TRANSESTERIFICATION FOR BIOFUEL.

(R.COO)3.C3H5 + 3MeOH → 3 RCOOMe +

C3H8OH
In presence of catalyst and lots of water.
 Interesterification

Interesterification involves an exchange of acyl group

among triglycerides.

Acyl groups may exchange positions within a

triglyceride or among triglyceride molecules.
Interesterification
 Catalysts

• High temperature catalysts: KOH and NaOH

• Low temperature catalysts: Sodium Methoxide (NaOCH 3)

 Reaction Mechanisms

1. The formation of enolate ion

2. The formation of Beta-Keto ester

3. Interesterification
Catalyst Function in Interesterification

Initial removal of an -proton by the base catalyst

leads to the charge delocalized enolate anion.
O -
+ OH H2O +
CH3 C CH3

O O-
-
CH3 C CH2 CH3 C CH2

O -
CH3 C CH2
 Mechanism for Intramolecular Ester-Ester Interchange

_ _
O O O H O
O C CH R1 O C O C C C CH2R2
H
C R1 R1
O COCH2R2 O C CH2R2 O-
O
O COCH2R3 O COCH2R3 O COCH2R3

I II III
Enolate ion formation
Beta-Keto ester formation

_ Intraesterification
_
O H O _
O C C C CH2 R2 O O COCH2R2
R1 O H O O
O O C C C CH2R2 O C C R1
R1 H
O COCH2 R3 O COCH2 R3 O COCH2R3

III IV V
 Random Esterification

Interesterification can be carried out to an equilibrium

condition, at which point the fatty acids assume an
almost random distribution among triglycerides.
Intraesterification, Interesterification and Equilibrium Mixture.

S
O
L
Catalyst

O O L
L S O
S L S
Continued reaction

S S S S S S O S L
S S O L S O S L S
S O S L O O L L
S

L L O O O O
L O L L O O
L L L O L O

SSS (SUS SSU) (SUU USU) UUU

 Direct Interesterification

Interesterification can be directed away from

its usually random end-point if the fat is
allowed to crystallize during reactions.
The trisaturated glycerides crystallize first.
 Intraesterification, Interesterification and Equilibrium Mix

S
O
L
Catalyst

O O L
L S O
S L S
Continued reaction

S S S S S S O S L
S S O L S O S L S
S O S L O O L L
S

L L O O O O
L O L L O O
L L L O L O

SSS (SUS SSU) (SUU USU) UUU

 Directed Interesterification

1. Stearic-Stearic-Stearic 33.3 mole % solid

2. Oleic-Oleic-Oleic 8.3 mole % liquid
3. Linoleic-Linoleic-Linoleic 8.3 mole % liquid
4. Oleic-Oleic-Linoleic 24.9 mole % liquid
5. Oleic-Linoleic-Linoleic 24.9 mole % liquid
 Applications

Shortenings: The proportion of palmitic acid in the

2-position is reduced from about 64% to 24% on
random interesterification.

Natural lard
Randomized lard

Randomization of lard improves its plastic range and

thus makes it a better shortening than natural lard.
 Plasticity and Consistency
Plasticity is the changes in consistency as a function of
temperature.

Consistency is the apparent hardness at a temperature

 Margarines – High Stability Margarine Blends

1. 75 % (co-randomized 40 % coconut oil / 60 % palm oil),

2. 10 % (co-randomized 50% coconut oil / 50 %
hydrogenated canola oil) and
3. 15 % hydrogenated soybean oil

Good spreadability, high temperature stability, and good

eating qualities.
 Nutritional Margarine Blends

High polyunsaturated content and low-to-zero

trans-acid containing margarines are produced by
interesterifying a blend of liquid oil and a fully
hydrogenated oil.
 Confectionary Fats

Hydrogenated palm kernel oil is a hard butter melting

at 46C and produces a waxy feel in the mouth.
On randomization, its melting point is reduced to
35C. By blending hydrogenated palm kernel oil and
its randomized product, a whole series of hard butters
with highly desirable melting qualities (rapid melt in
mouth) are obtained
BLOCK DIAGRAM FOR KRAFT PROCESS
 Gaseous Waste
KRAFT PROCESS
Reference: El-Halwagi, M. M., Pollution Prevention through Process Integration: Systematic Design Tools . Academic Press, 1997.

Wood
Chips

Recovered
Multiple Effect
Steam White Liquor
Evaporators
Strong Weak Digester
Black Black
Liquor Liquor Pulp to
Gases further
Off
Gas processing

Steam

Blow Tank Washers

Condensate
Lime Slaking &
Flue
Gas
Recovery Causticizing

Furnace
Smelt Air
Off
Water
Gas
Settling &
Dissolving Lime Kiln Calcium
Carbonate Filtration
Tank Green
Liquor Gases
 Tier III – Problem Statement

Energy in the Kraft pulping process

The Kraft pulping process is a very energy-intensive process: electricity end-uses common to all
pulp and paper mills include pumping, air-handling, and lighting. In addition, steam needs and
the large number of process streams makes this sector of the industry a good candidate for
improved heat integration. Black liquor concentration is usually the biggest single steam using
operation in a Kraft pulp mill. Evaporators installed in the 1960s and 1970s were built with four
or five effects, whereas most Kraft mills today use five or six effect evaporators, with a
concentrator to further increase solids content. Firing the recovery boiler with the black liquor at
higher solids content improves overall boiler performance and is a general trend in the industry.
To counter this energy consumption problem, a Kraft pulp mill uses biomass. In fact, in addition
to being the feedstock for pulp and paper production, biomass is also a major energy resource
for the industry. The industry also has access to residues of pulpwood harvesting, some of
which can be removed from the forest on a sustainable basis. All black liquor and most mill
residues are used at mill sites to fuel cogeneration systems, providing steam and electricity for
on-site use. Cogeneration also known as Combined Heat and Power (CHP) is the simultaneous
production of electricity and useful heat from the same fuel or energy. A typical cogeneration
system consists of an engine, steam turbine, or combustion turbine that drives an electrical
generator. A waste heat exchanger recovers waste heat from the engine and/or exhaust gas to
produce hot water or steam.