Biodiesel with methanol

Biodiesel is a fuel derived from renewable natural resources such as soybean and rapeseed and consists of alkyl esters derived from transesterification of triglycerides with methanol. In spite of all the advantages of biodiesel, such as low emissiotts, biodegradability, non-toxicity, and lubricity, the major hurdle in penetration of biodiesel is its high cost because of the expensive food grade refined vegetable oil feedstock. 

To produce biodiesel, refined vegetable oils are reacted with methanol in the presence of alkali catalysts such as sodium hydroxide, potassium hydroxide, and sodium methylate. The overall base-catalyzed process has several problems that also... 

Biodiesel is a mixture of methyl esters of fatty acids and is produced from vegetable oils by transesterification with methanol (Fig. 10.1). For every three moles of methyl esters one mole of glycerol is produced as a by-product, which is roughly 10 wt.% of the total product. Transesterification is usually catalyzed with base catalysts but there are also processes with acid catalysts. The base catalysts are the hydroxides and alkoxides of alkaline and alkaline earth metals. The acid catalysts are hydrochloride, sulfuric or sulfonic acid. Some metal-based catalysts can also be exploited, such as titanium alcoholates or oxides of tin, magnesium and zinc. All these catalyst acts as homogeneous catalysts and need to be removed from the product [16, 17]. The advantages of biodiesel as fuel are transportability, heat content (80% of diesel fuel), ready availability and renewability. The... 

The transesterification of triglycerides with methanol is a simple and straightforward process. It is commercially practiced worldwide in the production of FAMEs, which have become popular as a replacement for diesel known as biodiesel . The process consists of three separate equilibrium reactions that can be catalyzed by both acids and bases. (4) The overall process is described in Figure 3. Phase separation of the glycerin is the predominant driving force for this process. 

In general, alcohols, such as methanol, ethanol, propanol, butanol, amyl alcohol, etc., can be used with acid-catalyzed transesterifications to obtain high biodiesel yields. " Methanol is preferred due to its low cost and wide availability, but bioderived ethanol would be ideal for the synthesis of a fully biogenerated fuel. On the other hand, the use of heavier alcohols like butanol... 

Alkaline earth metal oxides and hydroxides have also been tested in transesterification reactions. Ca(OH)2 did not show significant catalytic activity in the transesterification of rapeseed oil with methanol at conditions normally used to prepare biodiesel.Peterson et al. reported relative alcoholysis activities of a series of supported CaO catalysts under near reflux conditions of methanol-rapeseed oil mixtures at 6 1 molar ratios.Among the catalysts tested, the most active was CaO (9.2 wt% CaO) on MgO. For instance, in a 12 h reaction the total oil conversion using this catalyst was over 95%, similar to... 

In homogeneous catalysis, the catalyst is in the same phase as the reactants and products. Here we will concentrate on homogeneous catalysis in the liquid phase. In the classic case, the reactant (also called the substrate) molecules and the catalyst are reacted in a solvent. For example, the transesterification of fatty acid triglycerides with methanol (Figure 1.10) is catalyzed by hydroxide (OH-) ions. This is an important process for making fatty acid methyl esters which are then used as biodiesel. 

Biodiesel was prepared in various supercritical alcohol treatments with methanol, ethanol, 1-propanol, 1-butanol, or 1-octanol to study transesterification of rapeseed oil and alkyl esterification of fatty acid at temperatures of 300 and 350°C. The results showed that in transesterification, the reactivity was greatly correlated to the alcohol the longer the alkyl chain of alcohol, the longer the reaction treatment. In alkyl esterification of fatty acids, the conversion did not depend on the alcohol type because they had a similar reactivity. Therefore, the selection of alcohol in biodiesel production should be based on consideration of its performance of properties and economics. 

The products obtained were analyzed for composition using high-performance liquid chromatography (HPLC) (LC -10AT Shimadzu, Kyoto, Japan), which consisted of a column (STR ODS-II, 25 cm in length x 4.6 mm in id Shinwa Chemical, Osaka, Japan) operated at 40°C at a flow rate of 1.0 mL/min with methanol as a carrier solvent. The column was packed with silica particles (5-pm particle diameter and 12-nm pore diameter). The cloud and pour points of the obtained biodiesel were then determined by a mini-cloud/pour point tester (Model MPC-102 Tanaka Scientific, Tokyo, Japan) based on ASTM D2500 for cloud point and ASTM D6749 for pour point (14). 

The addition of cosolvent in combination with supercritical conditions seems to be an efficient means to reduce significantly the operating temperature [4], For example, soybean oil could be converted with methanol into biodiesel with 98% yield by using propane, at least in 0.05 molar ratio to methanol, at 280 °C and 12.8 MPa. Similar results have been reported with C02 in a molar ratio of 0.1 with respect to methanol. In both cases the optimal ratio methanol/oil was 24 and residence time of 10min [5]. 

Santacesaria, E., Tesser, R., Di Serio, M., Guida, M., Gaetano, D., Garcia Agreda, A. 2007. Kinetics and mass transfer of free fatty acids esterification with methanol in a tubular packed bed reactor a key pretreatment in biodiesel production. Ind. Eng. Chem. Res., 46, 5113-5121. 

The conventional method of preparing biodiesel is an alkaline catalysed transesterification reaction of refined vegetable oils with methanol to produce biodiesel according to E.U. (EN14214) or U.S. (ASTM D6751) standards. 

Water is added in a 20% weight ratio and the mixture is stirred for 15 minutes, after which the water layers are separated. The FAME layer is washed with water until neutral, then dried and distilled at 200-220 °C/10mbar resulting in a biodiesel of excellent quality. From the residue, sterols can be isolated by trituration with methanol. Technologies are available to isolate tocopherols from the residue but are not performed in this study. 

FIGURE 10.3 Methyl biodiesel production by conventional tiansesterification of seed oil with methanol. 

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