Sustainable Auto-Oxidation of Glucose to Ethyl Formate in Ethanol: Pathways for Hydrogen Storage and Future Energy Applications through Formic Acid Derivatives
Abstract
Formic acid, as the simplest carboxylic acid, holds significant potential as a hydrogen carrier due to its high storage efficiency and ease of transport. Its sustainable production from renewable feedstocks, such as glucose, offers promising prospects, particularly for resource-rich countries like Indonesia. Previous studies have demonstrated the feasibility of producing formic acid by oxidizing glucose with hydrogen peroxide, which can be generated directly from air in water via manganese (Mn)-catalyzed oxidation, thereby circumventing harmful Fenton reactions. In this context, copper (Cu⁺) and manganese (Mn²⁺) ions have been recognized as effective catalysts for this oxidation process. This study investigates the auto-oxidation of glucose into formic acid or ethyl formate, employing air as the oxidant and Cu(II)-Mn(II) acetate as the catalytic system. The experimental variables included the Cu:Mn ratios (1:10 and 1:20), the Mg:Cl ratios in the drying agents, specifically magnesium chloride (MgCl₂) and calcium chloride (CaCl₂), in proportions of 1:1 and 1:2, and the %TEOA volume as the chelating agent. The primary objective was to assess the effects of these variations on ethyl formate yield. In the experimental setup, glucose was combined with the catalytic mixture, amine, drying agents, and a base in ethanol. Air was injected into the system, and the mixture was distilled to approximately 78°C. Titrimetric analysis revealed that the optimal reaction conditions were achieved with a Cu:Mn ratio of 1:10, a Ca:Mg ratio of 1:1, and a 50 % volume of TEOA, resulting in a 4.32% yield of ethyl formate after 2.5 hours of reaction time. These findings underscore the potential for efficiently and sustainably producing ethyl formate or formic acid via a green catalytic oxidation process.
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