Shelf‐life of biodiesel by isothermal oxidation induction period at variable temperatures

Robert O. Dunn
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Abstract

Biodiesel (fatty acid methyl esters [FAME]) is a renewable biomass‐based diesel (BBD) fuel made from plant oils, animal fats and waste greases. One of the main disadvantages of biodiesel is its poor oxidative stability, which is caused by the presence of high concentrations of unsaturated FAME. When stored in fuel terminals, vehicle tanks and fuel systems, biodiesel can react with oxygen in ambient air, causing it to degrade, which can adversely affect its viscosity and ignition quality. The shelf‐life (SL) of biodiesel is an important property that defines how long it can be stored at low temperatures. The objective of this work is to develop reliable mathematical models to estimate the SL of biodiesel at T = 25°C (298.15 K). This was done by measuring oxidation induction period with a Rancimat instrument (IPR) at variable temperatures. The data were analyzed by linear regression to determine ln(IPR) as a function of T (Model A) and T−1 (Model B) for canola, palm and soybean oil FAME (CaME, PME and SME), methyl oleate (MeC18:1) and methyl linoleate (MeC18:2). Statistical analysis of the Model A and Model B type equations showed that all inferred equations were good fits of the experimental data (adjusted coefficients of determination, R2 ≥ 0.985). The most dependable results were obtained from extrapolation of Model B type equations to predict the SLB values. For CaME, PME, SME and MeC18:1, SLB = 559.0, 1135, 378.3 and 4515 d were inferred. However, the reliability of SLA (extrapolated from its Model A type equation) and SLB values calculated for MeC18:2 (3.1 and 4.8 d) were questionable as estimates of its SL at 298.15 K.
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在不同温度下通过等温氧化诱导期延长生物柴油的保质期
生物柴油(脂肪酸甲酯 [FAME])是一种可再生的生物质柴油(BBD)燃料,由植物油、动物脂肪和废油脂制成。生物柴油的主要缺点之一是氧化稳定性差,这是由高浓度的不饱和脂肪酸甲酯造成的。生物柴油储存在燃料终端、车辆油箱和燃料系统中时,会与环境空气中的氧气发生反应,导致生物柴油降解,从而对其粘度和点火质量产生不利影响。生物柴油的保质期(SL)是一项重要特性,它决定了生物柴油在低温条件下可以储存多长时间。这项工作的目的是建立可靠的数学模型,以估算生物柴油在 T = 25°C (298.15 K)时的保质期。具体方法是使用 Rancimat 仪器(IPR)测量不同温度下的氧化诱导期。通过线性回归分析,确定了油菜籽油、棕榈油和大豆油 FAME(CaME、PME 和 SME)、油酸甲酯(MeC18:1)和亚油酸甲酯(MeC18:2)的 ln(IPR)与 T(模型 A)和 T-1(模型 B)的函数关系。对模型 A 和模型 B 型方程的统计分析表明,所有推断方程都很好地拟合了实验数据(调整后的决定系数 R2 ≥ 0.985)。用模型 B 型方程外推预测 SLB 值的结果最为可靠。对于 CaME、PME、SME 和 MeC18:1,分别推断出 SLB = 559.0、1135、378.3 和 4515 d。然而,从 MeC18:2 的 SLA(根据其 A 型方程推断)和 SLB 值(3.1 和 4.8 d)来估计其在 298.15 K 下的 SL 值,其可靠性值得怀疑。
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