Transesterification of Production Of Biodiesel

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The direct use of crude vegetable oils in diesel engines is envisageable, but could lead to numerous technical problems. For example, their characteristics (high viscosity, high density, difficulty to vaporize in cold conditions) cause deposits in the combustion chamber, with a risk of fouling and an increase in most emissions (Basha et al., 2009). These drawbacks can be mitigated, but not without some modifications of the diesel engine (Altin et al., 2001). To overcome all these inconveniences, the transformation of microalgae lipids in corresponding esters is essential.

In the transesterification process, a catalyst and an alcohol are added to a blend of microalgae lipids. The reaction reduces the molecular weight, the viscosity and increases the volatility of microalgae lipids. Different parameters can influence the yield of transesterification like the ratio of alcohol-oil, catalyst types and concentration, reaction time, temperature and agitation rate.

Microalgae lipid content
The yield of the transesterification reaction depends on the nature of lipids. For example, monoglycerides like palmitic acid (C16:0) produced a FAME yield of 93% (g FAME /g lipid) while triglycerides like triolein had a yield of 88% (g FAME /g lipid). Furthermore, phospholipids and glycolipids gave a lower yield of 54 to 65% (g FAME /g lipid) and 47 to 56% (g FAME /g lipid), respectively (Nagle & Lemke, 1990). The nature of lipids is an important data for biodiesel production because some microalgae can contain up to 93% (g/g lipid) of phospholipids and glycolipids (Williams & Laurens, 2010). Moreover, some microalgae can also contain lipids such as unsaponifiable lipids carotenoids and other elements (chlorophyll) which are considered as by-products (Bai et al., 2011).

Methanol is the most commonly used alcohol because of its low price. However, other alcohols such as ethanol or butanol can also be employed (Chisti, 2007). In traditional alkalibased catalyst transesterification of vegetable oil, the most used methanol to oil molar ratio for transesterification is 6:1 (Marchetti et al., 2007) even if the stoichiometric value is 3:1 for triglycerides (Berriosa & Skelton, 2008). For microalgae lipids transesterification, the optimal methanol to oil ratio is higher. For example, performing a direct transesterification during 8h at 25˚C, Ehimen et al. (2010) obtained a decrease in the specific gravity (SG) of the biodiesel from 0.8887 to 0.8849 when the molar ratio methanol to oil was increased from 105:1 to 524:1.

Catalysts used for transesterification of microalgae lipids are mainly homogenous or heterogeneous. Another method of transesterification using methanol in the supercritical state (without catalyst) has been developed, but the cost of this technology renders its use impossible to date (Tan & Lee, 2011).

Homogenous alkaline catalysts used for transesterification of vegetable oils mainly include sodium or potassium hydroxide (NaOH or KOH) and sodium or potassium methoxide (CH3ONa or CH3OK)) while homogenous acid-catalysts includes H2SO4, HCl and sulphonic acids (R-SO3H) (Helwani et al., 2009). In industrial vegetable oil biodiesel, homogenous alkali-catalysed transesterification is commonly used because homogenous acid-catalyzed transesterification is around 4000 times slower (Chisti, 2007) and these catalysts (NaOH or KOH) are relatively less expensive (Helwani et al., 2009).

Reaction time, temperature and stirring
Increasing the reaction time has a positive effect on the SG of the biodiesel produced. For example, performing a direct transesterification of Chlorella microalgae at 30˚C with H2SO4 as catalyst, Ehimen et al. (2010) found that the SG decreased from 0.914 to 0.884 when the reaction time was increased from 0.25 to 12h.

The temperature seems to have less effect on the microalgae biodiesel production than reaction time except for high temperatures. For example, Miao & Wu (2006) used H2SO4 catalyst (2.25 mol/L) and found similar biodiesel yield of 56 and 58% (g biodiesel/g lipid) at temperatures of 30 and 50˚C, respectively. At 90˚C, the biodiesel yield dropped of about 38% (g biodiesel/g lipid).

Stirring can have a positive effect on the biodiesel quality. For example, Ehimen et al. (2010) observed a decrease of the SG from 0.9032 (stirring at 500 rpm) to 0.8831 (no stirring).

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