The Synthesis of Dimethyl Carbonate by the Oxicarbonylation of Methanol Over Cu Supported on Carbon Norit

Abstract

The catalytic activity of Norit supported Cu, Ni and Cu-Ni catalysts was investigated in the synthesis of dimethyl carbonate (DMC) by the oxidative carbonylation of methanol. Cu/Norit showed the best catalytic activity. The reaction was carried out in a continuous flow system at atmospheric pressure usually at 393 K. The main products were methyl formate, DMC and CO 2 . The methanol conversion on Cu/Norit achieved in steady state was about 22 % and the DMC yield 13.2 %. Based on the XPS data we can establish that copper reduced to its metallic form during reduction but oxidized in the reaction mixture, and is mostly in the Cu ? state, with some Cu 2? . It is possible that the DMC formation rate depends on the surface concentration of oxidized Cu and on the ratio of Cu ? and Cu 2? . Based upon the IR measurements adsorbed DMC was found on the surface of the Cu/Norit catalyst during the catalytic reaction.

Solid base catalysts derived from Ca-M-Al (M = Mg, La, Ce, Y) layered double hydroxides for dimethyl carbonate synthesis by transesterification of methanol with propylene carbonate

“…Various methods has been developed for the synthesis of DMC, including the oxidative carbonylation of methanol [5,6], the transesterification of methanol with cyclic carbonates [7][8][9][10], the alcoholysis of urea [11][12][13] and direct synthesis from carbon dioxide and methanol [14][15][16]. Among these, the transesterification of methanol with propylene carbonate (PC) is a promising route with the advantages of minimal potential for equipment corrosion, a high degree of safety and good yields [17,18].…”

Greener synthesis of dimethyl carbonate from carbon dioxide and methanol using a tunable ionic liquid catalyst

“…With this in mind we pursued the direct synthesis of DMC from CO 2 and MeOH. Different types of catalysts have been reported in DMC synthesis such as: organotin [6], copper-based catalysts [7], homogeneous and heterogeneous catalysts [8,9], organometallic complexes [10], phosphines [11], organic bases [12], metal oxides [13][14][15], acid-base bifunctional systems [2], zeolite-smectite catalysts [12], and supported organic base catalysts [16]. However, many of these catalytic systems require extreme reaction conditions and produce low yields.…”

Poly(ethylene glycol) based bis-diol as a functional medium for highly efficient conversion of urea and methanol to dimethyl carbonate

“…1,2 Due to a high oxygen content, DMC can be used as a good gasoline octane enhancer. 3 DMC can be produced by the reaction of phosgene with methanol, 4 oxidative carbonylation of methanol, 5,6 oxidative reaction of carbon monoxide and methyl nitrite, 7 transesterification of methanol with cyclic carbonates, which come usually from epoxides. 8 To avoid utilizing toxic, corrosive and explosive reactants, some researchers have tried synthesis of organic carbonate, including DMC from alcoholysis of urea, as shown in eqn (1).…”