Non-catalytic biodiesel process with adsorption-based refining

摘要

Different feedstocks of varying acidity ranks and water contents were subjected to a series of discontinuous steps that simulated a biodiesel production process. The three steps comprised: (i) the non-catalytic transesterification with supercritical methanol at 280 ℃; (ii) the distillation of the unreacted methanol, water and volatile products: and (iii) the adsorption of the impurities with adequate adsorbents. Refined soy oil. chicken oil and waste cooking oil were subjected to the same simple procedure. The process produced biodiesel complying with the water, acid, glycerides and methyl esters content specifications of the EN 14214 standard. Biodiesel production by the reaction of oils in supercritical methanol at 280 ℃ and methanol-to-oil molar ratios of 15 and 20 produced amounts of glycerol as small as 0.02%. This simplified the subsequent refining of the biodiesel and is considered an advantage over the classic alkali-catalyzed process (that produces 10% of glycerol by-product) because washing steps can be spared. The contents of methyl esters, water and free fatty acids showed a volcano pattern when plotted as a function of the reaction time. In the case of the free fatty acids this was attributed to the initial reaction of water and triglycerides to form acids and glycerol that increased the acidity of the product mixture. At longer reaction times these acids were likely transformed into methyl esters or were decarboxylated to hydrocarbons and CO_2. Water formation was attributed to glycerol decomposition and esterification of free fatty acids. The design of a simple process for biodiesel production using a single reaction step with negligible glycerol production and an adsorption-based refining step was thus studied. A possible scheme integrating reaction, methanol recycling, biodiesel purification and heat recovery was discussed. Advantages and disadvantages of process units were analyzed on terms of operating cost and simplicity.