Methaoxides Reaction time 45min

Temp rapture 60C

1.5 Wt %
Yield is more than 98%


Disadvantage in General for Both NaOH and KOH mostly KOH:
Presence of water content generally manifests itself through excessive soap production. Apart
from that, the soaps of saturated fatty acids tend to solidify at ambient temperatures and thus a
reaction mixture with excessive soap may gel-up and form a semi-solid mass which is very
difficult to recover.

Methaoxides:
The formation of methyl esters by transesterfication stoichiometrically requires three moles of
alcohol for every mole of triglyceride However, transesterification is an equilibrium reaction in
which a large excess of the alcohol is required to drive the reaction close to completion.
Fortunately, the equilibrium constant favors the methyl esters such that only a 6:l molar ratio of
methanol: triglyceride is sufficient to cause a 95-98% yield of ester. It might be anticipated that,
in such an equilibrium system, the observed phase separation of the by product, glycerol, would
play a major role in achieving conversions close to 100%. Fuel standards currently developing
for biodiesel methyl esters severely limit the mono-and diglyceride contents. Because of this, and
the high cost of the raw material, very high conversions are important, and if achieved, could
eliminate the necessity for distillation beyond that required for removal of the excess alcohol.
The 6: l methanol: oil ratio, which appears to be that being adopted in commercial processes, was
also used in the kinetic study of 1986.
In this sense, the reactions that used sodium or potassium hydroxide were faster than the
reactions with the sodium or potassium methoxides. Regarding both types, the transesterification
with the sodium catalyst was faster than the reaction with the potassium catalyst. Thus, the near
100% methyl ester concentration was obtained at 30 min with sodium hydroxide, at 45 min when
using sodium methoxide or potassium hydroxide and after 4 h with potassium methoxide.
The preferred catalysts for large continuous-flow production processes are Sodium and
potassium methaoxide which is now commercially available as well. In transesterification, the
effective species of catalysis is the methoxide radicals (CH3O). The activity of a catalyst
depends upon the amount of methoxide radicals available for the reaction (Komers et al., 2001a,
b). For sodium or potassium hydroxide, methoxide ion is prepared in situ by reacting hydroxide
and methanol:
This reaction also yields water that remains in the system. Hydrolysis of triglycerides and alkyl
esters may occur due to the presence of water, which further leads to the formation of free fatty
acids and thus to undesired soap. Saponification will also occur if a strong base, e.g., NaOH or
KOH, is present in the system by reacting with esters and triglycerides directly. On the other
hand, the water problem can be avoided if sodium and potassium methoxide solutions, which can
be prepared water-free, are applied. Additionally, although the use of methoxides cannot avoid
soap formation if the feedstock contains free fatty acids, which is also true for use of KOH or
NaOH, but very little saponification of esters or triglycerides occurs because methoxides behave
as weak Lewis bases.
However all these base reactions differ at different conditions for example at 65 C and molar
ratio 3:1 Sodium methaoxides yields more biodiesel but by increasing the molar ratio and
decreasing temperature Potassium metha oxide will result in higher yield of biodiesel and lower
yield of soap formation:


Optimization in transesterifying methanol and canola oil using four alkaline catalyst
formulations by examining their effects on biodiesel yield and soap formation at different
catalyst molar concentrations, reaction temperatures, and methanol-to-oil molar ratios. Optimum
operating conditions for maximizing biodiesel yield and minimizing soap formation were
determined by statistically analyzing the experimental data using a multiple response
optimization statistical software and further verified through experimentation.

According to Freedman et al. (1986) NaOCH3 is a more effective catalyst formulation than
NaOH and almost equal oil conversion was observed at 6:1 alcohol-to-oil molar ratio for 1%wt
NaOH and 0.5%wt NaOCH3. Vicente et al. (2004) reported higher yields with methoxide
catalysts, but the rate of reaction was highest for NaOH and lowest for KOCH3 at 65C, a
methanol-to-oil ratio of 6:1, and a catalyst concentration of 1%wt. It was observed that
potassium based catalysts gave better yield than sodium-based catalysts and methoxide catalysts
gave higher yields than their corresponding hydroxide catalyst. The trend observed can be
modelled as follows:
KOCH
3
> NaOCH
3
> KOH > NaOH

The table below summarizes the results obtained among the four catalyst formulations:

Generally, the catalyst formulation on soap showed that potassium based catalysts resulted in
higher soap formation than the corresponding sodium-based catalysts. Only KOH was found to
have a significantly higher level of soap formation than the other three formulations in terms of
soap formation:
NaOCH
3
> NaOH > KOCH
3
>>KOH



It was observed that methoxide catalysts led to better biodiesel yields than hydroxide catalysts.
The methoxide catalysts not only accelerated the reaction but also elevated the conversion
equilibrium. Based on statistical optimization, the operating conditions for maximizing biodiesel
yield and minimizing soap formation were potassium methoxide as catalyst at a concentration of
0.2 mol/mol (1.59%wt), reaction temperature of 50
o
C, and methanol-to-oil molar ratio of 4.5:1.
This resulted in an optimum yield of 95.8% with a total soap formation of 0.75%.











Refrences :
Gemma Vicente, Mercedes Martinez, Jos Aracil, Integrated biodiesel
production: a comparison of different homogeneous catalysts systems,
Bioresource Technology, Volume 92, Issue 3, May 2004, Pages 297-305, ISSN
0960-8524, http://dx.doi.org/10.1016/j.biortech.2003.08.014.
(http://www.sciencedirect.com/science/article/pii/S096085240300230X)

Man Kee Lam, Keat Teong Lee, Abdul Rahman Mohamed, Homogeneous, heterogeneous
and enzymatic catalysis for transesterification of high free fatty acid oil
(waste cooking oil) to biodiesel: A review, Biotechnology Advances, Volume
28, Issue 4, JulyAugust 2010, Pages 500-518, ISSN 0734-9750,
http://dx.doi.org/10.1016/j.biotechadv.2010.03.002.
(http://www.sciencedirect.com/science/article/pii/S0734975010000388)