Reducing Trans

in Existing Reaction Systems

How to reduce trans isomers in partially hydrogenated oils in

existing reactors by modifying process conditions

Author: Kieran Furlong,

Product Manager (Edible Oils & Oleochemicals)
Johnson Matthey Catalysts
Contents

Introduction ..................................................................... 3

What are trans? ............................................................... 3

How are trans formed? ................................................... 5

Hydrogen Concentration ................................................ 7

Summary........................................................................ 10
Introduction
Trans fatty acids have been a topic for research and a subject of concern since the
nineteen seventies. This paper will not address the nutritional or health aspects of
trans fatty acids – there is an abundance of literature available on this topic – but
instead on the formation of trans during hydrogenation. Given recent legislation in a
number of countries requiring the labelling of trans contents or in some, limiting the
trans content, there is a drive from food companies to reduce or eliminate the trans
fat content in their products.

A number of oils used in the world today still need to be modified in some way for
further use in the food industry. Soybean and canola oil are two examples of oils
which require further processing in order to increase their resistance to oxidation or
adjust their melting properties/functionality. Partial hydrogenation is one of the ways
of effecting these changes, but this also causes the formation of trans isomers in the
fatty acid chains of the triglycerides.

This paper will demonstrate how partial hydrogenation of oils like this can be carried
out while REDUCING the amount of trans isomers formed.

What are trans?

Oils and fats are triglycerides – that is they consist of molecules composed of
glycerine and three fatty acids. The fatty acids are long chain of carbon atoms
bonded to each other and some surrounding hydrogen and oxygen. If all of the bonds
between the carbon atoms are single bonds (alkane bonds C-C), the chain is said to
be “saturated”, whereas a double bond (alkene bond C=C) between adjacent carbon
atoms means the chain is unsaturated. This is the origin of the terms “saturated” and
“unsaturated” when used in relation to fats and oils. In unprocessed vegetable oil
practically all of the double bonds present will be in the “cis” configuration. In the cis
form the carbon chain enters and leaves the double bond the same side, giving a
characteristic bend to the chain. (See figure 1).
 H H

H C C H

H C C H

H H
H C C H

H H
C C
H H

Figure 1. Schematic structure of a cis carbon–carbon double bond in an unsaturated

fatty acid

A trans fatty acid is a fatty acid chain where at least one carbon-carbon double bond
is in the trans form – that is the carbon chain enters the bond on one side and exits
on the other side. The effect of this isomerisation is to straighten out the fatty acid
chain. (See figure 2). The straighter chain affects the melting point of the triglyceride,
elevating it to a higher temperature than the chemically similar but geometrically
different cis isomer. Saturating the double bond with hydrogen also raises the melting
point. In hydrogenation the aim is to saturate some double bonds to increase the
oxidative stability of the oil and also to raise its melting point. In some products, trans
isomers are desirable in order to give the fat functionality – a specific melting
behaviour, and “mouth-feel”. However, given the concerns on the health implications
of trans fatty acids, other approaches are being taken to give the necessary melting
behaviours and there is a move to reducing the trans content in oils and fats.
 H

H C
H
H C
H
H C
H
H C C
H
H C
H
H C
H
C
H

Figure 2. Schematic structure of a trans carbon–carbon double bond in an

unsaturated fatty acid

How are trans formed?

The object of the hydrogenation of edible oils is – broadly speaking – to increase the
degree of saturation of the oil. This results in improved resistance to oxidation,
increased melting point, modified solid fat content and so on. During the
hydrogenation, some of the unsaturated carbon-carbon double bonds (C=C) will be
opened due to the presence of the nickel catalyst and react with hydrogen to form a
saturated carbon-carbon bond (C-C) – see figure 3, step c.

If there is sufficient hydrogen present, both carbons will react with hydrogen and the
bond will be saturated – see figure 3, step d. If there is not sufficient hydrogen, side
reactions can occur, however. Once one of the pair of carbon atoms has reacted and
bonded to a hydrogen atom – see figure 3, step e, a number of subsequent
reactions can occur. As described above, with plentiful hydrogen, the second carbon
atom can also react and the bond will be saturated. It can occur – especially when
hydrogen concentration is low – that the “half-reacted” bond will desorb from the
nickel. Now there is a free rotating axis between the two carbons. As the “half-
reacted” situation is unstable, a hydrogen atom will be released by a carbon and the
double bond reformed. There may have been a rotation of the bond and the
formation of a trans bond is possible – see figure 3, step f. It is worth noting that
this reaction mechanism is not unique to nickel and can occur with any metal that
would catalyse the hydrogenation reaction (Cu, Pt, Pd, etc).

If a double bond is reformed, there is a higher probability that it will assume the trans
configuration, as this is thermodynamically preferred. Due to the nature of the
reactants in a typical edible oil hydrogenation – hydrogen as a gas and the oil as a
liquid – there is never sufficient hydrogen for all double bonds that open and hence
some double bonds always form trans isomers.

Ni surface adsorbed molecules

H H H C C H H C H e H H
R1 R2 R1 C H
Oil phase
R2

c d
H H H R4 H H
C=C C=C R C C R2
R1 R2 R3 H
f 1
H H

cis- trans-
unsaturated unsaturated saturated

Figure 3. Formation of trans isomers within a catalyst pore.

In short, it is impossible to have a partial hydrogenation using existing technology

and get zero trans product. Even novel technology such as electrochemical
hydrogenation, which generates a plentiful supply of hydrogen at the point of
reaction, will still produce some trans isomers in a partial hydrogenation. (As trans
are only present when there is a double bond, fully hydrogenated oils have zero
trans).

However the amount of trans isomers present in partially hydrogenated oil can be
significantly altered depending on the hydrogen concentration during the reaction.
Hydrogen Concentration
Trans content at a given degree of hydrogenation or saturation (usually referred to as
the iodine value, IV) can be lowered or raised by controlling the amount of hydrogen
available for reaction. As has been described above, if there is an abundance of
hydrogen the probability of trans being formed is much lower. The corollary is that if
the reaction is starved of hydrogen, there is a much higher probability of trans being
formed.

Therefore, if the aim is to produce as few trans isomers as possible during a partial
hydrogenation, process conditions must be selected which allow for a generous
supply of hydrogen at the point of reaction.

The main control parameters in a hydrogenation reactor are temperature and

hydrogen pressure. They can be described as “pull” and “push” factors. As
temperature increases in the reactor it “pulls” more hydrogen from the supply of
dissolved gas in the liquid. This is due to the increased diffusion in and out of the
catalyst pores, which speeds up the reaction of available hydrogen. The bulk
hydrogen concentration in the oil will drop as the reactor system dispersing the gas
struggles to keep up with the demand for hydrogen. With this lack of hydrogen comes
an increased probability of the formation of trans due to the mechanism described
above. Therefore to make a lower trans hydrogenated oil, it is advisable to run at
lower temperatures. This is possible in existing reactor equipment, although some
reactors are limited by cooling capacity. (Note: Typical hydrogenation is carried out
between 150ºC and 200ºC. Commercial low trans hydrogenation is usually in the
range 100ºC to 150ºC although experimental tests have been carried out at much
lower temperatures).

Pressure is a “push” force. At a higher hydrogen pressure, there is stronger driving

force pushing hydrogen into the oil. This increases the hydrogen concentration in the
oil and hence lowers the probability of forming trans. A lower trans hydrogenation
should be carried out at a high pressure. In research at Johnson Matthey we have
seen a large drop in trans formation by increasing pressure in the range 1 to 20
barG. Above that pressure the effect becomes muted. Unfortunately, many reactors
in the edible oil industry are not rated for operation at higher pressures and 5 bar is
often the maximum achievable.
So if the hydrogenation reaction is carried out with a high hydrogen concentration
(low temperature and high pressure), the product will be an oil containing lower trans
isomers. This can be seen in figure 4 where the results from two separate
hydrogenations are compared. The same oil, catalyst and reactor were used in both
hydrogenations. Reaction A was carried out at lower hydrogenation concentration
(lower pressure, 1.5barg, and higher temperature, 180°C), while Reaction B was
carried out at higher hydrogen concentration (higher pressure, 3.0barg, and lower
temperature, 100°C). The other difference was that Reaction B was carried out with a
higher catalyst dosage, to ensure a reasonably similar reaction time.

Samples were taken at various points during the reaction and the IV and trans
content were measured. The plot of IV versus trans content is in figure 4 and the
difference in trans content is evident. Reaction B has almost half of the trans content
of Reaction A at every IV point. This demonstrates the strong influence that hydrogen
concentration has on the trans formation during a hydrogenation reaction.

50
180°C; 1,5 bar
45
100°C; 3,0 bar
40
trans content (%)

35 Catalyst: PRICAT 9920

30
Oil: rb Soybean Oil
25
Dosage: 0.03% - 0.1%
20
15 Pressure and
temperature held
10 constant during
5 reactions

0
70 80 90 100 110 120
iodine value

Figure 4. Hydrogenation of soybean oil at different hydrogen concentrations (as

controlled by temperature and pressure) and the effect this has on trans content.
This experiment demonstrates the strong influence that hydrogen concentration has
on the trans content of partially hydrogenated oils. The same tendency can be
observed in industrial scale reactors. For anyone trying to reduce trans in partially
hydrogenated oils, they should consider the hydrogen concentration and change their
process conditions in a manner to increase the hydrogen concentration in the oil. For
an existing reactor this means increasing the pressure and/or decreasing the reaction
temperature. However, the hydrogen concentration can also be increased by
improving the dispersion of hydrogen into the liquid phase. This is often a limiting
factor, especially for older stirred tank reactors. Improvement can be made to reactor
impellers or the reactor type can be changed altogether (e.g. to a loop reactor) to
increase the dispersion effectiveness.

Process Hydrogen Probability of Hydrogenation

parameter concentration more trans time
at catalyst forming*
surface
Pressure ⇑ ⇑ ⇓ ⇓

Temperature ⇑ ⇓ ⇑ ⇓

H2 dispersion ⇑ ⇑ ⇓ ⇓

⇑ increasing ⇓ decreasing

Figure 5. Table showing movement in pressure, temperature and subsequent

movement in hydrogen concentration and resultant movement in trans content.

Of course, this change in trans cannot be made in isolation. By changing the

hydrogen concentration in the oil phase, other reactions are affected. The
hydrogenation will be less polyene selective. Given the higher concentration of
hydrogen, double bonds in any unsaturated fatty acid chain will have the opportunity
the react. Linolenic, linoleic and oleic will all be hydrogenated. In contract, when a
reaction is severely deprived of hydrogen, the linolenic is much more likely to react
than the more saturated fatty acids. Therefore a “low trans” hydrogenation will be
less “selective” and this impacts the solid fat content, melting point and oxidative
stability at a given degree of saturation. This is something that must be made clear to
the food companies purchasing the partially hydrogenated oils, as they often are
looking for a lower trans version of a fat, but with the same functional characteristics.
As the low trans conditions make a reaction less polyene selective, if characteristics
such as good oxidative stability and low stearic content are required, a selective
catalyst – such as PRICAT 9920 – should be used.

Time is another factor in the formation of trans. The longer unsaturated oil is in
contact with a catalyst, the closer the cis:trans ratio will approach equilibrium. This
equilibrium favours trans so the reaction time should be kept to a minimum. One of
the consequences of operating at a lower temperature is that this slows down the
mass transfer and hence the rate of reaction. To counteract this decrease, it is
generally recommended that an increased catalyst dosage be used for low
temperature, low trans reaction. If the only change made is to increase pressure the
catalyst dosage can remain the same or may even be reduced.

The reductions in trans content that can be achieved by changing process conditions
are generally far greater than those that have been observed by using novel
catalysts. In fact many of the novel systems under investigation (such as the use of
precious metal catalysts) make use of the process conditions to lower the trans
content.

One commercial example of low trans hydrogenation using PRICAT 9920 is the
production of a stable frying oil with low trans content by partial hydrogenation of
soybean oil. Linolenic content is typically less than two weight percent and the trans
content in is the low teens percent.

Research is ongoing in Johnson Matthey on catalyst that will reduce the trans
content in partially hydrogenated oils. However large reductions on “typical” trans
contents are possible by manipulation of the reaction process conditions.

Summary

The key to reducing the trans content in a partially hydrogenated fat is to have a
higher hydrogen concentration in the oil during the hydrogenation reaction. This will
limit the tendency for carbon-carbon double bonds to open and reform in the trans
isomer. To increase the hydrogen concentration in the oil, a higher hydrogen
pressure and a lower reaction temperature should be employed. A typical example of
these low trans operating conditions would be 10barG hydrogen pressure and 100°C
temperature. However moving in the direction of higher pressure and lower
temperature for any partial hydrogenation will decrease the trans content. An
increased catalyst concentration may be required to keep the reaction time
reasonable and enable the reaction to start at the lower temperature.