Sahila Chemical Engineering Department, Industrial Technology and Systems Engineering Faculty, Institut Teknologi Sepuluh Nopember, Jl. Teknik Kimia, Keputih, Sukolilo District, Surabaya, 60111, East Java, I
Christiyani Sirait Chemical Engineering Department, Industrial Technology and Systems Engineering Faculty, Institut Teknologi Sepuluh Nopember, Jl. Teknik Kimia, Keputih, Sukolilo District, Surabaya, 60111, East Java, I
Christopher P.E. Purba Chemical Engineering Department, Industrial Technology and Systems Engineering Faculty, Institut Teknologi Sepuluh Nopember, Jl. Teknik Kimia, Keputih, Sukolilo District, Surabaya, 60111, East Java, I
Donny Satria Bhuana Chemical Engineering Department, Industrial Technology and Systems Engineering Faculty, Institut Teknologi Sepuluh Nopember, Jl. Teknik Kimia, Keputih, Sukolilo District, Surabaya, 60111, East Java, I
Mahfud Mahfud Chemical Engineering Department, Industrial Technology and Systems Engineering Faculty, Institut Teknologi Sepuluh Nopember, Jl. Teknik Kimia, Keputih, Sukolilo District, Surabaya, 60111, East Java, I
Email to Corresponding Author

Abstract
Surfactant Production of Methyl Ester Sulfonate from Virgin Coconut Oil using Aluminum Oxide with Microwave Assistance

As a surfactant, methyl ester sulfonate (MES) can be produced from virgin coconut oil (VCO) raw materials through the following stages: transesterification, sulfonation, and purification. The transesterification process was carried out to produce methyl esters by reacting VCO with methanol in a mole ratio of 1:41 using a 1% KOH catalyst at a microwave power of 300 W for 60 min. The effects of microwave power and mole ratios between methyl esters and sodium bisulfite in the sulfonation process were investigated. The sulfonation process was carried out using a 1% aluminum oxide catalyst. The purification process was carried out by reacting MES with 35% v/v methanol at 150 W of microwave power for 10 min. The resulting MES was analyzed using gas chromatography and Fourier transform-infrared (FT-IR) spectroscopy. The optimum conditions for surfactant production included a microwave power of 450 W and reactant mole ratio of 1:1, which resulted in a surface tension of 37.9 dyne/cm, pH of 4.21, density of 0.87 g/mL, and viscosity of 3.33 cSt. Based on the FT-IR analysis, the vibrational strain of the sulfonate group was detected at a peak value of 1014.42 for symmetrical S-O and 722.24 cm-1 for asymmetrical S-O.

Methyl ester sulfonate; Microwave; Sulfonation; Transesterification; Virgin Coconut Oil

Introduction

        Surfactants are active ingredients in detergents, personal-care products, pharmaceuticals, mining, and the paper industry. In addition, surfactants have the characterisctic of reducing surface tension so that they can be used as flocculation and wetting agents, adhesives (Singh et al., 2007), the enhancement of oil recovery (Irawan et al., 2017), stabilization of emulsion (Mulligan, 2009), and foam production (Zhang et al., 2017). However, they are still primarily used as synthetic surfactants. Globally, the production of synthetic surfactants has reached 13 million tons/year, and it has been economically profitable. In fact, in 2014, the market research institute Ceresana, Germany, reported that the world market for surfactants has exceeded 33 billion US dollars and that the annual revenue for surfactants is estimated to increase by 2.5% by 2022 (I et al., 2016). Some commonly used synthetic surfactants include cetyltrimethyl ammonium bromide, sodium dodecyl sulfate, and polyoxyethylene sorbitan monolaurate, which are derived from fossil fuel compounds (petrochemicals) (Panda et al., 2020).
  However, most commercial synthetic surfactants still have negative effects on human health and the environment because they are corrosive and toxic. Furthermore, the use of surfactants developed from petrochemical compounds can increase environmental problems, such as global warming, and the shortage of fossil resources (Alwadani & Fatehi, 2018). Thus, it is necessary to replace surfactant raw materials with materials sourced from natural materials (oleochemicals) because they are less toxic and can be more stably decomposed into the environment (Muntaha & Khan, 2015). In addition to the above two factors, global detergent manufacturers have increasingly focused on oleo-based feedstocks, such as surfactants developed from biodegradable vegetable oils, and have used them in enhanced oil recovery (Tulathammakit & Boonyarach, 2014). In fact, biodegradable materials for industrial production have become a research-intensive area due to the increasing demand to conserve limited petrochemical resources and the need to protect the environment from persistent petrochemical products (Soy et al., 2020).
The surfactants have hydrophobic tails and hydrophilic heads that have evolved into nonionic, anionic, cationic, and amphoteric surfactants, and have been widely distributed and used worldwide (Khoshsima & Dehghani, 2016; Rozaini et al., 2012). Based on these four types of surfactants, the most widely used anionic surfactants with active ingredients are derived from carboxylates, phosphates, sulfates, and sulfonates (Alwadani & Fatehi, 2018). In addition, the use of anionic surfactants as bio-based surfactants is less toxic, biodegradable, and compatible with humans and the environment (Adiwibowo & Slamet, 2018).
   Sulfonate-based surfactants can be developed from vegetable oil, with soybean and coconut oils being the most popular raw materials used to derive oleochemical feedstocks, such as fatty alcohol and esters (Hill, 2001). Comparing the two sources, coconut oil has a higher fatty acid content, especially lauric acid (up to 44%–52%) (Sari, 2018). The derivative of the material is usually methyl ester sulfonate (MES), which exhibits suitable surface-active properties, excellent active ingredients as the main ingredients in laundry detergents, and good biodegradability (Tobori & Kakui, 2019).
 Transesterification and subsequent sulfonation are the two main processes involved in developing this surfactant. Sheats and MacArthur (2001) reported that the sulfonation-transesterification process using falling film reactor equipment at a ratio of coconut oil and SO3 of 1:1.2 was able to produce 83.6% methyl ester sulfonate product for a reaction time of 1.5 hours. Jin et al. (2016) produced MES from soybean oil, reused oil, and waste cooking oil (WCO) through the sulfonation process of methyl esters using chlorosulfonic acid reactants for 3 h at 60°C. Methyl ester was produced from WCO with a yield of up to 78%, which is slightly lower than the yield of soybean oil (i.e., 82%) but comparable with that of the reused cooking oil (i.e., 76%). The surface tension value of MES produced from WCO was 32.3 mN/m, which is slightly higher than that of soybean oil (i.e., 31.5 mN/m) but comparable with that of the reused oil (32.6 mN/m) (Jin et al., 2016). Furthermore, similar research was conducted by Slamet and Wulandari (2017), who studied MES manufacture from crude palm oil using a natrium bisulfite (NaHSO3) reactant at 100°C. The optimum conditions for surfactant production included a reactant ratio of 1:1.5 with a sulfonation time of 4.5 h and a surface tension of 35.70 dyne/cm (Slamet & Wulandari, 2017). Several studies that have been conducted with conventional heating suggest that the process completion requires a long time and, thus, a process that is less time-consuming is urgently required.
     Based on these studies, the technology that has recently received considerable attention is the use of microwaves. Ning and Niu (2017) reported that microwaves can spee up the transesterification process by up to 30 times compared to conventional waves. This is because, as compared to conventional technology, microwave reactors produce longer wavelengths that focus directly on the sample; moreover, the reactions use less energy and are less time-consuming. This technology can effectively avoid material aggregation with the long reaction time required by conventional technology (Huang et al., 2020). Therefore, microwave radiation is a suitable method to speed up the reaction and facilitate a more effective heat-transfer process (Motasemi & Ani, 2012).
    Hence, a transesterification–sulfonation microwave process needs to be developed to produce an MES surfactant from virgin coconut oil (VCO). It is also important to investigate parameters such as variation of reactants and microwave power to convert methyl esters to surfactants because no report has explained this so far. Therefore, we study the effect of microwave power (150, 300, 450, and 600 W) and variations in the mole ratios between methyl esters and sodium bisulfite (1:0.6, 1:0.8, and 1:1 (w/w methyl ester)) in producing an MES as a surfactant.

Conclusion

      In this study, an MES surfactant was successfully developed from VCO using the Al2O3 catalyst through the sulfonation process using microwave radiation, which could reduce the sulfonation time. The MES production was affected by the reactant mole ratio and microwave power, where the optimum conditions included a reactant mole ratio of 1:1 and 450 W of microwave power with a viscosity of 3.33 cSt, density of 0.87 gr/cm, surface tension of 37.9 dyne/cm, and pH of 4.21. In addition, the results of the FT-IR analysis suggested that a sulfonate group was present in the sample at the absorption peak of ? = 1020–690 cm-1. Moreover, in the last three years, 3050 papers have discussed this surfactant. This is due to the demerits of synthetic surfactants and the tendency of people to prioritize natural ingredients. Therefore, multidisciplinary research related to MES development is required to review the cost aspect so that a simpler method with a lower cost can be developed. In addition, it is necessary to further review the critical micelle concentration and hydrophilic–lipophilic balance to measure the strength balance of the hydrophilic and lipophilic groups of the surfactants formed. As a renewable and environmentally friendly bio-based anionic surfactant, substantial ongoing efforts are expected in the next few years to build green products and reduce the use of synthetic surfactants.

Acknowledgement

        This study has been thoroughly supported by the research funds from Institut Teknologi Sepuluh Nopember under the project scheme of the Publication Writing and IPR Incentive Program (PPHKI) No. T/2029/IT2/HK.00.01/2021. The authors thank all individuals associated with this research work, especially the Chemical Process Laboratory Crew of the Chemical Engineering Department of Institut Teknologi Sepuluh Nopember.

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