Tech Edible Oil 3nd

Jurusan Teknologi Hasil Pertanian
Fakultas Pertanian Universitas Lampung

elaborated under certain conditions by particular moulds that can grow on grains,
seeds, and nuts (47). If present during processing, they can contaminate oils that are
derived from these sources.
Regulations on maximum allowable levels for these contaminants have been
legislated in various countries: heavy PAHs5 mg/kg and for sum of heavy and
light PAHs25 mg/kg, German Society for Fat Science (45); dioxins0.75 pg
TEQ
WHO
/g fat in the EU (50) where TEQ
WHO
means Toxic Equivalence expressed
as the sum individual toxicities for 17 toxic polychlorinated-p-dibenzo dioxins and
furans as identied by the World Health Organization; aatoxin B
1
5 mg/kg (51)
in the EU. Regulatory limits for PAHs, PCBs, and dioxins have not yet been set in
the United States; the Food and Drug Administration (FDA) has established an
action level of 20 ppb for aatoxins in human foods (52).
4.1. Effect of Lipid Constituents on Oil Quality;
Determination of Oil Quality
Trace constituents in oils are removed (or destroyed) in varying degrees during
rening, bleaching, and deodorization steps. Figure 7 summarizes the various steps
in oil processing and the major constituents removed in each of them. The main
objectives of oil processing are to enhance appearance, avor, and oil stability
and to ensure safety for human consumption.
Phospholipids, if not removed from oils before deodorization, can lead to
dark-colored oils and serve as off-avor precursors (53, 54). Chlorophyll (55),
pheophytins and pyropheophytins (56), and metal ions (57, 58) are prooxidants
that decrease oil stability. Iron and copper at levels as low as 0.01 and 0.1 ppm,
respectively, are capable of lowering avor and oxidative stability (59). Free fatty
acids, besides representing a rening loss, have also been shown to act as prooxi-
dants (60) and to lower smoke points (61) of oils during frying. Linolenic acid has
Figure 7. Major impurities removed by different processing steps.
TRACE CONSTITUENTS IN LIPID OILS AND FATS 299
O I L P U R I F I C AT I O N
1
D E G U MMI N G
DEFINISI:
! Memisahkan/mengeluarkan gum (senyawa phosphate)
dalam minyak kasar (crude oil).
TUJUAN:
! Menmudahkan proses penyimpanan dan pengangkutan.
! Memudahkan proses pemurnian berikutnya (caustic
rening dan bleaching).
! Menghasilkan lecithin.
2
Figure 6. Degumming and lecithin processing.
1
7
DEGUMMING
Crude oil
from
extraction
Filtration Blending Hydration
Centrifuge
separation
Bleaching
Drying
Blending
Drying
Solids Acid
Water
Peroxide
OIL
GUM
Fatty Acids
OIL
LECITHIN
To Bleaching,
caustic rening
D E G U MMI N G
3
D E G U MMI N G
METODE DEGUMMING:
1) Dry Degumming.
! Proses degumming dilakukan bersamaan dengan
proses bleaching.
! Dilakukan pada crude oil yang kandungan gum-nya
sangat rendah, seperti crude coconut oil dan crude
palm kernel oil.
2) Wet Degumming.
! Proses digumming pada minyak yang banyak
mengandung gum (senyawa (hydratable phosphate).
! Gum yang dihasilkan dapat diproses menjadi lecithin.
! Prosesnya: Steam diinjeksikan ke dalam minyak, gum
akan menyatu, dan dipisahkan dengan sentrifugasi.
4
D E G U MMI N G
METODE DEGUMMING:
3) Acid Degumming.
! Ac i d d e g u mmi n g d i l a k u k a n b e r s a ma a n
menghilangkan senyawa phosphate (hydratable dan
non hydrateable).
! Non-hydratable phosphate adalah jenis phospholipid
yang mengandung ion Ca, Mg, dan Fe, dihasilkan dari
ekstraksi b!i-b!ian yang telah mengalami kerusakan.
! Prosesnya: Asam encer (asam phosphate atau asam
sitrat) ditambahkan ke dalam minyak, dilanjutkan
dengan proses hidrasi (injeksi uap panas ke dalam
minyak).
! Pemisahan gum dengan cara sentrifugasi.
! Hasil akhir minyak dengan kadar gum < 3 ppm.
5
D E G U MMI N G
6
D E G U MMI N G
Crude Soybean Oil Degummed Soybean Oil
7
N E U T R A L I S I N G
! Bertujuan untuk menetralisasi atau menghilangkan
asam lemak bebas.
! Disebut juga: Caustic Rening atau Alkali Rening.
! Juga menghilangkan gum dan mineral kalsium dan
magnesium yang tersisa dari proses degumming.
! Proses netralisasi:
a. Larutan alkali (16-24 Be) dicampurkan ke dalam
degummed oil, diaduk dan didiamkan selama 5 menit.
b. Minyak dan sabun dipisahkan dengan sentrifugasi.
c. Minyak masih mengandung sabun sekitar 500 ppm.
d. Minyak selanjutnya dicampur dengan air panas sebanyak
15-20%, untuk mencuci sabun.
e. Minyak dan air sabun di pisahkan dengan sentrifugasi.
f. Minyak hasil netralisasi mengandung sabun <50 ppm,
dan K.A. <0,5%.
8
Figure 7. Caustic rening.
2
2
DI AGRAM ALI R NETRALI SASI
9
B L E A C H I N G
! Merupakan proses pembersihan minyak secara
absorpsi.
! Absorbent yang digunakan karbon aktif (activated
carbon) dan lempung aktif (activated clay).
! Bahan asing yang dipisahkan meliputi:
! Komponen warna (chlorophyll dan carotenoids),
! Gum (phospholipid), Sabun (soap stock),
! Logam (besi, Fe dan tembaga, Cu),
! Komponen hasil reaksi oksidasi.
! Pretreatment bleaching dengan ditambahkan asam
(sitrat dan fosfat) untuk mengikat logam, mencegah
oksidasi.
10
DI AGRAM ALI R BLEACHI NG
Figure 8. Bleaching/dry degumming.
2
6
11
ABSORBENT FOR BLEACI NG
Activated Carbon Activated Clay (Earth)
12
DI AGRAM ALI R BLEACHI NG
13
BLEACHI NG PROCESS
14
D E O D O R I S I N G
! Disebut juga sebagai physical rening.
! Ditujukan untuk mengeluarkan komponen volatile.
! Deodorisasi dapat digunakan sebagai pengganti
proses netralisasi (chemical rening).
! Komponen volatil yang dikeluarkan terdiri:
! Komponen aroma (avor dan tastes dari bahan baku),
! Asam lemak bebas (physical rening).
! Selain menghilangkan komponen volatil, deodorisasi
juga memucatkan warna minyak, pigmen carotenoids
rusak akobat pemanasan.
15
DI AGRAM ALI R DEODORI ZATI ON
Figure 13. (b) Continuous deodorizer.
4
6
16
DI AGRAM ALI R DEODORI ZATI ON
17
1. Deaeration:
Proses pengerluaran udara untuk mencegah oksidasi.
Minyak dipanaskan pada suhu 80
o
C dalam kondisi vakum
(50 mm Hg).
2. Stipping:
Minyak yang telah di deaerasi, dipanaskan dengan steam
hi ngga suhu dan tekanan yang di i ngi nkan untuk
menguapkan komponen volatile impurities (FFA dan odor).
PROSES DEODORI ZATI ON
phosphatide content after degumming (<15 ppm). If not, chemical rening will
yield better results.
Another important factor is the free fatty acid content of the crude oil. In general,
physical rening only becomes advantageous when the acidity of the crude oil is
sufciently high. For relatively cheap oils, like soybean oil, the higher oil yield
with the physical rening is less important than the higher bleaching earth con-
sumption, making chemical rening more attractive. For other unsaturated oils
with a higher value, such as peanut oil and sunower seed oil, physical rening
will be more attractive.
2. DEODORIZATION PRINCIPLE
Although the process is commonly named deodorization, it is actually a combina-
tion of three different effects on the oil: (1) stripping: Stripping of volatile compo-
nents (free fatty acids, odorous compounds, tocopherols, sterols, and contaminants
such as pesticides and light polycyclic aromatic hydrocarbons, etc.), (2) actual
deodorization: Removal of different off-avors, and (3) temperature effect:
Thermal destruction of pigments and unwanted side reactions such as cis-trans-iso-
merization, polymerization, conjugation, and so on.
Optimal stripping parameters (temperature, time, operating pressure, and
amount of stripping gas) are governed by the properties of the ingoing product,
the specications of the outgoing product, equipment limitations, and the need to
minimize costs. In Table 1, some typical deodorization conditions for edible oils are
given. As observed, steam rening applied during physical rening requires more
severe conditions than deodorization in case of chemical rening. This is mainly
because of the removal of FFA by distillation, which is more signicant in physical
rening, as the initial FFA levels are considerably higher.
To obtain the required nal FFA content of 0.030.05% by physical rening, it is
necessary to adjust the operating conditions. The easiest way is to increase the
TABLE 1. Typical Operating Conditions for Deodorization of Vegetable Oils.
Chemical
Physical
Conditions U.S. Europe Europe
Temperature (
C) 250260 220240 230250

Pressure (mbar) 34 23 2
Sparge steam (%) 0.52
(a)
0.51.5 12
Deodorization time (min) 2040 4060 6090
Final acidity (% FFA) 0.030.05 !
Trans fatty acids (%) 0.51 !
Tocopherol loss (%)
(b)
up to 60 max 25 max 25
a
To remove tocopherols, a higher amount of steam is required.
b
For example, for soybean oil in the United States, the minimum is 500 ppm; in Europe, it is 900 ppm.
DEODORIZATION PRINCIPLE 343
18
3. Retention:
Menahan (membiarkan) minyak pada suhu dan tekanan
deodorisasi (stripping) selama 10-30 menit, untuk
menghilangkan pigmen (carotenoid).
Disebut juga dengan Heat Bleaching (bleaching dengan
panas).
4. Scrubbing (Condensation):
Mengkondensasi dan merekoveri komponen volatil (FFA)
menjadi Faty acid destilate.
5. Cooling:
Mendinginkan minyak setelah proses deodorisasi.
Ditambahkan asam sitrat untuk mengikat logam dan
mencegah oksidasi.
PROSES DEODORI ZATI ON
19
H Y D R O G E N AT I O N
Hidrogenasi adalah proses penambahan molekul hidrogen (H
pada ikatan tak jenuh dengan bantuan katalisator.
! Tujuan Hidrogenasi:
1. Meningkatkan stabilitas rasa dan aroma, serta daya
simpan minyak/lemak.
2. Mengubah sifat fungsional minyak/lemak untuk aplikasi
tertentu.
! H2
atas 480
suhu rendah.
! Katalisator Hidrogrenasi: nickel, alumina, silica, platinum,
palladium, rhodium, dan ruthenium.
20
DI AGRAM ALI R HI DROGENASI
Figure 10. Hydrogenation.
3
5
H2 gas

21
Ef ek Hi drogenasi Terhadap As. Lemak
As. Lemak
Rantai
Karbon
Titik Leleh
(
Laju
Oksidasi
Laju
Hidro-
genasi
Linolenat C18:3 -13 150 40
Linoleat C18:2 -7 100 20
Oleat C18:1 cis 16 10 1
Stearat C18:0 70 1 -
Oleat C18:1 trans 44 10 1
22
The manufacture of lightly hydrogenated, winterized soybean oil led to the
new terms selective hydrogenation and selectivity catalyst. Selective hydro-
genation technically denes the preferential conversion of 18:3 18:2 relative to
18:1 >18:0. In practical terms, this process reects the selective removal of double
bonds via hydrogen addition such that saturated fatty acid (stearic) formation is
minimized (7).
Catalyst selectivity is somewhat meaningless unless the term is dened. There
also are selective catalysts that do not meet the technical or practical denition of
hydrogen selectivity. Such catalysts are sulfur-poisoned catalyst. Sulded nickel
catalyst produces high trans-isomers, has lower activity than conventional nickel,
exhibits longer reaction times, and is used for specialty applications (e.g., coating
fats and hard butters).
Most unsaturated bonds in vegetable oils naturally occur in the cis-form. During
partial hydrogenation, part of the cis-isomers is changed to trans-isomers. Trans-
isomers have a dramatically higher melting point (42
C) as compared with cis-

isomers (6
C). The creation of trans-isomers is desirable in margarine oil in that

a higher melting point can be achieved without developing a higher level of nutri-
tionally undesirable saturated compounds. Altering hydrogenation conditions to
produce higher (or lower) trans-isomers is termed trans-isomer selectivity.
Factors inuencing cis-trans-isomerization are shown in Table 2.
A typical hydrogenation converter is shown in Figure 1. The converter is the
heart of the complete hydrogenation system. Proper design and maintenance of the
hydrogen gas distributor, the agitator, and the heating cooling coils are mandatory
for optimum productivity and consistency of basestocks produced. Most conver-
ters are 30,000-pound, 40,000-pound, or 60,000-pound batch sizes with some
now as large as 90,000 pounds. The common agitator design provides approxi-
mately 100 rpm, and radial ow impellers are used. The lower impeller is posi-
tioned slightly above the hydrogen gas distributor; therefore, the diameter of the
gas distributor and the tip-to-tip dimension of the lower impeller are critical.
Originally, the middle and top impellers were of the radial ow type also. Some
converters have now been operating for many years with an axial ow impeller
at the top position. Although the lower and middle radial ow impellers are ideally
suited for gas dispersion, the top impeller pumps the oil downward, and if posi-
tioned properly, hydrogen gas in the headspace re-enters the oil. This design has
enhanced the success of dead-end hydrogenation, dramatically reducing the amount
TABLE 2. Factors Inuencing cis-trans-isomerization.
High trans Low trans
Temperature High Low
H
2
pressure Low High
Catalyst dosage Low High
Agitation Slow Fast
Catalyst Ni-S Ni
INTRODUCTION 387
Ef ek Hi drogenasi Terhadap Trans As.
Lemak
" Proses hidrogenasi, suhu 204
o
C, nickel katalisator 0,02%,
tekanan H2 15 psia, menghasilkan asam lemak trans 44%.
" Proses hidrogenasi, suhu 70
o
C, konsentrasi katalis 0,11%,
dan tekanan H2 250 psia, menghasilkan as. lemak trans 22%.
23
HI DROGENASI
Faktor mempengaruhi laju hidrogenasi:
a. Suhu awal minyak,
b. Suhu reaksi,
c. Aktivitas katalisator,
d. Konsentrasi katalisator,
e. Laju serapan hidrogen,
f. Kemurnian hidrogen,
g. Kualitas minyak,
h. Intensitas pengadukan.
24
I NTERESTERI FI CATI ON
" Didenisikan sebagai:
Penataan ulang susunan asam lemak, baik secara random
atau terarah, dalam trigliserida dengan tujuan untuk
memodikasi sifat minyak atau lemak tanpa mengubah
komposisi asam lemaknya.
" Reaksi transesterikasi dapat terjadi antara minyak/lemak
dengan alkohol, asam, atau minyak/lemak.
1. Alcoholysis: pertukaran dengan mono atau polihidrat
alkohol.
2. Acidolysis: pertukaran dengan asam karboksilat.
3. Methanolysis: pertukaran dengan methanol.
4. Interesterication: Pertukaran dengan trigliserida lainnya.
25
236 Modifying lipids for use in food
reaction can be completed within 30 minutes. The reaction is stopped by the
introduction of water, and subsequent processing usually includes washing,
bleaching and deodorization to obtain the final randomized product.
Figure 11.1 illustrates the difference between chemical and specific lipase-
catalyzed interesterification in two triacylglycerols. For the chemical
randomization of ACA and BBB governed by thermodynamics and statistics,
theoretically all 18 isomers (27 if stereoisomers are included) might be
detected in the end reaction mixture. For comparison, with 1,3-specific lipase-
catalyzed reaction governed mainly by enzyme specificity and dynamics,
only four new isomers (six if stereoisomers are included) are expected,
apart from the original ACA and BBB. The formation of isomers with acyl
group C at the 1- or 3-positions and A at the 2-position of the glycerol
backbone is theoretically impossible if acyl migration can be ruled out. The
randomization of triacylglycerols can also be driven by non-specific lipases,
yielding similar results to chemical interesterification. In practice, only a
very few lipases are strictly non-specific. Most lipases are specific to a
certain extent (Matori et al., 1991). That is to say, the result of the reaction
catalyzed even by a non-specific lipase will not be exactly the same as that
with a chemical catalyst.
The widely used chemical catalysts are Na-K alloy or sodium alcoholate
(e.g. CH
3
ONa). However, they are believed not to be the real catalysts due to
their ease of consumption during reaction. Glycerate is the real catalyst of
interesterification. This mechanism explains the formation of both monoalcohol
ester and diacylglycerol, the latter being formed by glycerate hydrolysis (Ucciani
and Debal, 1996). Dijkstra et al. (2005) proposed a new mechanism in order
to explain the experimental observations.

This mechanism assumes that the
reaction of a base (such as sodium methanolate) with the oil will eventually
lead to the abstraction of an -hydrogen from a fatty acid moiety and that the
enolate anion thus formed acts as the catalytic intermediate. This enolate can
re-abstract a proton from the hydroxyl group of a partial glyceride, whereupon
the resulting alcoholate attacks the carbonyl group. This leads to a new ester
and a glycerolate anion which then regenerates a new enolate anion.
1,3-specific lipase
chemical catalyst
or nonspecific lipase
A
C +
A
B
B
B
A
C +
A
B
B +
B
A
C +
B
A
B +
A
B
B +
A
B
C
B
C C A
C C B
C A C
C B C
B B C
B B A*
B A B
B C B*
A A B
A A C
A B A*
A C A*
A B C
A C B*
B A C
A A A
B B B*
C C C
+ + + +
Fig. 11.1 Schematic illustration of the difference between randomization and 1,3-
specific interesterification, exemplified by the reaction between ACA- and BBB-type
triacylglycerols. Underlined molecules are starting materials and those with star are
possible products for 1,3-specific lipase-catalyzed reaction.
(e.g. CH
3

1,3-specific lipase
chemical catalyst
A
C +
A
B
B
B
A
C +
A
B
B +
B
A
C +
B
A
B +
A
B
B +
A
B
C
B
C C A
C C B
C A C
C B C
B B C
B B A*
B A B
B C B*
A A B
A A C
A B A*
A C A*
A B C
A C B*
B A C
A A A
B B B*
C C C
+ + + +
(e.g. CH
3

1,3-specific lipase
chemical catalyst
A
C +
A
B
B
B
A
C +
A
B
B +
B
A
C +
B
A
B +
A
B
B +
A
B
C
B
C C A
C C B
C A C
C B C
B B C
B B A*
B A B
B C B*
A A B
A A C
A B A*
A C A*
A B C
A C B*
B A C
A A A
B B B*
C C C
+ + + +
Tujuan:
Merubah titik leleh, memperlambat oksidasi, menghasilkan
minyak/lemak yang cocok untuk deep frying dan
pembuatan margarin.
Metode:
! Interesterifikasi Kimia: Menggunakan katalis sodium
metoksi dan logam alkali.
! Interesterifikasi enzim: Menggunakan enzim lipase.
26
11.3.2 Enzymatic acidolysis for the production of structured lipids
Structured lipids (SL), in this text, means fats that are modified or restructured
from natural oils and fats, or the fatty acids therefrom, with regio-positional
preference of each fatty acid or each group of fatty acids in the glycerol
backbone. Structured lipids are designed for a particular functionality or
nutritional property for edible or pharmaceutical purposes. This definition
Fig. 11.4 Morphology of the blend (palm stearin/coconut oil, 70/30) and
enzymatically interesterified products at different degrees of conversion (measured by
HPLC). (Samples with 50 % added rapeseed oil were melted at 70 C, and one drop
was put on a slide. They were then cooled to room temperature. The morphology was
observed after one hour at room temperature by polar light microscopy)
(adapted from Zhang et al., 2004b).
58 %
conversion
31 %
conversion
71 %
conversion
100 %
conversion
Blend
58 %
conversion
31 %
conversion
71 %
conversion
100 %
conversion
Blend
58 %
conversion
31 %
conversion
71 %
conversion
100 %
conversion
Blend
58 %
conversion
31 %
conversion
71 %
conversion
100 %
conversion
Blend
58 %
conversion
31 %
conversion
71 %
conversion
100 %
conversion
Blend
Palm stearin/coconut oil (70/30)
31% conversion
58% conversion 71% conversion 100% conversion
27
of fats). This process has great potential as the ramications of natural versus mod-
ied fats continue to be debated.
Figure 11 depicts a typical interesterication process. This random inter-
esterication uses a reactor quite similar in design (if not identical) to the hydro-
genation dead-end reactor. Oil is heated after being neutralized and dried to around
90120
C and is blended in the reactor with a catalyst, such as sodium methoxide

(0.20.3%) or an alkali metal (0.10.2%). During reaction, the reactants become
orange-brown in color (the rst quality check of reaction process). Once the color
develops, the reaction is normally completed within 30 min, where an equilibrium
exists of the random distribution of fatty acids on the glycerol molecule. When
completed, water is introduced to stop the reaction, vacuum is released, and the oil
discharged to a holding tank. As a soap residue is normally present in the oil, the
mixture may be washed and centrifuged from the oil. The oil is dried and bleached
and deodorized in the normal manner.
Continuous interesterication processes exist but to date none have been com-
mercialized. Interesterication is generally performed in small batches by specialty
processors. An alternate method of increasing interest is directed interesterication
using enzymes. The process is generally applied to palm-oil-based materials such
as cocoa butter substitutes and to coconut oils. There is some concern about the
effectiveness of interesterication with physical rened oils as low levels of FFA
must be present or the reaction will not proceed as planned (5). Although not a
hazardous process, interesterication is often included in the hydrogenation section
of the renery because of the similarity of the reactors.
As the debate concerning health effects of saturated products and that of trans
isomers generated during hydrogenation continues, interesterication may offer a
viable alternative to the rener. Outside the United States interesterication is used
to produce hardened fats without trans isomers. These products are available in
Canada and continental Europe. This technology has been available for quite some
time, as a patent on the product was granted to Unilever in 1961 (22). The ability
to tailor the melting point and functional crystallization characteristics without
Figure 11. Interesterication.
38 A PRIMER ON OILS PROCESSING TECHNOLOGY
Proses:
Minyak (degummed, rened), dipanaskan (90-120
o
C) dalam
vakum, ditambah katalisator (sodium metoksi, 0,2-0,3%:
metal alkali, 0,1-0,2%), reaksi dimulai saat timbul warna
kuning-kecoklatan. Reaksi (30 menit) dihentikan dengan
penambahan air dan pendinginan.
28

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Jurusan Teknologi Hasil Pertanian

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C) 250260 220240 230250

C) as compared with cis-

C). The creation of trans-isomers is desirable in margarine oil in that

C and is blended in the reactor with a catalyst, such as sodium methoxide

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