Biodiesel is made by reacting triglycerides (the chemicals in oils and fats) with an alcohol.
The
chemical reaction is known as transesterif ication. In transesterif ication of oils and/or fats, which
are the glycerol esters of fatty acids (figure 2), the glycerol needs to be transesterified by
another alcohol, most commonly methanol. The three fatty acids (R1 , R2 , and R3 ) react with
the alkyl groups of the alcohol to produce fatty acid esters, or biodiesel. Those fatty acids from
the triglyceride are replaced by the hydroxyl groups from the alcohol to produce glycerol, a by-
product. The glycerol can be separated from the biodiesel by gravity, but the process is typically
accelerated through a centrifugation step. If methanol (CH3– OH) is used as the alcohol for the
transesterification reaction, methyl groups attach to the liberated triglyceride fatty acids (Rx–
CH3 ), as illustrated in figure 2. The resulting mixture after glycerol separation is referred to as
fatty acid methyl esters (or FAME as commonly called in Europe), and biodiesel after further
refining. Without the glycerol skeleton, the mixture of FAME is much less viscous than the
original vegetable oil or animal fat, and its fuel properties are suitable for powering diesel
engines. The transesterification of oils and fats involves a series of three consecutive reactions.
Each fatty acid group is separated from the glycerol skeleton and transesterified individually.
The intermediate products are diglycerides (when two fatty acid groups remain on the glycerol
backbone) and monoglycerides (when one fatty acid group remains on the glycerol backbone).
Transesterification reactions are also reversible. The diglyceride and monoglyceride
intermediate products can react with a free fatty acid and reform triglycerides and diglycerides,
respectively, under certain conditions. The degree of reverse reaction depends on the chemical
kinetics of transesterification and the reaction conditions. In practical application, approximately
twice the stoichiometric methanol requirement is added in order to drive the forward reactions
and to ensure more complete conversion of oils and fats into biodiesel. The excess methanol
can be recovered and purified for reuse in the system. The density of vegetable oil at 25°C is in
the range of 903– 918 kg/m3 (7.53– 7.65 lb/gal) depending on the specific feedstock (Forma
et al., 1979). The density of biodiesel is approximately 870– 880 kg/m3 (7.25– 7.34 lb/gal)
(Pratas et al., 2011). Comparison reveals that vegetable oil is approximately 4% heavier than
biodiesel. While planning for biodiesel production, it is an acceptable assumption that each
volume of biodiesel produced requires an equal volume of vegetable oil. To calculate the exact
volume of chemicals (i.e., reactant methanol and catalyst) needed for the transesterification, the
molecular weight of the vegetable oil is needed. However, as seen from table 3, vegetable oils
vary in fatty acid composition depending on oil source and even on the specific plant cultivar.
There is no defined molecular weight for all vegetable oil, but an average molecular weight is
used for calculations. Based on the hydrolysis of fatty acid esters of glycerol, the molecular
weight of vegetable oil (a mixture of fatty acid glycerol esters), MWave , can be calculated as:
AKUU AKUU AKUU GAMBAR
The water is subtracted in the equation because three individual fatty acids are joined to the
single glycerol molecule in a condensation reaction that produces three water molecules in the
process. The opposite reaction, hydrolysis, would split the fatty acid from the glycerol through
incorporation of the water molecule ions into the products. The overall average molecular weight
of vegetable oil fatty acids is calculated as:
AKUU AKUU AKUU GAMBAR
The difference between the weight of the methyl group (– CH3 ; 15 kg/kmol) and that of the
hydrogen atom (– H; 1 kg/kmol) on the carboxyl group of fatty acids is 14 atomic mass units. To
find the average molecular weight of fatty acid methyl esters (FAME) or biodiesel, MWave,FAME
, the following formula can be used:
AKUU AKUU AKUU GAMBAR
Use of a Catalyst The transesterification reaction will occur even at room temperature if a
vegetable oil is mixed with methanol, but would take an extraordinarily long time to approach
equilibrium conditions. A catalyst and elevated temperatures are typically used to Figure 3.
Chemical reaction between methanol and potassium hydroxide to form potassium methoxide.
help the reaction move forward and dramatically reduce the reaction time. The catalysts suitable
for transesterification of oils and fats are either strong acids or strong bases; the latter are most
commonly used, especially for virgin vegetable oils. Sodium hydroxide (NaOH) and potassium
hydroxide (KOH) are inexpensive choices for use as base catalysts; they are typically available
commercially as solid flakes or pellets. Before being used as a catalyst for transesterification,
the solid form of NaOH or KOH needs to be prepared by reacting with methanol to form a
homogenous solution. This dissolving process is a chemical reaction to form soluble methoxide
(– OCH3 ), as shown in figure 3. The methoxide is the active species for catalysis in the system.
Therefore, the solution of sodium methoxide (NaOCH3 ) or potassium methoxide (KOCH3 ) in
methanol are the preferred form of the catalysts for large continuous- flow biodiesel production.
Solutions of NaOCH3 or KOCH3 in methanol are commercially available in 25– 30%
concentrations.