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In-depth understanding of soluble base deactivation during the carbonate transesterification process
Fuel ( IF 6.7 ) Pub Date : 2020-09-19 , DOI: 10.1016/j.fuel.2020.119201
Yue Yu , Lei Shi , Jianjun Guo , Xin Li , Wenbing Yang , Zhigang Zhang , Guangwen Xu

Soluble strong bases such as NaOH or CH3ONa were industrially applied in production of multiple carbonates via the transesterification route. However, the catalytic efficiency decreased significantly after recycling and insoluble solids were formed, leading to a complicated and non-eco-friendly manufacture process. In this study, the influence of Na-based soluble basic catalysts (C4H9ONa, C2H5ONa, CH3ONa, NaOH, Na2CO3, and NaHCO3) structures, amounts, reusability, reaction atmospheres, and different reactants treatment were systematically studied for in-depth understanding the deactivated processes and mechanism. The results indicated dimethyl carbonate (DMC) was responsible for the deactivation and with decreasing the pKb (alkalinity coefficient) value, the alkali strength, nucleophilicity, and catalyst efficiency increased. The properties of fresh, DMC-treated and recycled NaOH or CH3ONa samples were characterized by means of XRD, FT-IR, Raman, TG, and SEM. Nearly all the characterizations proved that the final deactivation species was Na2CO3 after long-time treatment or recycle. A possible deactivation mechanism of soluble bases during the transesterification process was proposed. The presence of trace H2O was the induction of CH3ONa deactivation, whereas the interaction between DMC and NaOH led to the formation of Na2CO3. This finding will contribute to the development of strategies to design homogeneous catalysts with high activity and stability for carbonate transesterification.



中文翻译:

深入了解碳酸盐酯交换过程中的可溶性碱失活

可溶性强碱,如NaOH或CH 3 ONa,已通过酯交换途径工业化用于生产多种碳酸盐。但是,回收后催化效率显着下降,形成了不溶性固体,导致制造过程复杂且不环保。在这项研究中,Na基可溶性碱性催化剂(C 4 H 9 ONa,C 2 H 5 ONa,CH 3 ONa,NaOH,Na 2 CO 3和NaHCO 3的影响系统地研究了其结构,用量,可重复使用性,反应气氛和不同的反应物处理方法,以深入了解失活的过程和机理。结果表明,碳酸二甲酯(DMC)引起了失活,并且随着pK b(碱度系数)值的降低,碱强度,亲核性和催化剂效率得到了提高。通过XRD,FT-IR,拉曼,TG和SEM表征新鲜的,经DMC处理的和循环使用的NaOH或CH 3 ONa样品的特性。几乎所有的表征都证明最终的失活物种是Na 2 CO 3经过长期治疗或回收。提出了一种可能的酯交换过程中可溶性碱失活的机理。痕量H 2 O的存在是CH 3 ONa失活的诱导,而DMC和NaOH之间的相互作用导致Na 2 CO 3的形成。这一发现将有助于开发设计具有高活性和稳定性的均相催化剂的策略,以用于碳酸盐酯交换反应。

更新日期:2020-09-20
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