HYDROGENATION OF OILS AND

FATS AND CATALYSTS

Albert J. Dijkstra
 Wilhelm Normann (1870-1939)

17 October 2011 AOCS Short Course 2

Cartagena, Colombia
 Purposes of hydrogenation process
• To convert a liquid oil to a solid fat
– Redresses balance between supply and demand
for solid fats used in margarine and shortenings
– Reduces price of solid fats
• To increase the stability of edible oils
– In the US, linolenic acid was considered to cause
oil instability
• To utilise otherwise useless raw materials
– Formerly whale oil and fish oil
– Now (?) linseed oil, a drying oil not fit for
consumption
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Cartagena, Colombia
 Hydrogenation reactor

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Cartagena, Colombia
 Reactor characteristics
• Pressure vessel (up to 5 bar or more)
• Capacity from 5 to 25 tons
• Temperature up to 220°C
• Heat exchange coils used to
– heat the oil to reaction temperature (> 140°C)
– remove heat of reaction by cooling
• Strong agitator that
– keeps catalyst particles in suspension
– causes gas bubbles to dissolve in the oil
– circulates oil over heat exchange coils
• Hydrogen supply system that may comprise recircu-
lation of hydrogen that escaped to the head space
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Cartagena, Colombia
 Reactions of fatty acid moieties
during hydrogenation
• Oils contain different unsaturated fatty acids
– Monounstaurated (oleic acid, C18:1), diunstaurated (linoleic
acid, C18:2), triunsaturated (linolenic acid, C18:3), etc
• The most simple reaction is the saturation of a mono-
unsaturated fatty acid

H2

H H2
C H2 C
C C
H H2

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Cartagena, Colombia
 Double bonds can isomerise
• Positional isomerisation
• Double bonds shift along the carbon chain
• So hydrogen atoms move from one carbon to another
• via a two-step hydrogen addition/removal (nickel catalyst)
• or two-step hydrogen removal/addition from polyenes (copper
catalyst)

H H2 H2
C C H
C C C
H C
H

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Cartagena, Colombia
 Geometrical isomerisation
• During geometrical isomerisation, double bonds with a
cis-configuration are converted into bonds with a trans-
configuration
• The reaction is reversible
• Thermodynamically, trans is favoured over cis (~3 : 1)
• Trans-isomers are less bent than cis isomers and
therefore fit better in crystal lattice and raise the
melting points of triglycerides

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Cartagena, Colombia
 Conjugation of polyunsaturates
• The double bonds in nearly all polyunsaturated fatty acids are
interrupted by methylene groups
– These groups are doubly allylic and prone to oxidative attack
• During hydrogenation, positional isomerisation can lead to a
conjugated double bond system
– Can easily be determined by UV-spectroscopy
– Precedes copper-catalysed hydrogen addition
• Such systems have more strongly activated pentadienyl
hydrogen atoms that are more prone to oxidative attack

CH2
C C
H2 H2

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Cartagena, Colombia
 Simplification by assuming the
“common fatty acid pool”
• In 1946, there was only scant evidence (Bushell &
Hilditch, 1937) that the reaction rates of O3, O2S and
OS2 were not proportional to their oleic acid content
• So Bailey (1946) proposed the hypothesis (“common
fatty acid pool”) that their rates would be proportional
– This hypothesis soon became a dogma
• In 1983, I showed that linoleic acid in LLC reacts
more slowly than in LCC (C=short, caprylic, capric)
• In 1997, I rejected the “common fatty acid pool”
concept during my Chang Award Address
• Even so this concept has stimulated research and
facilitated understanding
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Cartagena, Colombia
 EFFECT OF TEMPERATURE ON FAME AND TRANS
ISOMERS
140 C vs. 200 C (3.0 bar)
80

% COMPOSITION (FAME)
RED = 140 C
70
GREEN = 200 C C18:1
60
C18:2
TRANS
50
40
30
C18:0
20
C18:3 10
0
140 130 120 110 100 90 80 70 60 50
IODINE VALUE (Courtesy BASF)

17 October 2011 AOCS Short Course 11

Cartagena, Colombia
 Observations
• C18:3 and C18:2 decrease almost linearly
• Causing C18:1 to increase linearly
• Trans content also increases linearly
• C18:0 hardly increases until C18:2  15%
– At this point in time the reactivity of the reaction mixture has
decreased to such an extent that [H2] starts to increase
appreciably
– Monoene isomerisation is replaced by saturation
• The concentrations of all unsaturated fatty acids
decrease; trans also starts to decrease
• Stearic acid is now increasing quite rapidly
– Linoleic acid selectivity drops to much lower level

17 October 2011 AOCS Short Course 12

Cartagena, Colombia
 Selectivities in hydrogenation

Linolenic acid selectivity

k3
Ln + H2 L SLn = k3/k2
k2
L + H2 O
k1 Linoleic acid selectivity
O + H2 S
SL = k2/k1

Isomerisation index = - trans / Iodine value

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Cartagena, Colombia
 Effect of increasing process para-
meters values on [H2] and selectivities
Hydrogen Linoleic acid Trans
concentration selectivity selectivity
Temperature down up up

Pressure up down down

Rate of agitation up down down

Catalytic activity down up up

Oil unsaturation down up up

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Cartagena, Colombia
The Horiuti-Polanyi mechanism (1934)
• Hydrogen addition is a two-step reaction
• A first hydrogen atom is added to the double bond to
form a half-hydrogenated intermediate (H-HI)
– This is a reversible reaction
• A second hydrogen atom is added to the H-HI
– This reaction is irreversible and exothermic
H H H H
H R1
R1 R2 H R2

H H H H
R1 H R1 R2
H R2 H H

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H = hydrogen
D = diene
M = monoene
S = stearic acid
* = adsorbed

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 The adsorption and dissociation of
hydrogen
1 2
H2 H2* 2 H*

• Molecular hydrogen is made to dissolve in the oil

• By agitation and diffusion, the hydrogen reaches the
catalyst surface
• The hydrogen molecule is adsorbed onto the catalyst
surface; this is indicated by an asterisk *
• The adsorbed hydrogen molecule dissociates into
two hydrogen atoms that are both adsorbed H*

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Cartagena, Colombia
 Isomerisation of linoleic acid
c,c-D c,t-D t,t-D
3 6 9
4 5 7 8
c,c-D*+ H* c-DH* c,t-D*+ H* t-DH* t,t-D* + H*

• Linoleic acid (c,c-D) is adsorbed (c,c-D*) in reaction 3

and reacts with adsorbed hydrogen atom (H*) in step 4 to
form adsorbed half-hydrogenated intermediate (c-DH*)
• The half-hydrogenated double bond is neither cis or trans
• On dissociation, this intermediate (c-DH*) forms (c,t-D*)
by step 5 or reverts to (c,c-D*) via step – 4
• On desorption, c,t-D* and c,c-D* retain configuration
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Cartagena, Colombia
 Various possibilities for H-HI c-DH*
4 5
c,c-D* + H* c-DH* c,t-D*+ H*
+
H*
10

c-M

1. Dissociate and re-form cis,cis linoleic acid (c,c-D)

2. Dissociate and form trans isomer of linoleic acid (c,t-D)
3. React with adsorbed hydrogen atom to form oleic acid
[H*] determines the relative rates
When [H*] is low, dissociation is favoured
When [H*] is high, reaction leading to saturation is favoured
[H*] increases when [H2] increases (proportional to 2)
Suppressing trans formation leads to more saturation
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Cartagena, Colombia
 Formation of stearic acid
14 15
c-M*+ H* MH* t-M* + H*
+
H*
16

• Half-hydrogenated monoene (MH*) can dissociate or

react to form stearic acid
• Which reaction is favoured depends again on [H*]
• Please note that saturation reactions are irreversible
• Please note that saturation products immediately
desorb from the catalyst surface (exothermic reaction)

17 October 2011 AOCS Short Course 20

Cartagena, Colombia
 Formation of trans isomers
14 15
c-M*+ H* MH* t-M* + H*
+
H*
16

S
• When the hydrogen concentration at the catalyst surface [H*] is
low, dissociation is favoured
• This is the cause of cis-trans isomerisation
• Poisoning the catalyst lowers [H*] at its surface
• Poisoning also lowers catalytic activity
• This can be counteracted by using more (poisoned) catalyst
• Using a high concentration of poisoned catalyst allows cis-trans
equilibrium to be reached in reasonable time
• Product is raw material for cocoa butter replacers
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Cartagena, Colombia
 Relative stabilities of half-
hydrogenated intermediates (H-HI)
• H-HI formed from polyunsaturated fatty acid still has at
least one double bond left
• This bond has affinity for catalysts surface
– So the H-HI: c-DH* and t-DH* are retained onto catalyst
– until they eventually react with H* (partial saturation)
• H-HI formed from monoene has little affinity
– It readily dissociates and forms trans isomers
• During a normal hydrogenation process:
– polyunsaturated fatty acids hardly isomerise but are partially
saturated (linoleic acid selectivity)
– whereas monoenes predominantly isomerise

17 October 2011 AOCS Short Course 22

Cartagena, Colombia
 Hydrogen concentration
• During a hydrogenation reaction the rate of
hydrogen consumption depends upon
– Reactivity of reaction mixture
• Amount and activity of catalyst
• Degree of unsaturation of the triglycerides
– Hydrogen concentration in the oil
• The rate of hydrogen dissolution depends on
– Rate of agitation
– Hydrogen concentration in the oil
– Hydrogen solubility
• Pressure in the autoclave; temperature

17 October 2011 AOCS Short Course 23

Cartagena, Colombia
Actual hydrogen concentration in the
oil is the result of dynamic equilibrium
• In early stages, when IV and reactivity are high,
limited H2-supply causes [H2] to be low
• When IV and reactivity decrease, reaction rate is
maintained by allowing [H2] to increase
– Higher [H2] favours saturation over isomerisation
– Selectivity decreases
– Stearic acid is formed
• In industrial reactors, [H2] starts at a few percent of
solubility and increases to a value close to solubility
– Especially when full hydrogenation (IV = 0) is aimed for

17 October 2011 AOCS Short Course 24

Cartagena, Colombia
 Noble metal catalysts
• Palladium and platinum also catalyse the
hydrogenation via Horiuti-Polanyi mechanism
• They are both more active than nickel
– Higher density of triglyceride adsorption sites
– Lower catalyst loading suffices
• Pd is similar to nickel (saturates and trans)
• Pt produces lower trans but more saturates
– Could be explained by assuming higher density of
hydrogen atoms on catalyst surface
• They are too expensive for industrial use
17 October 2011 AOCS Short Course 25
Cartagena, Colombia
 Copper-chromium catalysts
• Cu-Cr (15% Cr) hydrogenation catalysts have a
number of unique characteristics:
– They do not catalyse the saturation of monoenes
• Unless at elevated pressures (> 200 bar)
– They catalyse the partial saturation of conjugated double bond
systems
– They also catalyse the conjugation of methylene interrupted
polyenes that can then be hydrogenated
– Conjugation is by abstraction of a bis-allylic hydrogen from the
interrupting methylene followed by hydrogen addition to a
radical position
– When this leads to the formation of a conjugated double bond
system, partial saturation can proceed

17 October 2011 AOCS Short Course 26

Cartagena, Colombia
 Hydrogenation products

• Partially hydrogenated whale oil

– Stopped when whaling stopped
• Partially hydrogenated fish oil
– Fish oil is now mainly used in aquaculture feed
• Partially hydrogenated vegetable oils
– Much reduced because of current trans scare
– Much preferred in bakery products for performance reasons
• Fully hydrogenated vegetable oils
– Can be randomised with liquid oil to produce hardstock
• Hydrogenated palm kernel stearin
– Used as cocoa butter substitute

17 October 2011 AOCS Short Course 27

Cartagena, Colombia
 DIXI

(I have spoken)

17 October 2011 AOCS Short Course 28

Cartagena, Colombia