Efficient Synthesis of Dimethyl Carbonate via Transesterification from Ethylene Carbonate with Methanol Using KAlO₂/γ‐Al₂O₃ Heterogeneous Catalyst

Abstract

Dimethyl carbonate (DMC) is an important environmentally‐friendly organic compound. The need for efficient synthesis of DMC has given a fillip to search for new catalysts and their cost‐effective preparation. In this work, a series of KAlO2/γ‐Al2O3 heterogeneous catalysts were rapidly prepared by impregnation method. These catalysts were characterized by FTIR, XRD, XPS, TG‐MS, ICP‐OES, BET and Hammett acid‐base titration and tested for the synthesis of DMC via transesterification from ethylene carbonate (EC) with methanol. The results demonstrated that KAlO2, as the active species, was produced in large quantities during the calcination process. The catalyst with a calcination temperature of 700 °C and a K2CO3 loading of 45 wt % exhibited the best catalytic activity. The optimum conditions for the process resulted in a catalyst amount of 1.0 wt %, a reaction temperature of 100 °C and a reaction time of 80 min, in which the EC conversion and DMC selectivity were 80.2 % and 98.9 %, respectively. In addition, the TON, TOF and reaction rate were 80.3, 61.2 h−1 and 3.91 gDMC⋅gcat−1⋅min−1. The reusability of the catalyst with best catalytic activity was also studied.

Effect of Cobalt Doping on the Stability of CaO‐Based Catalysts for Dimethyl Carbonate Synthesis via the Transesterification of Propylene Carbonate with Methanol

“…In addition, DMC is also widely used as a fuel oil additive due to its high oxygen content (53 %) [4] and employed as a key solvent in the synthesis of commodity polymers [5] . There are several routes for producing DMC, such as the oxidative carbonylation of methanol, [6] direct synthesis from CO 2 and methanol, [7,8] methanolysis of urea, [9] and transesterification of cyclic carbonate (propylene carbonate or ethylene carbonate) with methanol [10,11] . Therefore, DMC synthesis via the transesterification of propylene carbonate (PC) with methanol under mild conditions is a clean catalytic route eliminating the use of toxic and corrosive reagents and is recognized as a promising and environmentally benign route for DMC.…”

On-Line Thermally Induced Evolved Gas Analysis: An Update—Part 1: EGA-MS

“…A series of KAlO 2 /γ-Al 2 O 3 heterogeneous catalysts were prepared and characterized by spectroscopic techniques, TG-MS, ICP-OES, BET, and Hammett acid-base titration and tested for the synthesis via transesterification from ethylene carbonate with methanol. EGA was especially helpful during the calcination process [ 63 ]. Ionic liquids were investigated to provide relevant information on the thermal behavior [ 64 ].…”

Shape‐Dependent Basicity of Nanoscale La2O2CO3 Catalysts in the Dimethyl Carbonate Synthesis from Propylene Carbonate with Methanol

“…Additionally, it is also a carbonylation and methylation agent to replace phosgene, dimethyl sulfate and other highly toxic reagents because of its environmentally friendly features [1] . Various routes have been employed to synthesize DMC, including the phosgenation of methanol, [2] the oxidative carbonylation of methanol, [3] the transesterification of cyclic carbonates with methanol, [4] the methanolysis of urea [5] and the direct synthesis of DMC from methanol and CO 2 , [6] have been intensively studied. Among these routes, transesterification of propylene carbonate (PC) with methanol, an environmentally and effective benign alternative process to produce DMC (Scheme 1), recently receives significant attention due to higher reactivity, mild reaction conditions and equipment without corrosion [7] .…”