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寡聚物催化剂:用于生物柴油合成的低聚酯作为准均相催化剂

Oligocat: Oligoesters as Pseudo-Homogenous Catalysts for Biodiesel Synthesis.

作者信息

Vlnieska Vitor, Muniz Aline Silva, Oliveira Angelo Roberto Dos Santos, César-Oliveira Maria Aparecida Ferreira, Kunka Danays

机构信息

Chemistry Department, Federal University of Paraná (UFPR), Rua Coronel Francisco Heráclito dos Santos 100, Jardim das Américas, Curitiba 81531-980, PR, Brazil.

Swiss Federal Laboratories for Materials Science and Technology (EMPA), Überlandstrasse 129, 8600 Dubendorf, Switzerland.

出版信息

Polymers (Basel). 2022 Jan 5;14(1):210. doi: 10.3390/polym14010210.

Abstract

Biodiesel production from first-generation feedstock has shown a strong correlation with the increase in deforestation and the necessity of larger areas for land farming. Recent estimation from the European Federation for Transport and Environment evidenced that since the 2000s decade, an area equal to the Netherlands was deforested to supply global biodiesel demand, mainly originating from first-generation feedstock. Nevertheless, biodiesel is renewable, and it can be a greener source of energy than petroleum. A promising approach to make biodiesel independent from large areas of farming is to shift as much as possible the biodiesel production chain to second and third generations of feedstock. The second generation presents three main advantages, where it does not compete with the food industry, its commercial value is negligible, or none, and its usage as feedstock for biodiesel production reduces the overall waste disposal. In this manuscript, we present an oligomeric catalyst designed to be multi-functional for second-generation feedstock transesterification reactions, mainly focusing our efforts to optimize the conversion of tallow fat and sauteing oil to FAME and FAEE, applying our innovative catalyst. Named as Oligocat, our catalyst acts as a Brønsted-Lowry acid catalyst, providing protons to the reaction medium, and at the same time, with the course of the reaction, it sequesters glycerol molecules from the medium and changes its physical phase during the transesterification reaction. With this set of properties, Oligocat presents a pseudo-homogenous behavior, reducing the purification and separation steps of the biodiesel process production. Reaction conditions were optimized applying a 4 factorial planning. The output parameter evaluated was the conversion rate of triacylglycerol to mono alkyl esters, measured through gel permeation chromatography (GPC). After the optimization studies, a conversion yield of 96.7 (±1.9) wt% was achieved, which allows classifying the obtained mono alkyl esters as biodiesel by ASTM D6751 or EN 14214:2003. After applying the catalyst in three reaction cycles, Oligocat still presented a conversion rate above 96.5 wt% and as well an excellent recovery rate.

摘要

第一代原料生产生物柴油已显示出与森林砍伐增加以及更大面积土地耕种的必要性之间存在强烈关联。欧洲运输与环境联合会最近的估计表明,自21世纪以来,相当于荷兰面积的区域被砍伐森林,以满足全球生物柴油需求,主要源于第一代原料。然而,生物柴油是可再生的,并且它可能是比石油更环保的能源来源。使生物柴油独立于大面积耕种的一种有前景的方法是尽可能将生物柴油生产链转向第二代和第三代原料。第二代具有三个主要优点,即它不与食品工业竞争,其商业价值可忽略不计或没有,并且其作为生物柴油生产原料的使用减少了总体废物处理。在本论文中,我们展示了一种设计用于第二代原料酯交换反应的多功能低聚物催化剂,主要致力于优化牛脂和煎炸油转化为脂肪酸甲酯(FAME)和脂肪酸乙酯(FAEE)的转化率,应用我们的创新催化剂。我们的催化剂名为Oligocat,它作为布朗斯特 - 劳里酸催化剂,向反应介质提供质子,同时在反应过程中,它从介质中螯合甘油分子,并在酯交换反应期间改变其物理相。凭借这组特性,Oligocat呈现出准均相行为,减少了生物柴油工艺生产的纯化和分离步骤。应用4因子规划优化反应条件。评估的输出参数是通过凝胶渗透色谱法(GPC)测量的三酰甘油向单烷基酯的转化率。经过优化研究,实现了96.7(±1.9)wt%的转化率,这使得所获得的单烷基酯可根据ASTM D6751或EN 14214:2003归类为生物柴油。在三个反应循环中应用该催化剂后,Oligocat仍呈现出高于96.5 wt%的转化率以及优异的回收率。

https://cdn.ncbi.nlm.nih.gov/pmc/blobs/1f03/8747590/a4085aac751c/polymers-14-00210-g001.jpg

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