Production of Biodiesel from Waste Cooking Oil using A Zinc-Based Metal-Organic Framework (Zn-MOF) As Catalyst

Okpara Sergeant Bull, Sunday Monsuru Adewale, Eyu Okpa
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Abstract

- Due to fossil fuel diminishing reserves, global warming, and high petroleum prices, there is a need to generate alternative, sustainable, renewable, and biodegradable biodiesel. In this paper, a zinc-based Metal-Organic Framework (Zn-MOF) was solvothermally synthesized, characterized and then used as a catalyst in place of the traditionally used toxic acids and bases as catalysts in biodiesel production. The Zn-MOF was synthesized using zinc nitrate hexahydrate, (ZnNO 3 ) 2. 6H 2 O as the source of metal ion (a Lewis acid), while benzene-1,4-dicarboxylic acid (BDCA) served as a ligand (a Lewis base). A mixture of dimethylacetamide (DMA) and H 2 O (1:1 ratio) functioned as solvent. In a clean and dry beaker, 0.297 g (0.999 mmol) of Zn(NO 3 ) 2. 6H 2 O was completely dissolved in 2 ml of distilled water. In another clean and dry beaker, 0.166 g (0.999 mmol) of BDCA was dissolved in 2 mL of DMA. Then, both solutions were mixed together and then transferred into a Teflon-lined autoclave. The Teflon-lined autoclave containing the mixture was put in an oven and heated at 150 °C for 24 h. After this period, the Zn-MOF was formed as colourless plate crystalline solids. The Zn-MOF remain unmelted even beyond 360 °C. Furthermore, the Zn-MOF was characterized by FTIR and powder X-ray diffraction. The FTIR shows the incorporation of the ligand into the Zn-MOF. The melting point and the powder X-ray diffraction results agree with the properties of MOFs in the literature. After that, the Zn-MOF was used as a catalyst in the transesterification of treated Waste Cooking Oil (WCO) for biodiesel production. The biodiesel was obtained by transesterification process at a temperature of 60 °C using a 1:5 molar ratio of oil to methanol. The biodiesel yield was 96%. The biodiesel diesel produced was physicochemically characterized. The analysis results revealed that the experimentally obtained values for viscosity, density, flashpoint, cloud point and pour point were 4.1 cSt, 821 kg/m³, 170 °C, below 0 °C and 2 °C, respectively. These values, when compared with standards (ASTM), were in agreement. The Zn-MOF recovered and recycled five times without degradation. Hence, it can be said that Zn-MOF is a good catalyst in the transesterification process of biodiesel production and can, therefore, replace the traditionally used toxic acids and bases.
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使用锌基金属有机框架 (Zn-MOF) 作为催化剂从废弃烹调油中生产生物柴油
- 由于化石燃料储量不断减少、全球变暖和石油价格居高不下,人们需要生产可替代、可持续、可再生和可生物降解的生物柴油。本文对一种锌基金属有机框架(Zn-MOF)进行了溶热合成和表征,然后将其用作催化剂,以取代传统上用作生物柴油生产催化剂的有毒酸和碱。Zn-MOF 是以六水硝酸锌 (ZnNO 3 ) 2. 6H 2 O 作为金属离子源(一种路易斯酸),以苯-1,4-二甲酸 (BDCA) 作为配体(一种路易斯碱)合成的。二甲基乙酰胺(DMA)和 H 2 O(1:1 比例)的混合物用作溶剂。在一个干净干燥的烧杯中,将 0.297 克(0.999 毫摩尔)Zn(NO 3 ) 2.在另一个干净干燥的烧杯中,将 0.166 克(0.999 毫摩尔)BDCA 溶于 2 毫升 DMA 中。然后,将两种溶液混合在一起,再转移到特氟龙内衬高压釜中。将装有混合物的特氟龙内衬高压釜放入烤箱中,在 150 °C 的温度下加热 24 小时后,Zn-MOF 形成无色板状结晶固体。即使温度超过 360 °C,Zn-MOF 仍未熔化。此外,Zn-MOF 还通过傅立叶变换红外光谱和粉末 X 射线衍射进行了表征。傅立叶变换红外光谱显示了配体与 Zn-MOF 的结合。熔点和粉末 X 射线衍射结果与文献中的 MOF 特性一致。随后,Zn-MOF 被用作催化剂,用于经处理的废食用油(WCO)的酯交换反应,以生产生物柴油。生物柴油是在温度为 60 ℃、油与甲醇的摩尔比为 1:5 的条件下通过酯交换反应获得的。生物柴油的产量为 96%。对生产的生物柴油进行了物理化学表征。分析结果显示,实验得出的粘度、密度、闪点、浊点和倾点值分别为 4.1 cSt、821 kg/m³、170 °C、低于 0 °C 和 2 °C。这些数值与标准(ASTM)相比是一致的。Zn-MOF 经过五次回收和再循环,没有发生降解。因此,可以说 Zn-MOF 在生物柴油生产的酯交换过程中是一种很好的催化剂,因此可以取代传统使用的有毒酸和碱。
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