Key Laboratory On Resources Chemicals and Materials of Ministry of Education, Shenyang University of Chemical Technology, Shenyang, 110142, China.
Institute of Industrial Chemistry and Energy Technology, Shenyang University of Chemical Technology, Shenyang, 110142, China.
Sci Rep. 2021 Oct 22;11(1):20931. doi: 10.1038/s41598-021-00323-5.
The activities of various MgO catalysts, which were prepared from different methods such as hydration synthesis, thermal decomposition, combustion, sol-gel and co-precipitation, were conducted in dimethyl carbonate (DMC) synthesis via transesterification of ethylene carbonate with methanol. MgO-P-NaCO-3.14 synthesized by the excess NaCO precipitation compared the best catalytic activity and stability, which could be reused for seven times without obvious deactivation. The DMC yield was as high as 69.97% at 68 °C. The transesterification reaction could be separated into two steps, and the samples obtained by NaOH precipitant exhibited better ring-opening capability, while the catalysts acquired by NaCO precipitant displayed superior transesterification ability. The structure-performance relationship was evaluated by multiple characterization methods. The results indicated that the as-synthesized catalyst derived from dried precursors with more crystalline magnesium carbonate was favorable for the promotion of DMC yield, and MgO-P-NaCO-3.14 with more Mg-O pairs, which were the active center for the transesterification of 2-hydroxyethyl methyl carbonate (HEMC) intermediate with methanol, resulted in more moderately basic sites left that was in accordance with the DMC yield variation. MgO-P-NaCO-3.14 with greater BET surface area and mesopore volume, relative low surface oxygen content and larger moderately basic sites amount compared the excellent activity in DMC synthesis.
采用水合合成、热分解、燃烧、溶胶-凝胶和共沉淀等不同方法制备的各种氧化镁催化剂,在碳酸亚乙酯与甲醇的酯交换合成碳酸二甲酯(DMC)中进行了反应。通过过量的 NaCO 沉淀合成的 MgO-P-NaCO-3.14 表现出最佳的催化活性和稳定性,可重复使用七次而没有明显失活。在 68°C 时,DMC 的收率高达 69.97%。酯交换反应可以分为两步进行,用 NaOH 沉淀剂得到的样品具有更好的开环能力,而用 NaCO 沉淀剂得到的催化剂则具有更好的酯交换能力。通过多种表征方法对结构-性能关系进行了评价。结果表明,由干燥前体合成的具有更多结晶碳酸镁的催化剂有利于提高 DMC 的收率,而 MgO-P-NaCO-3.14 具有更多的 Mg-O 对,这是 2-羟乙基碳酸甲酯(HEMC)中间体与甲醇的酯交换反应的活性中心,导致更多的中等碱性位残留,与 DMC 收率的变化一致。MgO-P-NaCO-3.14 具有更大的 BET 表面积和中孔体积、相对较低的表面氧含量和更大的中等碱性位数量,因此在 DMC 合成中具有优异的活性。