Mantovani Ana Carolina G, Romagnoli Érica S, Gonçales Filho Jose, Sartor Renan A, Branco Isadora G, Tupan Lilian F S, Valezi Daniel F, Mincache Anuar J, Borsato Dionísio, Angilelli Karina B
Engineering Department, Ingá University Center (Uningá), Rod. PR 317, 6114 Parque Industrial 200, Maringá, PR 87035-510, Brazil.
Chemistry Department - LPAC, State University of Londrina (UEL), Rd. Celso Garcia Cid, Pr 445, Km 380, Londrina, PR 86057-970, Brazil.
ACS Omega. 2025 Aug 16;10(33):37305-37316. doi: 10.1021/acsomega.5c02859. eCollection 2025 Aug 26.
Biodiesel is a renewable and biodegradable alternative fuel, but its susceptibility to oxidative degradation compromises its storage stability and performance. Synthetic antioxidants are commonly used to mitigate this issue. However, there is growing interest in natural antioxidants as sustainable alternatives. This study aimed to investigate the thermal-oxidative degradation of pure biodiesel (B100) and biodiesel with coffee leaf extract (B100E) using H NMR spectroscopy as well as to correlate the iodine value (IV) with NMR spectra and monitor the formation of oxidation products throughout the degradation process. Biodiesel samples underwent accelerated oxidation at 110 °C using the Rancimat method, followed by H NMR analysis to identify oxidation products. The degradation kinetics indicated that linolenate and linoleate compounds were oxidized faster than oleate groups, leading to an increase in the number of saturated compounds. A linear correlation was found between the percentage of olefinic hydrogen atoms from the H NMR spectra and the iodine value determined by the Wijs method. The addition of coffee leaf extract effectively delayed oxidation, as evidenced by the slower appearance of oxidation products and a reduced increase in saturated compounds. These findings highlight a novel and efficient methodology for evaluating biodiesel degradation and unsaturation by combining H NMR analysis with iodine value determination. In addition to enabling a rapid, nondestructive estimation of IV, H NMR also allowed the characterization of different stages of oxidative degradation through the identification and monitoring of specific oxidation products over time.
生物柴油是一种可再生且可生物降解的替代燃料,但其易受氧化降解影响,这损害了其储存稳定性和性能。合成抗氧化剂通常用于缓解这一问题。然而,作为可持续替代品的天然抗氧化剂越来越受到关注。本研究旨在利用核磁共振氢谱(¹H NMR)研究纯生物柴油(B100)和添加咖啡叶提取物的生物柴油(B100E)的热氧化降解情况,并将碘值(IV)与核磁共振谱相关联,监测整个降解过程中氧化产物的形成。生物柴油样品使用Rancimat法在110°C下进行加速氧化,随后进行¹H NMR分析以鉴定氧化产物。降解动力学表明,亚麻酸酯和亚油酸酯化合物的氧化速度比油酸酯基团快,导致饱和化合物数量增加。在¹H NMR谱中烯烃氢原子的百分比与通过韦伊斯法测定的碘值之间发现了线性相关性。添加咖啡叶提取物有效地延迟了氧化,氧化产物出现较慢以及饱和化合物增加减少证明了这一点。这些发现突出了一种通过将¹H NMR分析与碘值测定相结合来评估生物柴油降解和不饱和度的新颖且有效的方法。除了能够快速、无损地估计碘值外,¹H NMR还可以通过随时间识别和监测特定氧化产物来表征氧化降解的不同阶段。