Hydrogenation of Fatty Acids

Introduction
Oils and fats are essential nutrients in both human and animal diets. The principle
source of oils and fats are meats, poultry, fish, dairy products, fruits and nuts.
Major components of oils and fats are triglycerides i.e. esters of glycerine and
fatty acids (Fig 1). The properties of different triglycerides (oils and fats) are
dictated by the chain length of the fatty acid (mostly C4 - C24) and as well as the
presence of number of double bonds per molecule.
H
1 2 3 4
5
6
7 8
9 10 11 12 13 14 15 16 17 18
|
H-C-O-OC-CH2-CH2-CH2-CH2-CH2-CH2-CH2-CH2- CH2-CH2-CH2- CH2-CH2-CH2-CH2-CH2-CH3
|
H-C-O-OC-CH2-CH2-CH2-CH2-CH2-CH2-CH2-CH = CH-CH2-CH2- CH2-CH2-CH2-CH2-CH2-CH3
|
H-C-O-OC-CH2-CH2-CH2-CH2-CH2-CH2-CH2-CH = CH-CH2-CH = CH-CH2-CH2-CH2-CH2-CH3
|
H

Fig. 1 :

Structure of triglyceride (oil) molecule i.e. an ester of

glycerine and 3 fatty acids (say C18)

Mainly, fatty acids are obtained from hydrolysis of triglyceride (oil) and glycerine is
generated as byproduct. Distillation of free fatty acid from crude oil also generates
fatty acids, which are tough to hydrogenate. Unsaturated fatty acids are
hydrogenated and used as raw material to manufacture large number of oleo
chemicals.
H
|
H-C-OH
|
H-C-OH
|
H-C-OH
|
H

1 2

10

11 12

13

14 15 16

17

18

HO-OC-CH2-CH2-CH2-CH2-CH2-CH2-CH2-CH2-CH2-CH2-CH2-CH2-CH2-CH2-CH2-CH2-CH3 Stearic
HO-OC-CH2-CH2-CH2-CH2-CH2-CH2-CH2-CH = CH-CH2-CH2-CH2-CH2-CH2-CH2-CH2-CH3 Oleic
HO-OC-CH2-CH2-CH2-CH2-CH2-CH2-CH2-CH=CH-CH2-CH=CH-CH2-CH2-CH2-CH2-CH3 Linoleic

Glycerine

3 Fatty Acid Molecules of C18 Chain

Fig. 2 :

Glycerine and fatty acids obtained after hydrolysis of

triglyceride (oil) molecule

Hydrogenation of various feed stocks

Fatty acid part of triglycerides having double bonds is susceptible to attack by
atmospheric oxygen, resulting in rancid odour, which is not acceptable to
consumers. Unsaturated fatty acid molecules having 2 - 4 double bonds
(unsaturated) are hydrogenated fully to convert the double bonds into single
bonds (saturation).
Hydrogenation of C18 unsaturated fatty acids (oleic, linoleic or linolenic) give
stearic acid which has large number of industrial applications. In todays world,
fatty acids are hydrogenated using supported nickel metal as most appropriate
catalyst to remove the unsaturation. Though supported noble metal catalyst could
be used for similar applications, nickel catalyst offers comparatively higher
performance / price ratio.
Stearic acid manufacturers use selective nickel catalyst for complete
hydrogenation of unsaturated fatty acids. The product with lower iodine value has
large number of industrial applications i.e. in the manufacture of tyres, fatty
alcohols and cosmetics. If the product has negligible degree of unsaturation (I.V.
< 0.5), it offers stability in products with high temperature applications. Large
number of soap manufacturers use partially hydrogenated rice bran fatty acid (IV
95 - 97 to 50 - 55) in their formulations. In case of fatty acids (palm fatty acid)
which are naturally available with lower iodine value (50 -55), further
hydrogenation might be less relevant.

Fig. 1 : Stearic acid used in tyres

Fig. 2 : Fatty acid used in soaps

Monarch Catalyst Pvt. Ltd. has developed indigenous technology for the
production of dry reduced nickel catalyst for hydrogenation of edible oils and fatty
acids. Now, it is a market leader in manufacture of different grades of such
specialty nickel catalysts in India. Nickel catalysts available in international
market were frequently collected and their performance was compared with
Monarch catalysts in the laboratory on different oils and fatty acids. Though the
hydrogenation conditions viz., reactor size, stirring efficiency, temperature and
pressure varies from plant to plant, the catalyst consumption and reaction
selectivity follow the trend observed in the laboratory test methods.

Palm Fatty Acid Distillate (PFAD)

The free fatty acid present in crude palm oil (not linked to glycerine) is removed
either by alkali treatment or by vacuum distillation. The fatty acid removed from
distillation is obtained as light brown solid at room temperature and it melts to
brown liquid on heating. Some of the volatile impurities present in crude palm oil
are transferred to fatty acid during distillation. Therefore, hydrogenation of palm
fatty acid distillate (PFAD) to stearic acid gives a product with a final I.V. of 6 - 7
with relatively higher concentration of nickel catalyst dosage. Further lowering of
I.V. (to around 4 - 5) is achieved by carrying out distillation of the fully
hydrogenated product.

MONCAT 1991 is selective catalysts for hydrogenation of PFAD with initial I.V. of
55 57 to a desired lower iodine value of 5 -6.

I.V.

PFAD

16
14

Intl Ref-2

12
10
8

Intl Ref-1

6
4
1.4

Fig. 3 :

MONCAT 1991

1.8

2.2

Cat (kg/T)

2.6

Hydrogenation of Palm Fatty Acid Distillate

Degummed (P = 14 bar, T = 180 195 C, time =
80 min)

During fatty acid hydrogenation, a side reaction between nickel / nickel oxide and
carboxylic group of fatty acid results in formation of undesired nickel soap. Loss
in nickel as nickel soap could be minimized by carrying out hydrogenation reaction
at higher hydrogen pressure.

MONCAT 1991 = Catalyst for complete hydrogenation of fatty acid

MONCAT 2991 = Catalyst for partial hydrogenation of fatty acid

Palm Stearine Fatty Acid (PSFA)

Splitting of a) crude palm oil or b) curde palm stearine (CPS) or c) refined,
bleached, and deodorized palm stearine (RBDPS) gives glycerine and palm
stearine fatty acid (CPSFA or RBDPSFA) as the main product. The palm stearine
fatty acid obtained free from impurities is hydrogenated from initial iodine value of
about 32 to a very low iodine values of 0.5 - 0.8. Further distillation of such low
I.V. product results in achieving a very low I.V. i.e., 0.3 - 0.4, which is a premium

product. The nickel catalyst MONCAT 1991 is selective for hydrogenation of

palm stearine fatty aid (PSFA) into stearic aid.

I.V.

CPSFA

7
6

Intl Ref-2

5
4

MONCAT 1991

3
2
1
0
0.5

Fig. 4 :

Intl Ref-1
1.0

Cat (Kg/T)

1.5

2.0

Hydrogenation of Palm stearin fatty acid

(P = 20 bar, T = 180 195 C, Time = 70
min.)

During hydrogenation of softer substrate (RBDPSFA), iodine value less than 1.0 is
achieved at catalyst dosage of 1.0 kg/MT itself. Therefore, it is important to refine
palm stearine effectively before splitting it into palm stearine fatty acid to lower the
catalyst requirement for hydrogenation.

Rice Bran Fatty Acid

Rice bran oil (RBO) is extracted from the bran and it is known to contain higher
concentration (> 20%) of free fatty acid / phophatides. During physical refining of
RBO, free fatty acid (FFA) is distilled out to get rice bran fatty acid (RBFA).
However, splitting of RBO and vacuum distillation of fatty acid gives comparatively
whitish or light pinkish RBFA with minimum impurities. Hydrogenation of RBFA is

carried out to get lower iodine values (3 - 5) using MONCAT 1991. Distillation of
hydrogenated product (stearic acid) results in further lowering of I.V. to 1 2.

I.V.

RBFA

25
20

Intl Ref-2

15 MONCAT

1991

10

Intl Ref-1
5
0.6

Fig. 5 :

0.8

Cat (kg/T)

1.2

1.4

Hydrogenation of Rice Bran fatty acid (P = 14

or 20 Bar, T = 180 -190 C, time = 120 min)

Post Hydrogenation Filterability

When compared with competitors catalysts for filterability after hydrogenation

MONCAT catalysts gives quite comparable results when tested under identical
conditions (i.e. using same filtration equipment & other parameters).
Filtration Time (min)
30
25

MON C AT

20

Std C at

15
10
5
0
0

40

80

Oil Filtered
(ml)
5

120

160

Study of Nickel Soap Formation

During fatty acid hydrogenation, nickel or nickel oxide species of the catalyst
reacts with carboxylic group of fatty acid which results in formation of undesirable
nickel soap. Though the nickel content as nickel soap in the final product is found
to be in the range of 80 - 90 ppm, it is much less in the freshly hydrogenated fatty
acid.

A) During storage of hydrogenated product

Holding time of product in hot condition before filtration should be as low as
possible to bring down nickel ppm in the final product. The effect of holding time
on soap formation is shown below:
Product storage time
Immediately after hydrogenation
10 minutes
15 minutes
20 minutes
25 minutes
After completion of filtration (& cooling)

Ni soap (Ni ppm) in product

44.1
50.6
54.8
59.0
63.4
91.2

B) Due to Hydrogenation at varying reaction conditions

Comparatively lower reaction temperature and high pressure restrict nickel soap
formation. In case of inevitable longer holding or transfer time, it is important to
cool the product rapidly (~ 100 C) to minimise the nickel soap formation.
Substrate = Fatty Acid, Ni Dosage = 500 ppm and Reaction Time = 80 min
Varying reaction
Ni ppm at different hydrogenation pressure
Temp (OC)
Atm
5 Bars
10 Bars
25 Bars
100
38 ppm
24 ppm
9 ppm
< 2 ppm
135
98 ppm
76 ppm
52 ppm
29 ppm
185
311 ppm
204 ppm
112 ppm
63 ppm

MONCAT catalysts handling Information

Physical form:

MONCAT catalysts are manufactured in pastil form. The pastils are nothing but
small droplets made up of dispersion of active metal species in hydrogenated
vegetable oil (solid at room temperature). Catalyst pastils are not only easy to
handle but also give no dusting while transferring or charging the catalyst. Also,
coating of metal with vegetable fat renders active nickel metal less prone to
exposure to air and thereby minimizes loss in activity during storage.

Packaging:
Catalyst pastils are packed in standard metal and HDPE bags / drums. Also, they
are packed in customer specific packaging materials (Small bags, Jumbo bags &
Paper bags) to match the handling facility / practices at the customer end.

Shelf Life:
Catalyst stored in closed container retains performance for minimum one
year.
Store catalyst in cool and dry place.
Refer our MSDS for safety instructions.
Catalyst is Kosher Certified

Our Global Sales Partners

South East Asia & China:
Greenwell Global Chemicals Sdn. Bhd.
18 Jalan Bulan H U5/H Seksyen U5,
Sungai Buloh Batu 3,
40150 Shah Alam, Selangor, Malaysia.
Contact Person: Mr K H Tan
Ph: + 60 3 7846 8625 / 7846 9387
Fax: + 60 3 7846 8867
E-mail: greensc@tm.net.my

Europe:
H B International SAS
26 bis rue de l'Ermitage - BP 31,
95160 Montmorency, France.
Contact Person: Mr Valery Desroches
Ph: +33 1 3934 6614
Fax: +33 1 3412 4960
E-mail: valery.desroches@hbint.com

North America:
Mega Sourcing Inc
IL USA & KL Malaysia
Contact Person: Mr Dale Moline
Ph: +60 12 326 7763
E-mail: dmoline@pd.jaring.my

Factory & Head Office:

Monarch Catalyst Pvt.Ltd
A-94 MIDC Phase I, Dombivli (East),
Thane 421 203, Maharashtra, India.
Contact Person: Mr.Krishnan Muthukumar
Ph: +91 251 2471716
Fax: +91 251 2470269
E-mail: info@monarchcatalyst.com