Other Processes

Learning outcomes

 Students should be able to:

 Organise information on selecting extended process after
RBDPO
 Explain each extension process with correct process
variables and techniques
 Identify attributes of each extended processes such as
products, process flow and etc

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Others Processes

 Combination of Hydrogenation, Interesterification and

Fractionation offers the opportunity of economically meeting the
increasing demand for specialty products for foodstuff and
technical application from available raw material.
 Also known as value added process

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Hydrogenation

 Hydrogenation is the most widely used method of all the oil

modification processes, to reduce the degree of unsaturated in
the fatty acid groups of the glycerides

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Reaction Mechanism

 The trivalent alcohol glycerol, which is the basis of all

triglycerides, is completely saturated at all its C-C-
bonds and therefore does not react with hydrogen.
 Hydrogen is added only to the unsaturated bonds of
the fatty acid chains.
 The mechanism is a type of electrophilic addition of
hydrogen to the C=C double bond.
 The reaction proceeds in several steps according to
diagram below:

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Reaction Kinetics

 To characterize the progress of a reaction and

in particular the degree of hydrogenation of
fatty acids with different numbers of double
bonds, one usually speaks of selectivity.
 Selectivity takes into account that the single
steps in this sequence proceed more slowly
the more saturated is the oil/fat.
 Albright (1965) generalized it to the sequence
as below:

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Reaction Kinetics

 Selectivity is the ratio of the velocity constants K, of

the single reactions.
 The selectivity of single steps is marked by indices as
follows:

 Selectivity's with reaction rate constants higher than

k, have not yet been defined because they are of no
practical use.

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Reaction Kinetics

 Hydrogenation has been heterogeneous reaction, so the

industrial hydrogenation process is nearly always a batch
process followed by the removal of the catalyst by filtration.

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Hydrogenation

 Double bonds in fatty acid can be wholly or partially

saturated by adddition of hydrogen in the presence of
catalyst such as nickel, platinum or palladium.
 A "nickel" catalyst often used in hydrogenation,
called "Rayney's Nickel", is actually 50% nickel and
50% aluminium. Remnants of both metals remain
in products containing hydrogenated or partially
hydrogenated oils, and are eaten by people
 Can increase melting point
 Also known as hardening

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Hydrogenation

 Partial hydrogenation can lead to isomerization of cis

double bonds to trans double bonds.

H H H H

R-C=C-R + H2 R- C – C – R

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Hydrogenation

 Liquid oils with unsaturated triglycerides are thus transformed

into fats containing a higher % age of saturated triglycerides
 Hydrogenation is often called hardening of oils and soft fats.

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Hydrogenation

 The complex system consists of three phases:

 Liquid oil
 Gaseous hydrogen
 Solid catalyst.
 Hence there are many different internal surfaces through which
the hydrogen molecules have to pass until they reach the double
bonds of the unsaturated triglycerides adsorbed on the catalyst
surface.

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Hydrogenation

 As soon as the unsaturated bonds are

saturated, the triglyceride moves off the
catalyst surface, thus enabling the next
unsaturated molecule to be adsorbed and
processed
 The overall hydrogenation rage depends on:
1. The quality of the reactant involved.
2. The degree of refining of the oil to be
hydrogenated.
3. The activity and nature of the catalyst.

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Hydrogenation

 In addition, reaction parameters such as time, temperature,

hydrogen pressure (and thus solubility), mass transfer, catalyst
(kind, state and concentration) and substrate (i.e., oil and
fat)and processing, are possible influence.
 In spite of these numerous reaction parameters that affecting
the quality of the desired product, the operating conditions
required for the preparation of tailor-made fats plays significant
roles.

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Reaction Influence Factors:
Temperature

 Hydrogenation is an exothermic process with a little more than

30 kcal being set free per mole of double bond.
 This is equivalent to a temperature increase of 1.6-1.7 K per
lowering of each IV unit.
 The heat of reaction on the one hand makes heating
unnecessary after the activation energy has been introduced

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Reaction Influence Factors:
Hydrogen Pressure and Solubility

 The higher the solubility of hydrogen, the higher the probability

that it is available at the point of reaction, i.e., the contact
surface of catalyst and oil.
 Because hydrogen solubility is directly proportional to
temperature, an increase in temperature must be positive in this
sense.

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Reaction Influence Factors:
Hydrogen Pressure and Solubility

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Reaction Influence Factors:
Mass Transfer

 Hardening takes place in the three-phase system gas/liquid

solid.
 The gas and liquid reaction partners hydrogen and oil have to
be brought together on the solid catalyst surface for reaction.
 The reaction products have to be removed as quickly as
possible to enable new reactions, and consumed hydrogen in
the reaction has to be replaced.
 This is particularly important because the concentration of
double bonds in the oil is always very much higher than the
concentration of hydrogen

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Reaction Influence Factors:
Mass Transfer….PATHWAY
1. H, is brought into the oil.
2. H, is dissolved in the oil.
3. H, travels to the catalyst surface surrounded by
an oil film.
4. Oil molecules and H2 travel into the catalyst’s
pores toward the nickel surface.
5. H, is absorbed onto the active portion of the Ni
catalyst.
6. H, dissociates to hydrogen atoms capable of
reaction.
7. Oil molecules are absorbed at their double
bonds by the catalyst.
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Reaction Influence Factors:
Mass Transfer….PATHWAY

8. H, is added to the double bond of the oil molecule.

9. Desorption of the (partially) hardened oil molecule.
10. Diffusion from the catalyst’s pores.
11. Return to the bulk oil through the oil film
surrounding the catalyst particle.

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Reaction Influence Factors:
Kind, Condition, and Concentration of
Catalyst
 The structure of the catalyst is of great importance.
 Too narrow pores can be blocked by oil molecules and
render adsorption and desorption more difficult.
 Too large pores reduce the total catalyst surface.
 The same can be said for the particle size of the
catalyst as such; too large particles reduce the surface
area, too small particles make filtration more difficult.
 The structure of the catalyst also influences the trans
fatty acid formation

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Reaction Influence Factors:
Kind, Condition, and Concentration of
Catalyst

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Reaction Influence Factors:
Kind, Condition, and Concentration of
Catalyst

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Reaction Influence Factors:
Substrate

 The influence of by-products or impurities will not

be discussed in this section but rather the
influence of the oil and fat itself.
 The most prominent characteristic for an oil and
fat to be hardened is its degree of unsaturation,
i.e.,the number of double bonds represented by its
iodine value.
 The Iodine Value (IV) is a measure for the amount
of hydrogen that is consumed during reaction.

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Hydrogenation

 The raw materials are from refinery:

 Palm Fatty Acid Distillate (PFAD)
 Refined Bleached Deodorized (RBD) stearin

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 Hydrogenation
 Process Description:
 There are various kind of oils used as the feed of this
plant depends on the market demands, there are DFA,
PFAD, RBDSt, precut and split residue. Firstly, the fatty
acid feed from the storage tank (60 – 70°C) is pumped
to the feed preheater. In the feed preheater, the fatty acid
feed is heated up by the hot hydrogenated FA from plant
until 140 – 170°C, before entering the reactor for
hydrogenation process.
 Then, the hot feed is transferred to the reactor autoclave
for reaction. The reactor consisted of the nickel catalyst
which play an important role in the reaction

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Hydrogenation

 Process Description:
 Then, the hot feed is transferred to the reactor
autoclave for reaction. The reactor consisted of the
nickel catalyst which play an important role in the
reaction.

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Hydrogenation

 The roles of catalyst:

 To avoid modifiers, such as sulphur, likely to give higher “trans”
acid contents.
 Comparatively high temperature to accelerate reduction of poly-
unsaturated without formation of saturates.
 Reduced the hydrogen gas pressure.
 Lowering the iodine value to improve stability and good yield of
liquid oil when winterized.
 To remove materials responsible for clouding and solidification
at low temperatures

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 Hydrogenation

Oil& Catalyst
Hydrogen
Steam & water

Steam & water

Oil& Catalyst
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Drawback of Hydrogenation
Product
 Trans isomers have been linked to an increase in blood serum
cholesterol content (Katan, 1995) and this increase is generally
believed to cause heart disease, despite the fact that this causal
effect has not been demonstrated (Ravnskov, 2000)

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Fractionation

 Oils and fats are a mixture of triacylglycerols,

i.e., triple esters of glycerol with different fatty
acids.
 Therefore, fats and oils are not chemically
homogenous substances but a mixture of
different triglycerides; however, each of these
triglycerides has a defined melting point,
influencing the physical properties of the others.

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Fractionation

 As a mixture of substances, therefore, oils and fats have no

sharp melting point but a melting range.
 Oils are liquid at ambient temperature, at least to the eye, and
fats that are solid at room temperature.
 However, even when appearing liquid, oils may contain high
amounts of solid compounds with melting points significantly
above ambient temperature.

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 Fig:

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 Fig: Multistage fractionation of palm oil with possible food applications
for the various fractions
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Fractionation

 Fractionation uses this property of fats, i.e.,

being a mixture of different substances of the
same class.
 This enables separation a fat into fractions
that are products of different melting ranges.

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Fractionation

 Aim of fractionation is to remove undesirable

components or to isolate desired components with
special properties.
 The demand for liquid oils has increased in recent
years, mainly for salad and cooking uses and an
important property for such oils is low cloud point,
which is the temperature at which turbidity appears
when the oil is cooled under standard conditions..
 Simplification term “the process of fractional
crystallization”

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Fractionation

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Fractionation

 Fractionation of fats is carried out for 4 reasons:

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Fractionation

 Crystallization begins when a melt or a solution reaches

an unstable condition.
 This unstable condition can be reached by supercooling or
by partial removal of the solvent.
 The driving force for crystallization is that the system is
beyond its equilibrium, and there is a strong irresistible
drive to regain the equilibrium, which is the nature of all
processes.
 Thus, components crystallize as long as the equilibrium is
out of balance

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Fractionation

 The fractionation success can be determined by

calculating the ratio of the olein yield obtained and
the theoretical maximal yield and this is so-called
separation factor.
 The most important conditions for optimal
crystallization are:
 Stable crystal formation that can be influenced,
 Crystal growth that can be influenced,
 Heat transfer that occurs as quickly as possible.

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Fractionation

 Crystal growth begins with particles and crystallization

nuclei; these may consist of the crystallization substance
itself or of foreign material,
 When crystallization nuclei are seeded into the solution,
crystallization takes place more quickly. If the melt is
subcooled, i.e., if it is far outside its equilibrium,
crystallization can occur like an explosion.
 The process will undergo two conditions as below:
 Nucleation

 Crystal growth

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Means of nucleation

Main factor: (further reading)

Temperature
Saturation of crystal in solution
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Crystal growth

 Crystal growth depends on many factors such as the

temperature of the meltholution, relative to the AT of
the solidification point of a melt and the actual
temperature, the degree of supersaturation, the
particle size of the crystals and the relative speed
between meltholution and the crystal.
 Usually, one goal of a technical crystallization is to
combine a low rate of nucleus formation with a high
rate of crystal growth.

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Fractionation:Crystallize

 Crystallization process is carried out to remove the higher

melting glycerides which cause liquid oils to become
cloudy and more viscous at low temperature.
 There are 3 factors (temperature, time and agitation),
have a fundamental importance on the formation and
character of the crystal:
 The lowering of temperature causes, because of
supersaturating the higher melting component to
separate from a solution.
 Agitation facilitates the formation of small crystals.
 Time with a gradual decrease in temperature and
stillness, promotes the formation of longer crystals.

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Fractionation: Techniques

There are three techniques used:

 Dry Fractionation
 Wet Fractionation
 Lanza Fractionation

Wet and Lanza

Fractionation fall
Between Line A and B

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Fractionation: Techniques

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Fractionation: Techniques

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Fractionation: Techniques

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Interesterification

• it describes:
– The technology to rearrange fatty acids for
different melting and physical characteristics.
– These include acidolysis, alcoholysis, glycerolysis,
and ester interchange or transesterification, which
can be random, directed, or enzymatic
– Interesterification, also often referred to as
“rearrangement”
• is used to modify physical, chemical and/or functional
characteristics of the materials undergoing this
process.

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Interesterification

• The fatty acids of palm oil can be rearranged

in relation to their position on the triglyceride
molecules.
• The rearrangement, which occurs in a random
manner, is conducted in the presence of a
catalyst, and is termed interesterification.
• The rearrangement brings about a change in
the physical properties of the oil, which may
leave the products more useful for making
margarine, vanaspati and shortening.

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Interesterifcation

• Ability to modify the melting point and functional crystallization

characteristics without changing the fatty acid composition
• Early work involved functionality and was not directed at
nutritional issues.
• A number of patents exist for functionality improvement for
shortenings and cocoa butter substitutes (2-5).
• The improvements include stabilization of crystal structure in
the preferred (in this case, p’ form) and lowering of melting point

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Classes of Interesterification

 Acidolysis
 Alcoholysis
 Transesterification/Ester group interchange

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Interesterification..

 Acidolysis :
 Is an reaction of fatty ester with an acid( fatty acids)
 An example of process is the transesterification of coconut
oil with acetic acid yield lower fatty acid (C6-C10) yield fats
with properties similar to those of cocoa butter.
 following esterification of excess acid with glycerol
 Moiety

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Interesterification.

 Alcoholysis:
 Is an reaction of fat with alcohol.

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Interesterification

 Transesterification:
 Is an exchange of radical fatty acids between the esters
 “ rearrangement” can be divided by two:
 Random

 Directed

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Interesterification

 Transesterification:
 Random:
 Occur when fatty acids radical freely moves from one
position to another in single glyceride or from one
glyceride to another. Reach equilibrium based on
composition required
 Directed:
 Reaction directed along a path to produce particular
glycerides . Fatty acids were not mobile. Reach
equilibrium based on selective crystallization of one or
more of the higher melting glycerides.

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Interesterification
 Batch Reactor For Interesterification
Fat
Vacuum

Catalyst slurry

Steam or cooling
water

Nitrogen

Product
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Interesterification

 Acidolysis :
Legend:
native palm oil
Interesterified palm oil
Directly interesterified palm oil
Solids content,%

b
a c

0 60
temperature

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