Study of Physical Properties of Margarine from Carica Seeds Waste

Oil (Carica Pubescens) and Palm Stearin Oil

Dewi Larasati, Ery Pratiwi dan Ika Fitriana

Semarang University, Faculty of Agricultural Technology, Semarang 59160, Indonesia
*Email: dela_latief@usm.ac.id

ABSTRACT

The aim of this study is to determine the physical properties of various margarine
ratios comprised of Carica Dieng seed oil and palm stearin oil with interesterification
system. The experimental design used in this study is the completely randomized design
with 5 different Carica seed oil: Palm Stearin oil ratios, A1= 70:30, A2= 60:40, A3=
50:50, A4= 40:60 and A5= 30:70, wherein each ratios underwent 5 trials. Based on the
analysis of the physical properties (melting point, stability of the emulsion, spreadability
and texture) of the margarines produced, the results showed that the different carica seed
oil: palm stearin oil ratios significantly affect the physical properties of the resulting
margarine. Melting point (77.60 - 85.30 ° C), the stability of the emulsion (44.00 -
70.00%), spreadability (8.99 - 20:13 cm) and texture (15.23-24.21 g). Conclusively this
study has shown that different ratios of Carica Dieng seed oil: palm oil stearin, produce
different physical properties of margarine.

Keywords: Seeds, Carica, Oil, Stearin, Margarine

1
 INTRODUCTION

Carica seed oil is obtained from the extraction of carica dieng seed wastes of Dieng
carica candied fruit processing in Wonosobo-Central Java. According to Larasati et al (2010), the
yield of dieng carica seed oil using n-hexane solvent is 33.33%. Thus, dieng carica seed oil has
the potential to be used as cooking oil. One of the utilisation of carica seed oil as cooking oil is in
a form of margarine.
Margarine is an emulsion with water-in-oil (w/o) emulsion type. That is, the
water phase is in the oil or fat phase. It is more easily digested in the body than non-
emulsified fats such as cooking oil (Ketaren, 1986). Margarine is an emulsion food
product (w / o), either semisolid or liquid formed, made from edible fats and or vegetable-
based oils, with or without chemical changes including hydrogenation and
interesterification that have also been purified, as the main ingredient as well as water and
permissible food additives (Indonesian National Standard, 2002). In its manufacture,
margarine requires solid fat, one of which is stearin oil palm.
The stearin fraction is a by-product obtained from palm oil along with olein
fraction. Stearin can be used as hard fat (Gunstone, 2005) as well as low trans hard stock
for margarine (Sahri and Idris, 2010). Stearin can also be used to replace the demand for
animal fat and it also serves as shortening fat or frying fats (Basiron, 2005). Stearin as
the raw material for margarine must meet SNI 01-0021-1998 food standard with RBD
quality requirement for stearin is 0.15% maximum free fatty acid content, 40 g iod / 100
g maximum iod number, 0.1 ppm maximum arsenic contamination and 0.1 % maximum
water and dirt content. Standard RBD stearin must be met if stearin is going to be used
to make a food product. The chemical properties and physical properties of these
margarine fats are highly dependent on the composition of the ingredients. Hence, this
research will study the physical properties of margarine made from dieng carica seed oil
with palm stearin oil using interesterification process done at room temperature. In the
interesterification process, by adding a catalyst to the fatty margarine feedstock,
interesterification reactions will occur faster despite low temperatures, while the cost of
production is much cheaper. With the interesterification process, the margarine produced
will be free of trans-fat that easily dissolve in body temperature. Accordingly, the
resulting maragarin is also safer because it does not contain saturated trans fatty acids.
The purpose of this research is to know the physical properties of margarine from various
dieng carica seed oil and palm strearin oil ratios using the interesterification process.

2
 REASEARCH METHOD

The raw materials involved in making the margarine are ieng carica seeds obtained
from Dieng, Wonosobo regency of Central Java and pal stearin oil from PT Sinergi Oleo
Nusantara Medan, North Sumatra. Chemicals used in the analysis process include:
sodium ethoxide, citric acid, KOH, n-hexane, acetic acid, Chloroform, Benzene,
NH4CNS, Na2S2O3 and FeCl2 purchased from PT. Brataco Chemika – Laboratory
Chemistry Products Semarang.
The equipments used in this study include are electric stirring vessels, cabinet
driers, rotary vacuum evaporators, spectrophotometers, ovens, gas chromatography units
and glassware for analysis purposes.

Experimental Procedure
Initially, Dieng seed extract was obtained using n-hexane solvent. The oil obtained
is then purified through neutralization, deodorization and decolorization processes. Dieng
carica seed oil with stearin was stirred for several minutes at room temperature to blend.
Ratios of each substance blended sown in Table 3. To the mixture of raw fatty materials
of the margarine, 0.2% sodium ethoxide catalyst was added and stirred using an electric
stirrer at a rate of 1500 rpm for 60 minutes (interesterification). To deactivate the catalyst,
10 mL of citrate acid 20% was added to solution then stirred for 15 minutes. The reaction
product is separated using a separatory funnel and the top layer acquired was extricated.
Subsequently, homogenazation of the oil phase and the fraction dissolved in oil – i.e. the
emulsifier in the homogeniser – was done for 15 minutes. Then, 80% of the oil phase and
20% of the water phase were homogenized for 30 min at temperature of 50-60 o C. Further
crystallization was done by cooling with ice shards (15-20 oC) to obtain margarine.

Carica Seed Oil

Stearin
Kelapa Sawit

3
 Blending
A1= Dieng carica seed oil: stearin ratio (70:30)
A2= Dieng carica seed oil: stearin ratio (60:40)
A3= Dieng carica seed oil: stearin ratio (50:50)
A4= Dieng carica seed oil: stearin ratio (40:60)
A5= Dieng carica seed oil: stearin ratio (30:70)

Sodium Ethoxide catalyst 0,2 %

Stirred for 60 minutes at a rate of 1500 rpm

Citrate Acid 20%

Stirred for 15 minutes at a rate of 1500 rpm

Phase separation with separatory funnel

20 % water + 80 % oil phase

Mixed with
homogenizer for 30 minutes

Crystalisation (15-20 oC)

Analysis : melting point,

Margarine emulsion stability,
spreadibiliy and texture

Figure 1. Schematic of Experimental Procedure

4
Experimental Design
This research was conducted using Completely Randomized Design of
Experiment iterated 5 times under 5 different raw materials ratios as follows:
A1= Dieng carica seed oil: stearin ratio (70:30)
A2= Dieng carica seed oil: stearin ratio (60:40)
A3= Dieng carica seed oil: stearin ratio (50:50)
A4= Dieng carica seed oil: stearin ratio (40:60)
A5= Dieng carica seed oil: stearin ratio (30:70)
The statistical analysis was continued with further test (DMRT) to determine the
influential difference of each treatment. The observed variables were melting point,
emulsion stability, spreadibility and texture. The diagram of experimental procedure
schematic can be seen in Figure 1.

RESULTS AND DISCUSSIONS

Melting Point of Margarine

Analysis of various research results (appendix 2), showed that the ratios of dieng
carica seed oil and palm stearin oil significantly affect (p <0.05) the melting point of the
resulting margarine.

Table 1. Melting point of margarine of various ratios between dieng carica seed oil
and palm stearin oil.
Treatments (carica seed oil : pal stearin oil) Melting Points(o C)
70:30 43,60 a
60:40 43,80 a
50:50 44,20 b
40:60 45,00 b
30:70 45,00 b

5
 Description:
1. Results shown is the average of 5 trials conducted
2. An average that’s followed by a particular superscript shows substantial
differences between treatments (p< 0,05).

Table 1. shows that the resulting margarine melting point ranges from 43,60 –
45,00 oC. And after further test, significant differences was found. The highest melting
point was at the ratio of 30: 70 and the lowest at 70: 30 treatments. The melting points of
margarines produced showed an increasing order 43,60; 43,80, 44,20 dan 45,0 oC,
respective to the ratio order shown in the table. The more stearin added to the mixture the
higher the melting point. According to Hastuti (2003) palm stearin has a melting point of
52-54 oC. When compared with the melting point of stearin, the melting point of the
margarine produced from carica seed oil and stearin palm oil is higher. According to
Sudarmadji (1989), fat is a mixture of triglycerides, thus, fat does not have a clear melting
point but rather in a range of temperature because oil and fat are not pure compounds but
a mixture of triglycerides with specific and unique variations depending on its source.
The experimental results gathered by Mariati S (2001) showed that the margarine melting
point of cocoa butter, RBD of palm oil and hazelnut oil by interesterification, ranged from
33.0 – 54.95 oC.
The increase of the melting point of margarine is reciprocal to the increase of palm
stearin oil content. According to Larasati et al (2013), the melting point of carica seed oil
ranges from 5.33 – 8.66 oC while stearin has a slip melting point of about sekitar 44.5-
56.2oC and a boiling point of above 230°C, whrein the melting point is within the range
of slip melting point. This causes the higher the stearin content, the higher the melting
point. According to Lestarai (2010), analysis of the melting point of margarine ranges
from 55 ° C to 58 °C, based on the analysis conducted on two brands of margarine and
one brand of butter on the market. The resulting melting point found is as follows:
Blueband margarine 44 °C, Palmboom margarine 54 ° C and Weissman butter 42 ° C.
The analysis of the melting point of margarine in various proportions of tuna fish oil and
palm stearin oil and the addition of BHA antioxidant at various concentrations shows that
the melting point ranged from 31.70 ° C - 43.70 ° C (Ramadhana, 2016).

6
Emulsion Stability of Margarine
The result of analysis of variance showed that the emulsion stability of the various
margarines produced from carica seed oil and stearin palm oil displayed valid effects (p
<0,05). Table 2 revealed that the margarine emulsion stability of various carica seed oil
and palm stearin oil ratios is significantly different. The resulting margarine emulsion
stability tested ranged from 44.00 - 70.00%. The highest margarine emulsion stability
was found at the ratio of 50: 50 with 70% result and the lowest at 30: 70 ratio with 40%
result. This is because palm stearin oil is saturated fat which at room temperature is solid,
so at the time of mixing between oil / fat phase and water phase, emulsifier (lecithin)
cannot be dispersed. Factors affecting emulsion stability are: low interfacial tension,
mechanical strength and interfacial layer elasticity, electric double layer repulsion, small
relativistic dispersion phase.

Table 2. Emulsion stability (%) of Margarin of various ratios between dieng carica
seed oil and palm stearin oil.
Treatments (carica seed oil : pal stearin oil) Stability (%)
a
70:30 47,50
b
60:40 59,00
c
50:50 70,00
b
40:60 61,00
a
30:70 44,00
Description:
1. Results shown is the average of 5 trials conducted
2. An average that’s followed by a particular superscript shows substantial
differences between treatments (p< 0,05).

The stability level of margarine mixture of carica seed oil and palm stearin at
first increased with the increase of palm stearin oil up to ration of 50: 50, but after ratio
of 40: 60 there was a decrease of emulsion stability. According the research conducted

7
by Fitriyaningtyas and Widyaningsih (2015), the increase in stability is influenced by
emulsifiers and the higher the emulsifier concentration the more stable it will become.

According to Ramadhana et al (2016), the stability of margarine emulsion showed

an increase in the proportion of fish and stearin oil at 50: 50, but decreased with content
comprised of 40% tuna and 60% stearin oil, with the exception of the addition of BHA
antioxidants 200 ppm treatment. The emulsion stability test results qualitatively show that
all the resulting margarine has a stable emulsion below 0 ° C (stored in refrigerator).
However, when heated in an oven at 45 ° C, margarine product that was added with local
lecithin (soy protein isolate) is more stable than the margarine added with imported
Iecithin (extracted from egg yolk). In margarine containing imported lecithin, it appears
to be separated into layers of liquid and clan oil (Lestari, 2010)

Spreadability of Margarine

The result of analysis of variance showed that the various margarines produced from
different carica seed oil and stearin palm oil ratios displayed significant influence towards
its spreadibility (p <0,05).

Tabel 3. Spreadibility (cm) of margarin of various ratios between dieng carica seed
oil and palm stearin oil
Treatments (carica seed oil : pal stearin oil) Spreadibility (cm)
d
70:30 20.13
c
60:40 14.78
bc
50:50 12.53

40:60 10.11 ab

30:70 8.99 a
Description:
1. Results shown is the average of 5 trials conducted
2. An average that’s followed by a particular superscript shows substantial
differences between treatments (p< 0,05).

8
 Table 3 indicates that the spreadibility of carica seed oil and palm stearin oil mixture
ranged from 8.99 to 20.13 cm. The highest spreadibility of margarine was found at a ratio
of 70: 30 (20.13 cm) and the lowest at a ratio of 30: 70 (8.99 cm). In other words, the
higher the stearin ratio the lower the spreadibility. Research done by Ramadhana et al
(2016) showed that there was a decrease in spreadibility in respect to the increase of
stearin content in the formulation of margarine with fish oil. It was also said that the
difference of spreadibility is caused by the physical properties of stearin which is formed
out of saturated fat that has fatty acid chains with the presence of double bond on the
chain of carbon atoms so as to cause it to have a solid state at room temperature, a harder
texture and a high melting point. The mixing of stearin and liquid fish oil causes a semi-
solid plastic effect, in which the characteristics depends on the proportion of both
substances.
Spreadibility decreases in proportion to the increase of palm stearin oil. Palm stearin
oil is largely consisted of saturated fat, so the higher the stearin the higher the saturation.

Margarine Texture

The result of analysis of variance showed that the various margarines produced from
different carica seed oil and stearin palm oil ratios displayed significant influence towards
the structure of margarine. The range of margarine texture obtained was 15.23-24.21 g
(Tabel 4).

Tabel 4. Margarine texture (g) Margarin of various ratios between dieng carica seed
oil and palm stearin oil
Treatments (carica seed oil : pal stearin oil) Texture(g)

70:30 15.23 a

60:40 17.27 a

50:50 17.50 a

40:60 22.40 b

30:70 24.21 b

9
 Description:
1. Results shown is the average of 5 trials conducted
2. An average that’s followed by a particular superscript shows substantial
differences between treatments (p< 0,05).

In Table 4 it can be seen that the higher the ratio of carica seed oil, the lower the
texture produced and the higher the palm stearin oil ratio the higher the texture. High
texture values acquired gave the margarines firmer consistency whereas lower texture
values gave the margarines softer consistency. The lowest texture value was found at the
ratio of 70: 30 (15.23 g) and the rest of texture value obtained were 60: 40 (17.27 g),
50:50 (17.50 g), 40: 60 (22.40 g), with the highest at 30: 70 ratio (24.21 g).
Based on spreadibility and texture test, margarine product with addition of imported
lecithin and margarine product with local lecithin both adequate level of spreadibiliy and
texture(Lestari, 2010). It is also said that based on organoleptic test, the texture of
margarine product containing Iocal lecithin is more preferable because it resembles the
margarine sold in the market which are Blueband and Palmboom brands.
The increase in texture of margarine in respect to the increasing amount of palm
stearin oil is caused by the fact that palm stearin oil is solid at room temperature.
Furthermore, it is also due to the process crystallisation in the making of the margarine
so that blending of oil and water phase with the help of lecithin strengthen at low
temperature. Crystallization is done by cooling the oil and water phase mixture after the
homogenization process.

CONCLUSIONS

Based on this research, it can be concluded that:

1. Ratios of carica seed oil and palm stearin oil have significant effect on physical
properties of lmargarine, i.e. melting point, emulsion stability, spreadibility and
texture.
2. The results showed that the physical properties of margarine obtained were melting
point within the range of 43,60 – 45,00 oC, emulsion stability with 44.00 - 70.00

10
 percentage range, spreadibility range of 8.99 - 20.13 cm and texture range of 15.23-
24.21 g.
3. From the test conducted, the margarine with the best stability has carica seed oil to
stearin palm oil ratio of 50:50 with physical properties as follows:
44,20 oC melting point, 70.00 % emulsion stability, 12.53 cm spreadibility and 17.50
g texture.

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