WHAT DO WE DO WITH THE CRUDE OIL BEFORE WE

USE?
Refining 'Modification'
crude oil

hydrogenation
degumming
fractionation
neutralization interesterification

bleaching (blending)

deodorization

refined oil
HYDROGENATION
 Quick Refresher on Chemistry
fats: ester of 3 fatty acids with glycerol

glycerol saturated (stearic acid)

'cis' unsaturated (oleic acid)

'trans' unsaturated (elaidic acid)

hydrogen
carbon
oxygen
 What is Hydrogenation?

H H
H2 & catalyst
'cis' C C
saturated
R R
H H
isomerization H C C H
R R
H R
'trans' C C
H2 & catalyst
R H
 Why Hydrogenation?
1. Selective removal of PUFAs (POLYUNSATURATED
FATTY ACIDS)
• improvement of oxidative stability
2. Create trans fats
• changes a liquid oil into a solid fat
• specific melting characteristics
3. Have a source of saturated fats
• used as feedstock for interesterification
 H H

R
C C
R
'Catalysis'
1 H-H
H H 1
C C H H nickel atoms
2
R R
1. adsorption
H H catalyst carrier 2. first H insertion
C C H H (isomerization)
R R 3
3. second H
insertion
H H R
4. desorbtion
C C H
R 4
H
 Catalyst
• Small particles
– 10-100 m
– smaller , more effective, but harder to filtrate
• Usually Ni on porous material
– 100-200 m2/g
• Put in solid fat for easy dosing
 Triglyceride Meltingpoints

triglyceride mp 80

' melting point (oC)

saturated
(oC) 60
cis,cis-c18:2 (l) -25 40
cis-c18:1 (O) -10
20
trans-c18:1 (E) 16 di-unsaturated
0
c12:0 (L) 35 mono-unsaturated

c14:0 (M) 46 -20

20 30 40 50 60 70
c16:0 (P) 56
# of carbons in the triglyceride
c18:0 (S) 64
 Trans Fats' Unique Selling Point:
Steep Melting Curve
100
mp 80
trans

solids (%)
mp
60
SSS 64
OSS 42 ESS 57 40
saturated
OSO 43 ESE 43 20 slope

OOO -10 EEE 37 0

10 20 30 40
temperature (oC)
 Soybean Oil
100
6 %sat %trans
80 5 1 16
solids (%)

4
60 2 19 20
3 21 17
40
4 21 64
3
20 5 32 53
2
0 1 6 99

10 20 30 40
temperature (oC)
 Hydrogenation of Super Olein
100 %trans
13
80 high trans 18
solids (%)

21
60 24
27
40 31
33
20 low trans
34
super olein
0 35

10 20 30 40
temperature (oC)
 A Typical Reactor
stirrer: 2 kW / ton!
H2
• 5-20 m3
• 1-5 bar
• 120-180 oC
• 0.1-0.5 wt% catalyst
• gas sparged from bottom
• batch!

heating /
cooling coil

sparger
 Process
reuse
hydrogen catalyst spent catalyst bleaching earth

bleaching
oil reactor droptank filterpress vessel /
filterpress

heat exchange spent

bleaching earth
+ Ni residue
 Fatty Acids: Clinical Study of Health Effects

• Replace 1% of carbohydrate energy in diet with

fat
• measure HDL and LDL
– HDL: ‘good’ cholesterol, as high as possible
– LDL: ‘bad’ cholesterol, as low as possible

• ratio total / HDL should be as low as possible

 Comparing the Fatty Acids
(total / HDL) 0.06

bad 0.04
trans
0.02
SAFA MUFA PUFA
0

-0.02
good
-0.04
MUFA and PUFA most benificial; trans is bad!
Mensink et al. Am J Clin Nutr 2003;77:1146–55
 In Summary
• Hydrogenation: change melting behaviour
– trans fats: good functionality / bad for health
• Process
– large scale
– batch
– economics: catalyst reuse
• Economical source of saturated fatty acids
 introduction by P&G
of Crisco
first veg. oil shortening
Whale oil production high trans!!
1000
thousand barrels
800
600
first commercial
400 hydrogenation process

200
Wilhelm Normann
patents fat hardening 0
1900 1905 1910 1915
year

J.N. Tonnessen, A.O. Johnsen, The History of Modern Whaling, Univ. of California Press, 1992
 Pressure group
2006: Mandatory trans content
on packaging (US)

May 2003: Kraft promises to

remove trans fats from Oreo's

Trend: consumption of trans

fats must be reduced further
Challenge: achieve equal functionalities by (combinations)
of other processes
•fractionation
•interesterification of (liquid oil + fully hardened fat)
SUCCESS, AS SIMPLE AS ABC
= RIGHT ATTITUDE, KNOW THE BASIC, ABLE TO COMMUNICATE

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