HETEROGENOUS AND HOMOGENOUS

CATALYSIS ON BIODIESEL
M ARSLAN ASHRAF SP15-CHE-063
M NOUMAN ALI SP15-CHE-033

M NOMAN SAEED SP15-CHE-017

. Biodiesel

• Clean burning fuel

• Replacement of petroleum fuel
• Two source
Animal
Plant

Note: its not vegetable

oil
METHOD FOR PRODUCTION BIODIESEL

• Direct use and blending

• Micro emulsions
• Thermal Cracking
• Esterification / Transesterification
• Non catalytic transesterification
• Ultrasound assisted / Microwave assisted
ESTERIFICATION / TRANSESTERIFICATION

transesterification is the process of exchanging the alkoxy group of an ester

compound by another alcohol. These reactions are often catalyzed by the
addition of an acid or base - Source.

• Cost dependent.
• Overall cost reduce using catalyst.
REACTION EXAMPLE
CATALYST

catalyst

Homogenous Heterogenous Enzymes

Acid Base Acid Base

homogenous homogenous Heterogenous Heterogenous
BASIS CATALYSTS

• KoH
• NaoH
• Potassium methoxide ( CH3KO)
• Ca Ethoxides (C2H5OCa)
• Ca methoxides(CH3OCa)
• Cao
• Mgo
COMPARISON BETWEEN DIFFERENT CATALYSIS

• Calcium methoxides(CH3OCa) and Potassium methoxide ( CH3KO)

Are better than NaoH and KOH
• When comparing on bio diesel yield
• Alkaline catalyst is more commonly used
• No side reaction

• KoH
• 98.53% by using 1%wt KoH
• 9:1 Methanol to Oil ratio

• NaoH
• 95% by using 1.3%wt NaoH
• 9:1 Methanol to Oil ratio
HOMOGENOUS BASE CATALYSIS

• More preferable

• Very commonly used

• Proceeded on lower Temp

• Selectivity
CAO CATALYSIS

Mass Percent of
The Amount of The Catalyst Alcohol: Oil Reaction’s
the Catalyst Mass Efficiency
Oil (gr) Compound Mole Ratio Duration (hr)
Compound
40 CaO 6:1 1% 4 78.35
40 CaO 6:1 1.5 % 4 80.12
40 CaO 6:1 3% 4 80.18
40 CaO 7:1 1.5 % 4 92.39
40 CaO 7:1 3% 4 92.33
40 CaO 8:1 1.5 % 4 92.36
40 CaO 7:1 1.5 % 6 94.37
 COMPARISON BETWEEN CAO + MGO

Mass Percent of
The Amount of The Catalyst Alcohol: Oil Reaction’s
the Catalyst Mass Efficiency
Oil (gr) Compound Mole Ratio Duration (hr)
Compound
0.5 g CaO+
40 CaO + MgO 7:1 6 90.85
0.7 g MgO = 3 %
0.6 g CaO+
40 CaO + MgO 7:1 6 96.22
0.6 g MgO = 3 %
0.7 g CaO+
40 CaO + MgO 7:1 6 98.95
0.5 g MgO = 3 %
0.9 g CaO+
40 CaO + MgO 7:1 6 98.57
0.3 g MgO = 3 %
ADVANTAGES AND DISADVANTAGES OF USING
HETEROGENEOUS BASE CATALYST
• Easy separation of catalyst from
product.
• High possibility to reuse and
regenerate the catalyst.
• Relatively faster reaction rate than
acid-catalyzed transesterification
• Too much soap formation will
decrease the biodiesel yield and
cause problem during product
purification
• •Leaching of catalyst active sites may
result to product
contamination
BIOCATALYSTS
ENZYMES
NOVOZYM-435
LIPASE
• This happens in the presence of super critical carbon di oxide
• Very high conversions
• (>80%) were obtained within 10 min and nearly complete conversions were reported
within 40 min for the synthesis of biodiesel in supercritical alcohols
• However, conversions of only 60–70% were obtained in the enzymatic synthesis even
after 8 h under normal circumstances
LIPASE IMMOBILIZED ON HYDROTALCITE AND
ZEOLITES
• Waste oil transesterification
• catalyst loading 4 wt.%, molar ratio of methanol to oil 4:1
• reaction time 5 h
• yield was 95% even after 7th cycle of the reaction
NOVUZYMES
435 AND LIPOTASE 100T
• palm oil
• catalyst loading 20 wt.%
• molar ratio of oil alcohol 1:4
• reaction time 24 h and
• biodiesel yield 89.9% and catalyst recyclability was 4–8 times.
LIPOZYME1

• Sunflower seed oil with methanol

• Molar ratio1 for methanol to oil
• the encapsulated enzyme achieved 90% methanol conversion after 50 h at 40 ◦C.
• The recycling activity increased by 40% after the first test, then slowly decreased in the
next runs to reach an activity still 20% higher than the initial during the fifth test.
LIPOZYME TL IM

• corn oil
• The optimum combinations for the reaction were 25.9 U/g oil of Enzyme
• 0.58 volume ratio of t-butanol to oil
• 0.5, 0.5, 2.8 molar equivalent of methanol to oil added at the reaction time of 0, 2, and 4 h, respectively
• for a ME yield of 85.6%.
• Waste oil was found to be more suitable feedstock
• could give 93.7% ME yield under the optimum conditions described above.
• Adding triethylamine (TEA), an acylmigration enhancer, could efficiently improved the ME yield of the
methanolysis of corn oil, giving a ME yield of 92.0%.
ACID CATALYST

Advantages of solid acid catalyst over liquid catalyst

• They are insensitive to FFA content
• Esterification and transesterification occurs simultaneously
• Eliminate the washing step of biodiesel
• Easy separation of the catalyst from the reaction medium, resulting
in lower product contamination level
• Easy regeneration and recycling of catalyst and
• Reduce corrosion problem, even with the presence of acid species
HOMOGENOUS ACID CATALYSTS
HETEROGENOUS ACID CATALYST