Dialkyl carbonates are important organic compounds and chemical intermediates with the label of “green chemicals” due to their moderate toxicity, biodegradability for human health and environment. Indeed, owing to their unique physicochemical properties and versatility as reagents, a variety of phosgene-free processes derived from CO or CO2 have been explored for the synthesis of dialkyl carbonates. In this critical review, we highlight the recent achievements (since 1997) in the synthesis of dialkyl carbonates based on CO and CO2 utilization, particularly focusing on the catalyst design and fabrication, structure–function relationship, catalytic mechanisms and process intensification. We also provide an overview regarding the applications of dialkyl carbonates as fuel additives, solvents and reaction intermediates (i.e. alkylating and carbonylating agents). Additionally, this review puts forward the substantial challenges and opportunities for future research associated with dialkyl carbonates.

Recent advances in dialkyl carbonates synthesis and applications.

This review summarizes the state-of-the-art for direct synthesis of dimethyl carbonate (DMC) from carbon dioxide and methanol. In addition, conventional and alternative processes are also discussed in order to understand the advantages and disadvantages of the direct synthesis of DMC. Furthermore, the major applications of DMC are described: solvent, fuels additive, and building block for organic synthesis. The major drawbacks of the direct synthesis of DMC are the low yield and reaction rate, mostly induced by the highly stable carbon dioxide molecules. The development of novel catalyst and strategies to enhance the DMC yield – such as dehydrating agents that remove the water from the reacting mixture – are pointed out as the key solution for this route. Therefore, the main catalysts (homogeneous and heterogeneous catalysts) used so far are presented, together with the respective operating conditions and catalyst performance. The use of different dehydrating agents to increase the DMC yield is also discussed.

Review for the Direct Synthesis of Dimethyl Carbonate

Synthesis of diethyl carbonate by catalytic alcoholysis of urea

Organic carbonates are green compounds with a wide range of applications. They are widely used for the synthesis of important industrial compounds including monomers, polymers, surfactants, plasticizers, and also used as fuel additives. They can be divided into two main classes: cyclic and linear carbonates. Dimethyl carbonate (DMC) and diethyl carbonate (DEC) are the important linear carbonates. Carbonyl and alkyl groups present in DMC and DEC make them reactive and versatile for synthesizing various other important compounds. Ethylene carbonate (EC), glycerol carbonate (GC) and propylene carbonate (PC) are well-known cyclic organic carbonates. Phosgenation of alcohols was widely used for synthesis of organic carbonates; however, toxicity of raw materials restricted use of phosgenation method. A number of new non-phosgene methods including alcoholysis of urea, carbonylation of alcohols using CO2, oxy-carbonylation of alcohols, and trans-esterfication of alcohols and carbonates have been developed...

Synthesis of organic carbonates from alcoholysis of urea: A review

The aim of this work is to review different synthesis methods of dialkylcarbonates with special emphasis on diethyl carbonate synthesis methodologies. The novel synthesis route for dimethyl carbonate and diethyl carbonate based on the utilization of alcohol and carbon dioxide as the raw materials, together with heterogeneous catalysts, is presented.

Conventional synthesis methods of short-chain dialkylcarbonates and novel production technology via direct route from alcohol and waste CO2

A new process was proposed for the synthesis of dimethyl carbonate (DMC) from urea and methanol in a batch operation. Polyphosphoric acid (PPA) was used as the catalyst and the absorbent for the ammonia, which was produced during the reaction. The effects of various operation conditions, such as reaction temperature, pressure, reaction time and the molar ratio of the reactants were investigated in the terms of DMC yield. The experimental results indicated that the optimal reaction conditions were the molar ratio of methanol/urea of 14, reaction time of 4 h, reaction temperature of 413 K, PPA/urea mass ratio of 1 and initial pressure of CO2 of 0.8 MPa, respectively. The DMC yield of 67.4% was obtained in the optimal reaction conditions. The by-product, ammonia was also used as a starting material of a useful fertilizer in the proposed process.

Synthesis of dimethyl carbonate from urea and methanol using polyphosphoric acid as catalyst

Synthesis of dimethyl carbonate from urea and methanol catalyzed by the metallic compounds at atmospheric pressure

Reactive rectifying for producing dimethyl carbonate

Novel process for synthesis of 1,1,3,3-tetrabutyl-1-methoxy-3-isocyanatodistannoxane

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Synthesis of dimethyl carbonate from urea and methanol using polyphosphoric acid as catalyst

Synthesis of dimethyl carbonate from urea and methanol catalyzed by the metallic compounds at atmospheric pressure

Reactive rectifying for producing dimethyl carbonate

Novel process for synthesis of 1,1,3,3-tetrabutyl-1-methoxy-3-isocyanatodistannoxane