Epoxidation of melon seed (Citrullus colocynthis L) oil: A kinetic and thermodynamic approach for industrial applications

Akpoveta V. O., Fasasi M. A., Arigbede, J.
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Abstract

Unsaturated melon seed oil had its epoxidation process studied at varied temperatures (30OC -70OC) within a three hours reaction time, for possible oxirane formation because of its industrial significance. Oil was extracted from melon seeds and characterized for its physicochemical properties using standard methods. The specific gravity (30OC), iodine value, acid value, saponification value, peroxide value and percentage oil content were found as 0.931, 118.69 gI2/100g, 5.08 mg KOH/g, 165.7 mg KOH/g, 4.75 meq/kg and 60% respectively. Physicochemical characteristic of the oil reveals it is semi-drying oil which is rich in high molecular weight fatty acids, with good stability against rancidity. The epoxidation process which was monitored by its oxirane content is seen to proceed faster at the highest studied temperature of 70OC, giving the highest oxirane content of 5.87%. Optimization of the epoxidation process showed that optimum epoxidation of melon seed oil can be achieved at 70OC within one hour; as compared to other temperatures studied. Process kinetics evaluated in terms of its oxirane yield showed that the epoxidation process followed pseudo-zero order kinetics with respect to oxirane formation. Their rate constants were found to be 0.032 hr-1, 0.041 hr-1, 0.059 hr-1 and 0.24 hr-1 for the epoxidation process at 30OC, 50OC, 60OC and 70OC respectively; which shows that the epoxidation rate increases with increasing temperature. Thermodynamic parameters such as activation energy (Ea), activation enthalpy (∆H≠), activation entropy (∆S≠) and Gibb’s free energy (ΔG≠) were determined to be 133.11 kJmol-1, 18.22 kJmol-1, -0.21 kJmol-1 K-1 and 87.95 kJmol-1 respectively. The observed thermodynamic properties indicated strong temperature dependence of the epoxidation reaction rate, endothermicity and non-spontaneity of the process. The findings of this study will guide in maximizing oxirane yield and save cost significantly in the production of epoxidized melon seed oil employed for large scale industrial applications.
瓜籽油的环氧化反应:工业应用的动力学和热力学方法
研究了不饱和瓜子油在不同温度下(30℃-70℃)在3小时反应时间内的环氧化过程,因为它具有工业意义,可能形成氧环烷。以甜瓜籽为原料,采用标准方法对其理化性质进行了表征。比重(30℃)、碘值、酸值、皂化值、过氧化值和百分比含油量分别为0.931、118.69 gI2/100g、5.08 mg KOH/g、165.7 mg KOH/g、4.75 meq/kg和60%。该油的理化性质表明,它是一种富含高分子量脂肪酸的半干性油,具有良好的抗酸败稳定性。以氧环烷含量为监测指标的环氧化过程在最高温度为70℃时进行得更快,氧环烷含量最高为5.87%。环氧化工艺优化表明,在70℃条件下,1小时内可实现瓜子油的最佳环氧化;和其他温度相比。用环氧化反应的氧环烷产率对过程动力学进行了评价,结果表明,环氧化反应的氧环烷生成遵循准零级动力学。在30℃、50℃、60℃和70℃条件下,环氧化反应的速率常数分别为0.032、0.041、0.059和0.24 h -1;结果表明,环氧化速率随温度的升高而升高。热力学参数活化能(Ea)、活化焓(∆H≠)、活化熵(∆S≠)和吉布自由能(ΔG≠)分别为133.11 kJmol-1、18.22 kJmol-1、-0.21 kjmol1 K-1和87.95 kJmol-1。观察到的热力学性质表明,环氧化反应速率、吸热性和非自发性对温度有很强的依赖性。本研究结果将指导环氧化瓜子油在大规模工业应用中最大限度地提高氧环烷产量和显著节省成本。
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