HYDROGENATION

Hydrogenation

Hydrogenation : To treat oil with H2 and catalyst to decrease double bonds and
increase saturated bonds.

Reaction Result

Saturation of double bonds

Migration of double bonds
Trans-fatty acid formation

Advantages of Hydrogenation

Making fat suitable for manufacture of margarine, shortening, coating fats,

cooking oil and salad dressing oil.

Hydrogenation Reaction Rate

Nature of the substance to be hydrogenated

The nature and concentration of the catalyst
Pressure (reaction) – the concentration of hydrogen
The temperature
The degree of agitation

Hydrogenation of Oils

Steps in Partial Hydrogenation:

Transfer and/or diffusion

Adsorption
Hydrogenation/isomerization
Desorption

Transfer and adsorption steps are critical steps in controlling the degree of
isomerization and selectivity of reactions.

Transfer: Transfer of reactants and products to and from the bulk of the liquid oil
phase and outside surface of the catalyst.

Diffusion: Diffusion of reactant into the pores of the catalyst. Diffusion of products
out of the pores of catalyst.
Postulated Schematic Diagram of Hydrogenation

H H

H2 +
Catalyst Surface

C1 C2 C3 C1 C3
H H H H C2 H
H

C1
H C2 C3 H
H H H

C1 C2 C3

H H H

H H
C1 C2 C3 +

Catalysis

Oil + Catalyst à Oil-Catalyst Complex

Oil-Catalyst Complex + H2 à Hydrogenated Oil + Catalyst

Formation of Double Bond Migration and Transisomers during Hydrogenation

8 9 10 11
H H H H
R1 C C C C R2
H H
(A)

+H . +H .
H H H H H H H H
R1
R
C C . C C R2 R1 C C .
C C R2
H H H H H H
(B) (C)

-H . -H .
-H . -H .
H H H H H H
R1 C C C C R2 R1 C C C C R2
H H H H H H
H H H H
(D) (E)
R1 C C C C R2
H H
(F)
Conjugated Fatty Acids Formation

9 10 11 12 13 14 15 16
C C C C C C C C

9 11 15
C C C C C C C C
OR

10 12 15
C C C C C C C C

OR

9 12 14
C C C C C C C C

OR

9 13 15
C C C C C C C C
 Adsorption: Adsorption of the reactants on the catalyst surface is important in
controlling the selectivity and isomerization during hydrogenation.

Unsaturated Fatty Acid Composition of Partially Hydrogenated Oleic Acid

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Double bond Total unsat. % 100% trans

Trans % % Positional
of isomer
Position (42.5% trans) % total unsat. in trans form
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11 . . . . . . . 7.0 11.2 4.7 67.2

10 . . . . . . . 15.7 23.0 9.8 62.5
9 . . . . . . . 54.5 31.6 13.4 24.6
8 . . . . . . . 15.8 23.0 9.8 62.0
7 . . . . . . . 7.0 11.2 4.7 67.2
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Hydrogenation Scheme

Linoleic acid Oleic acid

Linolenic acid Stearic acid

Isolinoleic acid Isooleic acid

Selectivity

Preferential hydrogenation of more unsaturated acids with minimum formation of

completely saturated fatty acids.

Linoleic acid : Oleic acid

Very selective hydrogenation 50 : 1
Non-selective hydrogenation 4 : 1

Selectivity can be expressed as the ratio KLO/K O, which denotes the relative rate of
hydrogenation of linoleate to that of oleate.
Catalysts

Nickel Catalyst: Nickel on various supports

Commercial Ni Catalyst – 25% Ni in hard fat as flakes

Copper Catalyst:
Copper-Chromium (CUO 50% + Cr2 O3 40% + BaO 10%)
High selectivity for linolenic acid (KLO/K O – 6 to 13)
and almost infinite selectivity for linoleate
Less isomer than the nickel and few conjugated dienes

Copper dispersed on silicic acid. KLO/K O 13 to 18. Hydrogenation can be carried

out to an oleic acid 72% without increase in stearic acid.
Double-bond migration to form conjugated trans-fatty acids.
Reduction of one of the conjugated double bonds.

Example:
9 10 11 12 13 14 15 16
C C C C C C C C

9 11 15
(A) C C C C C C C C
OR

10 12 15
(B) C C C C C C C C

OR

9 12 14
(C) C C C C C C C C

OR

(D) 9 13 15
C C C C C C C C

From the hydrogenation of A; 9, 15 and 11, 15

From the hydrogenation of B; 10,15 and 12, 15
From the hydrogenation of C; 9, 12 and 9, 14
From the hydrogenation of D; 9, 13 and 9, 15
Triglyceride Stereospecificity

Hydrogenation of fatty acids in triglyceride is not a function of their location.

Catalyst Activity

Defined as iodine value decrease per unit of time during a hydrogenation under a
specific set of conditions.

The life of catalyst – how long a catalyst will remain active and useful.

Production of Simulated Olive Oil from Soybean Oil

by Chromium Carbonyl
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Hydrogenated
Soybean Oil Olive Oil

Iodine Value 95.3 77-94

Palmitate (%) 10.3 7-16
Stearate (%) 4.3 1-3
Other Saturates (%) 0.0 0.1-2
Monoene (%) 60.7 65-85
Diene (%) 23.9 4-15
Triene (%) 0.8
Trans-Acids (%) 6.8
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Production of Simulated Cocoa Butter from Cottonseed Oil Stearine by

Chromium Carbonyl
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Hydrogenated CSO, Cocoa
Stearine Fraction Butter

Palmitate (%) 58.0 24.4

Stearate (%) 1.0 35.4
Monoene (%) 37.6 38.1
Diene (%) 3.4 2.1
Trans-Acids (%) 7.2 -
Iodine Value 38.0 36.7
Melting Range (°C) 30-40 24-35
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FACTORS AFFECTING HYDROGENATION
Effects of Pressure and Temperature on Trans-Unsaturation at 80 I.V. Soybean Oil

Effects of Pressure, Temperature, and Catalyst on SR

Effects of Agitation and Catalyst Concentration on SR
Effects of Pressure and Temperature on SR
Effects of Agitation and Catalyst Concentration on Rate
Factors Affecting Hydrogenation

The Relationship between Process Conditions and their Effects on

Selectivity Ratio, Trans-Contents, and the Rates of Reaction

Selectivity Ratio Trans-Content Reaction Rate

Temperature

Pressure

Agitation

Catalyst