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PENGARUH INTERESTERIFIKASI

KIMIAWI DAN ENZIMATIS


TERHADAP BEBERAPA MINYAK
Jurnal Pendukung I: Chemical Intersterification of Blends with Palm Stearin and Patawa oil, 2017,
food chem.,  Sekar Lananingrum
Jurnal Pendukung II: Influence of enzymatic and chemical interesterification of Blends with RBD
Palm oil and Palm Kernel Oil, 2018, food Res. Int.,  Zulvana A. Harvian
SEKAR LANANINGRUM

18/434973/PTP/01634
ZULVANA ANGGRAENI HARVIAN
17/419897/PTP/01562
Global Demand

Palm Stearin RBD Palm Oil RBD Palm Kernel Oil Patawa Oil

HYDROGENATION

INTERESTERIFICATION

CHEMICAL ENZYMATIC
• random interesterification • regioselective or random
• Lower investment and crystallization interesterification
production costs process • depending on the lipase used
• easier to carry out • a very high activity under very
• a tried-and-true approach mild experimental conditions
• Low pressure and temperature
Chemical
Enzymatic interesterification
interesterification
Metode : MPOB Test Metode : MPOB Test
Enzim : Lipozyme TL IM Bahan : NO2, CH3ONa, citric acid, Na2SO4
Pre-treated  de-aerating and drying A liquefied sample was added into a 5.0 L reactor

Interesterification reaction  a 5.0 L glass batch reactor The sample was dried under nitrogen gas at 100 °C. After
equipped with a circulation pump with a mesh at the bottom 60 min, the temperature was lowered to 80 °C and 0.2%
(m/m) of sodium methoxide (CH3ONa) was added
A melted sample was fed into the column of the reactor and
was heated to 70 °C. Interesterifcation reaction  The blend was
heated to 110 °C under nitrogen for 30 min with
The pre-treated immobilised lipase was added into the reactor stirring at 250 rpm.
at 4% (w/w) from the weight of the sample.
After cooling to 80 °C, 5% citric acid solution
Oil sample was drawn from was added for catalyst deactivation
the outlet at the bottom of the reactor after 6 h
The mixture was washed about 3-4 times using excess hot
Product abbreviated as EI water  product abbreviated as CI
MATERIALS AND METHODS

Triacylglycerols
Enzymatic Chemical
Blend preparation (TAG)
interesterification interesterification
composition

Determination of
Crystal Thermal analysis
kinetic Polymorphism
morphology properties
parameters

Calculation of
kinetic Statistical analysis
parameters
Analisis

• Komposisi Asam Lemak


• Indeks Atherogenocity dan Thrombogenocity
• Komposisi TAG
• Analisis Thermal
• Melting Point
• Solid Fat Content
• Konsistensi
a. Komposisi Asam Lemak

• Interesterfikasi tidak merubah komposisi asam lemak


• Nilai UFA/SFA palm stearin = 0,93 cocok untuk bahan interesterfikasi
• Nilai AI dan TI mengalami penurunan setelah proses interesterifikasi
b. Komposisi TAG

• Komposisi TAG menunjukkan terjadinya penyusunan kembali molekul asam lemak pada TAG
• Perubahan signifikan pada SSS dan SSU PPS , POP, PLP, POS (semua sampel)
• Perubahan tidak siginifikan terjadi pada TAG POO
Melting Point

• Terjadi peningkatan melting point pada semua campuran akibat peningkatan kandungan
disaturated dan trisaturated
Analisis Thermal

• Terjadi pergeseran puncak melting point antara sesudah interesterifikasi pada campuran rasio 50 :
50 dan 60 : 40
• Terjadi penurunan energi thermal pada campuran rasio 40:60, 50 : 50, dan 60 : 40
Analisis Thermal

• Terjadi perubahan suhu kristalisasi pada puncak 2 pada campuran rasio 50 : 50 (-4,44 menjadi –
2,76 C) dan 60 : 40 (-2,83 menjadi -0,53 C)
Solid Fat Content

• Campuran rasio 50 : 50 dan 60 : 40 SFC sesuai


untuk functional margarine pada suhu 20-35 ° C
• Campuran rasio 60 : 40 SFC sesuai untuk soft table
margarine pada suhu 25- 35 ° C
• Semua rasio pada campuran tidak ada yang sesuai
dengan SFC table margarine
Konsistensi

• Terjadi penurunan konsistensi pada semua rasio serta pada kedua suhu (5 dan 10 ° C)
• Nilai konsistensi yang sesuai yaitu 200-800gf/cm2 pada suhu 10 ° C campuran rasio 40 : 60
dan 50 : 50 terbaik
RESULTS AND DISCUSSION TRIACYLGLYCEROL COMPOSITION

1. Main TGA of RBDPO  POP, POO, PLO, PLP, PPP and POS (P is palmitic acid, O is oleic acid, L is linoleic acid and S is
stearic acid). a) NI b) EI c) CI

2. Main TGA of RBDPKO  LaLaLa, LaLaM, CaLaLa, CLaLa and LaMM (La is lauric acid, M is myristic acid, Ca is caprylic acid
and C is capric acid). g) NI h) EI i) CI
THERMAL BEHAVIOUR
• Melting of RBDPO-RBDPKO
THERMAL BEHAVIOUR
• Crystallization of RBDPO-RBDPKO
POLYMORPHISM

• RBDPO crystallised in mixture of β′ and β


polymorphs due to the high amount of POP and
PPP.
• RBDPKO crystallised exclusively in β′ form due
to the presence of fatty acids of varying chain
lengths in the TAG.
• no changes in the polymorphic form after CI
and EI of RBDPO and RBDPKO since not much
changes in TAG composition as a result of
intraesterification.
• The presence of POO (β′ former) and PPP (β-
tending) which led to the stability of β′ and β
polymorph mixture in the binary blends.
CRYSTAL MORPHOLOGY
a) NI 100RBDPO-0RBDPKO  Native RBDPO consists of small
plate-like crystals
b) EI 100RBDPO-0RBDPKO  Enzymatic interesterification
formed very fine crystals at 10 °C.
c) CI 100RBDPO-0RBDPKO  Interesterification caused
alteration in the microstructure of RBDPO as CI resulted in
increased of crystal size and loosely-packed crystals.
d) NI 75RBDPO-25RBDPKO
e) EI 75RBDPO-25RBDPKO
f) CI 75RBDPO-25RBDPKO
g) NI 50RBDPO-50RBDPKO
h) EI 50RBDPO-50RBDPKO
i) CI 50RBDPO-50RBDPKO
j) NI 25RBDPO-75RBDPKO
k) EI 25RBDPO-75RBDPKO
l) CI 25RBDPO-75RBDPKO
m) NI RBDPKO Addition of RBDPKO into the RBDPO decreased
n) EI RBDPKO number of crystal and formed loosely packed plate-like
o) CI RBDPKO crystals due to dilution effect of RBDPKO.

 The size and shape of crystals provide a characteristic texture


to the product.
CRYSTALLIZATION KINETICS

• The crystallisation kinetics of RBDPO, RBDPKO and their


binary blends were determined using Avrami equation:

• The equation fitted the data very well with correlation


coefficients of ln [−ln(1-f)] vs ln t plot higher than 0.99.
• RBDPO and crystallised with n = 3 at 20 °C, 22 °C and
25 °C
• Interesterification did not alter the crystallisation
mechanism at those temperatures.
• RBDPKO, the nucleation rate was very rapid at the
beginning with spherulitic growth (n = 3), but crystallised to
n = 2 at higher temperature (25 °C) due to the low melting
point.
• Chemical interesterification changed the crystallisation
mechanisms from n = 3 to n = 2.
• RBDPO and RBDPKO tend to crystallised with an Avrami
exponent of three which represent a sporadic or
heterogeneous nucleation followed by two-dimensional
growth
FINAL CONCLUSIONS
• Interesterifikasi dapat memperbaiki sifat fisik diantaranya sifat termal
dan morfologi krital dari campuran minyak.
• Interesterfikasi kimia pada campuran minyak palm stearin dan patawa
juga dapat memperbaiki nilai nutrisi yang baik karena kandungan
mono unsaturated fatty acid yang tinggi.
• Interesterifikasi enzymatic dapat bekerja secara specific sehingga
memungkinkan kandungan unsaturated fatty acidnya tinggi dan juga
cenderung menghasilkan produk dengan bentuk kristal yang lebih
halus dan lembut.
THANK YOU 
Kesimpulan

• Interesterifikasi kimia dapat digunakan untuk memperbaiki karakteristik


fisik dari campuran antara minyak patawa dan palm stearin

• Rasio campuran terbaik adalah 50 : 50 yang mana dapat memberikan


melting point sesuai, SFC yang sesuai dengan soft table margarine, plastis,
spreadable, memiliki konsistensi pada suhu refrigerasi, serta indeks
atherogenositas dan trombogenositas yang baik
CONCLUSIONS

• CI resulted more prominent changes in the TAG composition of RBDPO-PKO blends as compared to EI due to
random rearrangement of the fatty acid on the glycerol backbone.
• The changes in TAG composition influenced the thermal properties and crystal morphology, but the
polymorphism and crystallisation kinetics were not affected by interesterification.
• CI displayed higher complete melting and crystallisation temperature due to the reduction in high melting TAG.
• EI led to finer and small crystals while CI produced larger crystals size.
• EI blends are more preferable in the formulation of hardstock for margarine as compared to CI.
• EI blends are more natural than CI blends, with new and improved melting profile. This is because Lipozyme TL
IM is a sn-1,3 specific lipase, thus, the fatty acids at the sn-2, which is generally rich in essential unsaturated fatty
acid, is preserved.
• Blends with < 50% of PKO are more suitable since their Tm are close to human body temperature (< 37 °C) and
have lower Tc as compared to CI, which indicate better spread ability at refrigerator temperature.
• EI 50 RDBPO-PKO produced finer crystal (20 μm to 30 μm) that gives smoothness and mouthfeel desired in the
product.

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