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Glycerol carbonate (GC) was synthesized by transesterification of glycerol with dimethyl carbonate (DMC) using calcium oxide (CaO) derived from eggshell as a catalyst. The best results of 96% glycerol conversion and 94% GC yield were achieved under the following reaction conditions: 0.08 mole ratio of CaO to glycerol, 1:2.5 mole ratio of glycerol to DMC, 60 degrees C reaction temperature, and 3 hours reaction time. As expected, CaO showed deteriorated catalytic performance when recycling as observed by a rapid decrease in GC yield. This research showed that the active CaO phase first was converted to calcium methoxide (Ca[OCH3](2)) and calcium diglyceroxide (Ca[C3H7O3](2)) and finally to carbonate phase (CaCO3) which can be confirmed by XRD patterns. According to the phase transformation, the basicity decreased from 0.482 mmol/g to 0.023 mmol/g, and basic strength altered from strong basic strength (15.0 < H_ < 18.4) to weak basic strength (7.2 < H_ < 9.8), resulting in the lower catalytic activity of the consecutive runs. Despite the fact that the GC selectivity was almost 100%, the reaction products (methanol and GC) were not obtained in their stoichiometric ratio and their extents corresponded with that of the catalyst phase transformation to CaCO3. The mechanism of CaO catalyzed transesterification based on the condensation reaction of glycerol and catalyst was proposed, and in situ formation of water-derivative species was hypothesized as a cause of CaO transformation. CaO could react with DMC and water, generating methanol and CaCO3. This enabled unconventional monitoring of catalyst deactivation by checking if the mole ratio of methanol to GC was higher than 2:1 of its reaction stoichiometric ratio. It was also demonstrated that calcination of post-run catalyst at 900 degrees C to CaO exhibited almost constant catalytic activity, and the mole ratio of methanol to GC was constant at its reaction stoichiometry (2:1) for at least 4 times use.

Bonus BaltHealth

Synthesis gas, also known as syngas, produced from biomass materials has been identified as a potential source of renewable energy. Syngas is mainly consists of CO and H2, which can be used directly as fuel source for power generation and transport fuel, as well as feedstock for chemical production. Syngas is produced through biomass gasification process that converts solids to gas phase via thermochemical conversion reactions. This paper critically reviews the type of gasifiers that have been used for biomass gasification, including fixed bed, fluidized bed, entrained flow and transport reactor types. The advantages and limitations of these gasifiers are compared, followed by discussion on the key parameters that are critical for the optimum production of syngas. Depending on the biomass feedstock, the properties and characteristics of syngas produced can be varied. It is thus essential to thoroughly characterise the properties of biomass to understand the limitations in order to identify the suitable methods for gasification. This paper later focuses on a specific biomass – oil palm-based for syngas production in the context of Malaysia, where palm biomass is readily available in abundance. The properties and suitability for gasification of the major palm biomass, including empty fruit bunch, oil palm fronds and palm kernel shells are reviewed. Optimization of the gasification process can significantly improve the prospect of commercial syngas production.