Jurnal Bahan Alam Terbarukan

http://journal.unnes.ac.id/nju/index.php/jbat

Clove Oil Extraction by Steam Distillation and Utilization of Clove Buds Waste as
Potential Candidate for Eco-Friendly Packaging

Paramita Jaya Ratri, Meri Ayurini, Khabib Khumaini, Azka Rohbiya

DOI: https://doi.org/10.15294/jbat.v9i1.24935

Department Chemistry, Faculty of Science & Computer Science, Universitas Pertamina, Jalan Teuku
Nyak Arief, Simprug, Kebayoran Lama, 12220 Jakarta, Indonesia

Article Info Abstract

Article history: As a tropical country which has abundant of spices, Indonesia is challenged to increase the
Received economic values of spices commodity in raw material form (wet or dry). One way to raise
April 2020
the economic values of these commodities is by modifying into its derivatives. Clove is one
Accepted
of spices commodity which can be processed furthermore into an essential oil. By
June 2020
Published transforming clove from raw material to essential oil, the economic value increases from 2
June 2020 to 20 times per kilogram. In this present research, the extraction time of clove oil using
Keywords : steam hydro distillation is reported. The distillation procedure was conducted in various
Clove Buds; times, that was in 3, 4, 5, and 6 hours. Furthermore, the clove oil sample that obtained from
Essential Oil; optimum extraction time was characterized using FTIR and GCMS. Then the result was
Steam compared to the commercial clove oil (100 % of purity). In support of sustainability
Hydrodistillation; process, then the clove buds waste from steam distillation were challenging to be one of
Eco-Friendly eco-friendly packaging candidates. Two compositions of waste and additional material
Packaging have been investigated in this study. It found that the best composition was composed of
clove buds waste powder: recycled paper (7:3). During the casting process, some additives
material was added such as tapioca (20%) and chitosan (1 %) in acid solution in order to
improve its mechanical properties. Furthermore, thermal degradability of the eco-friendly
packaging was studied. It was started to degrade at 286.58oC. According to this research,
the cloves buds’ cardboard was quite potential to be developed as commercial eco-friendly
packaging.

INTRODUCTION et al., 2005), anticarcinogenic (Ali et.al., 2019),

antiallergic (Koshak, 2019), and antimutagenic
Clove (Syzygium aromaticum), one of activity (Miyazawa & Hisama, 2001).
Indonesian native species, is an aromatic flower In general, essential oils are composed of
buds. Java and Manado are parts of the largest terpenes and aromatic polypropanoid compounds.
clove productions in Indonesia. Beside used as Several techniques for essential oil isolation have
cooking ingredients directly, clove can be proceed been reported including hydrodistillation, steam
furthermore as medicinal properties. As medicinal distilation, solvent extraction, supercritical CO 2
effect, clove buds need to undergo the extraction extraction (Frohlich et al., 2019; Guan et al.,
process to obtain the essential oil. Several 2007), and so on. Guan et al. (2007) reported that
researchers have been studied the medicinal Eugenia caryophyllata Thunb., one of clove species,
application of clove such as on dental care are composed around twenty three identified
(Mandava et al., 2019), effective against a large compounds by gas chromatography using mass
number of other bacteria Eschericia coli (Friedman spectrometry detection (GC-MS). This result is
et al., 2002; Cressy et al., 2003), antifungal (Chami similar to Jirovetz et al. studies (2006). Basicly, the
© 2018 Semarang State University

Corresponding author: ISSN 2303-0623
Department Chemistry, Faculty of Science & Computer Science, Universitas Pertamina,
e-ISSN 2407-2370
Jalan Teuku Nyak Arief, Simprug, Kebayoran Lama, 12220 Jakarta, Indonesia
E-mail: [email protected]
 Paramita Jaya Ratri, Meri Ayurini, Khabib Khumaini, Azka Rohbiya / JBAT 9 (1) (2020) 47-54

primary compound in clove oil is Eugenol (Guan Mechanical properties of eco-friendly paper
et al., 2007; Jirovetz et al., 2006). Eugenol is useful candidate were conducted by Material Strength
as antioxidant (Ogata et al., 2000) and insecticidal Testing, Zwick Roell Z100. Thermal degradation
properties (Lambert et al., 2020). Ayoola et al. of eco-friendly paper candidate was measured by
(2008) reported about the antimicrobial activity of Discovery-650 SDT (Simultaneous DSC-TGA).
clove oil (Syzygium aromaticum). They isolated the
clove oil from the dry flower buds by steam Methods
distillation until no more difference in successive
readings of the light yellow oil volume. The yield Extraction of Clove Oil
percentage of the clove oil isolation was around Steam hydro distillation is selected as a
7% (w/w) (Ayoola, et al., 2008). method to isolate clove oil. A twenty-five gram (25
In this present paper, to support the g) of dried clove buds was put in steam flask as
sustainability process, we studied the isolation shown in Figure 1. The steam distillation was
process of clove oil by steam hydro distillation. conducted in several times such as 3, 4, 5, and 6 h.
Beside, we studied to utilize the residue of the The time started to be counted when first drop of
clove oil extraction as an eco-friendly packaging. distillate comes out. Then, the collected distillate
was extracted furthermore with n-hexane as
MATERIALS AND METHODOLOGY solvent using separatory funnel. Clove oil was
obtained by evaporating the n-hexane.
In this present study, the used materials
and methods are described as follows.

Materials

Chemicals
The raw material of clove buds
(Syzygium aromaticum) which was used in this
research was a species from Magelang, Central
Java, Indonesia. Chemicals including solvents
were used in extraction of essential oil process,
production of eco-friendly packaging candidate,
or during characterization. N-hexane technical
grade 96%, acetic acid glacial p.a. 100%,
ethanol p.a. 99.9%, and acetone p.a. 99.0% were Figure 1. Steam Hydro Destillation Set
purchased from Merck Chemicals. Chitosan
Characterization of Clove Oil
which was used for pulp production was
industrial grade with 30 to 80 mesh of particle The composition and characteristic of
size from CV. ChiMultiguna. The used paper clove oil were determined by using FTIR and GC-
was added so that mechanical properties MS spectrum analysis the results were then
improvement. The type of used papers in the compared to commercial product of clove oil
experiment is an HVS 80 gr. (100% purity). Some drops of clove oil were
measured by ATR-FTIR mode in order to check
Instrumentations the similarity based on functional groups of
Instrumentations such as Gas compounds. Beside ATR results, GC-MS has been
Chromatography Mass Spectrometer (GC-MS), used to measure the clove oil contents based on
Fourier Transform Infrared (FTIR), Universal mass-to-charge (m/z). The separation of clove oil
Testing Machine (UTM), and Thermogravimetric was conducted by TraceGOLDTM TG-1MS
Analysis (TGA) were used for characterization column (length 30 m; ID 0.25 mm; film thickness
and testing. The essential oil contents were 0.25 m). A 1 L of 1% diluted sample in
detected by Thermo Trace 1310 GC with Mass methanol was injected into the column using split
Spectrometer Thermo ISQ Single Quad Detector ratio of 1/50. Gradient elution has been applied to
and FTIR Spectrometer System Nicolet iS 5 in the instrument method so that gives good
Attenuated Total Reflectance (ATR) mode. separation for its compounds. At first, the system

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 Paramita Jaya Ratri, Meri Ayurini, Khabib Khumaini, Azka Rohbiya / JBAT 9 (1) (2020) 47-54

was equilibrated to 50oC. Then, the temperature heated from ambient temperature to 600oC by
was gradually raised to 100oC by rate 10oC/min 20oC/min heating rate.
and hold for 1 min, followed by gradually raised to
140oC by rate 5oC/min and hold for 1 min, to RESULTS AND DISCUSSION
160oC by rate 2oC/min and hold for 1 min, and
finally to 245oC by rate 5oC/min and hold for 1 Clove Oil Extraction And Characterization
min. The mass-to-charge (m/z) of clove oil In this present study, clove oil was
compounds were detected by electrospray extracted by steam hydro distillation method in
ionization mode (EI). The temperature of ion several hours followed by separatory funnel
source was maintained at 250oC, while injector extraction of the distillate using n-hexane. The
and detector temperatures were programmed at yield percentage are shown in Figure 2. According
280oC. The sample was eluted and separated along to Figure 2, the observed maximum yield of clove
the column by helium gas as mobile phase with oil extraction was achieved in 6 hours, which the
flow rate 1 mL/min. The chemical compounds of yield was 7.04 %. However, in this experiment,
clove oil are identified by comparing its m/z to longer experiment time need to study furthermore.
their mass spectra library (NIST MS).
8
Eco-Friendly Packaging Candidate Preparation 7.04
Clove bud’s residue from clove oil 6
extraction were collected and utilized furthermore
% Yield

as eco-friendly packaging candidate for supporting 4

the sustainability of industrial process. In general, 2.92
the process was divided into three main steps such 2

as making concentrated paper pulp, casting, and 1

0 0.28
drying. First, the clove buds waste was dried and
2 3 4 5 6 7
grinded to obtain a powder form. A 70 g of clove Extraction Time (Hours)
powder was mixed and blended together with 30 g Figure 2. The obtained Yield Percentage
of shredded used papers, 20 g tapioca flour Extraction of Clove Oil using Steam
commercial, and 1% of chitosan in 100 mL of Hydro distillation Method in Several
Hours.
acetic acid solution. In order to get the best pulp
casting, the water content was needed to reduce by
heating process. The eco-friendly packaging was commercial
made by pulp casting method. By casting and
Transmitance

drying, a thick paper which cardboard look like

was produced. extracted

Mechanical and Degradation Testing

The mechanical properties of clove bud’s
cardboard were analyzed furthermore by
comparing commercial cardboard and styrofoam. 1700 1500 1300 1100 900 700 500
Its properties were studied using material strength Wavenumber (cm-1)
testing (Zwick Roell Z100). Modified ASTM D638
Figure 3. FTIR Spectra of Obtained Extraction
was used as a standard method. The pre-load was
and Commercially Available of Clove
set to 0.1 MPa, while test speed and tensile Oils
modulus were 5 mm/min. Grip to grip separation
at the start position was 90.00 mm, and elongation The clove oil which collected for 6 h by
preset was 1 %. Degradation ability of the clove steam hydro distillation was characterized using
bud’s cardboard was analyzed by thermal process. FTIR and then compared to the commercially
The thermal degradation was studied by thermo- available clove (Syzygium aromaticum) oil (100
gravimetric analysis Discovery-650 SDT % pure) spectra. The comparison of FTIR
(Simultaneous DSC-TGA). The sample was spectra is shown in Figure 3. According to the

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 Paramita Jaya Ratri, Meri Ayurini, Khabib Khumaini, Azka Rohbiya / JBAT 9 (1) (2020) 47-54

Figure 4. Chromatography Spectra of Obtained and Commercially Available Clove Oils

Table 1. Chemical composition of clove oil from local traditional market from Java Island and
commercially available clove oil.
Commercially Available
Obtained Clove Oil
No. Compounds 100% Pure Clove Oil
RT % Area RT % Area
1 Methyl Salicylate 14.33 0.06 14.29 0.05
2 Chavicol 16.00 0.19 15.98 0.04
3 Eugenol 18.99 85.01 18.98 81.35
4 α-ylangene 20.27 0.04 20.23 0.11
4 Caryophyllene 21.55 1.14 21.52 5.05
5 Humulene 22.61 0.18 22.58 0.76
7 Eugenyl Acetate 23.93 13.06 23.90 12.50
8 Caryophyllene Oxide 26.88 0.32 26.83 0.14

FTIR spectra, by comparing the extracted clove results obtained either of extracted clove buds’ oil
buds’ sample and commercial essential oil sample, or commercially available clove oil, which are
both of samples have high similarity spectra which composed of two major compounds. The two
are around 98.88% of similarity. Therefore, it can major components are eugenol and eugenyl
be concluded that the extracted clove buds oil acetate. The eugenol and eugenyl acetate contain
contains of similar constituent compounds to the in extracted clove buds’ oil are around 85.01% and
commercially available clove oil. 13.06%, respectively. The percentage of these two
Moreover, the clove buds oil contents compounds are slightly different for commercially
were investigated by GC-MS spectroscopy. The available clove oil. In commercially available clove
chromatography spectra are shown in Figure 4. oil, the eugenol contents are 81.35% while eugenyl
According to GC-MS spectra, there are two major acetate 12.50%. These results are consistent to
constituents separated based on mass-to-charge literatures that eugenol contains in clove oil is
ratio (m/z). The detailed compounds that found in around 70-80%. According to these results,
clove buds’ oil are pointed out in Table 1. Similar Eugenol is the highest abundance in clove oil

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 Paramita Jaya Ratri, Meri Ayurini, Khabib Khumaini, Azka Rohbiya / JBAT 9 (1) (2020) 47-54

which is around 80 %. This constituent was weight. From 70 g of clove buds waste, it produced
reported as the most responsible components of three sheets of cardboard with size of 32.8 x 20.9
clove buds that have a medicinal application cm2. The resulted piece of candidate green
(Milind & Deepa, 2011). Moreover, both clove oils packaging of clove cardboard is shown in Figure 5
also contain caryophyllene and humulene. Percent with 0.33 mm in thickness. The texture of the
area of these components is in the middle cardboard is smooth on the back side and rough on
compared to the rest constituents (Santin et al., the front side. Apparently, the clove bud cardboard
2011; Amelia et al., 2017). According to the data is as hard as the other cardboard but slightly
from GC-MS, clove oil also has some minor brittle. The clove cardboard has a signature scents
compounds such as methyl salicylate, chavicol, as clove essential oil. It is quite good of structure
caryophyllene oxide, and α-ylangene which was which looks like cardboard with unique odour. Up
also reported in literatures (Amelia et al., 2017). to nine months, there is no change in colours and
no being mouldy when it is stored in dry place.
Utilization of Clove Buds Waste as a Potential
Candidates for Eco-Friendly Packaging
Since one of the components of clove buds
is cellulose, then clove buds waste from clove oil
isolation process can be utilized furthermore as a
piece of paper for environmentally friendly
packaging. This study will be supporting industrial
process sustainability. In this research, some trial
and error in composition of clove buds waste and
some additives were conducted in order to find the
best percentage to obtain good piece of hard paper.
Beside the clove buds waste as a main component, Figure 5. Piece of packaging cardboard from
the shredded used paper and some additive were clove buds waste (left: back side, right:
added to improve its mechanical properties. The front side).
additive material which used in this present study
are tapioca flour and chitosan. Tapioca flour is Furthermore, the mechanical properties of
chosen as thickener while chitosan can be having a clove bud’s cardboard were investigated using
role as an antimicrobial agent and an adsorbent. In tensile strength testing. For comparison, a
addition, both of tapioca flour and chitosan are commercial cardboard and Styrofoam were used.
quite cheap. The result is shown in Figure 6. According to the
At first, a 100 g of clove buds waste, 20 g curves in Figure 6, clove buds cardboard has
of tapioca, and 1 g of chitosan in 1% acetic acid ultimate tensile strength of 1.48 MPa. This is three
solution were blended and casted. However, from times higher when compared to Styrofoam (0,40
this composition, the casting paper result was very MPa) but under a half of commercial cardboard
brittle, perforated, and difficult to remove from the (3.34 MPa). However, percent elongation before
template without being broken. The break point for our sample was 2.11%. It was quite
characterization was difficult to perform. In order short compared to both Styrofoam and cardboard.
to increase its mechanical properties, the clove bud Therefore, in the next study, improvement in the
waste was decreased and combined with used percentage of elongation by addition of plasticizer
paper. In this study, the casting process was is needed.
successful by blending a 70 g of dried powder clove The thermal degradation was also studied
buds waste with a 30 g of shredded used paper by Thermal Gravimetric Analysis (TGA).
then added some additives such as tapioca (20 g) Degradation temperature was observed up to
and 1% chitosan in 1% acetic acid solution. This 600oC. Figure 7 shows at first the water
composition was obtained a cardboard look like. contentwill be vaporized. Then start at 286.58oC,
In each clove oil extraction time, around 25 g of the clove bud’s cardboard start to degrade up to
dried clove buds were used. The extraction process 369.50oC. Finally, at 600oC the mass of clove buds
produced waste almost the same as original paper decreased up to 27.63% of residue.

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 Paramita Jaya Ratri, Meri Ayurini, Khabib Khumaini, Azka Rohbiya / JBAT 9 (1) (2020) 47-54

Commercial Cardboard
3 E = 30.6097 MPa
s = 3.3456 MPa
Stress (MPa)

Clove Buds Cardboard

E = 11.8961 MPa
1 Styrofoam
s = 1.4881 MPa
E = 15.5026 MPa
s = 0.4034 MPa

0
0 2 4 6 8
Elongation (%)
Figure 6. Tensile Strength Test of Clove Buds Cardboard, Commercial Cardboard, and Styrofoam
Container.

100

Mass : 13.975 mg
80 % Mass : 95.736%
Onset : 286.58 oC
End : 369.50 oC
Midpoint : 326.06 oC
Weight (%)

60

Residue : 4.034 mg
40 % Residue : 27.631%

20
0 100 200 300 400 500 600
Temperature (oC)
Figure 7. Thermal degradation ability testing of clove paper by Thermal Gravimetric Analysis

CONCLUSSION supporting the sustainability process, the clove

At the present research, steam hydro buds waste was successfully proceeds become an
distillation was used as a method to isolate clove eco-friendly packaging as a cardboard. According
oil. According to the result, we need to lengthen to the mechanical properties, the clove bud’s
the extraction time to observe the optimum result. cardboard has quite good ultimate tensile strength,
By increasing the extraction time from 2 to 6 1.48 MPa. However, this candidate of packaging
hours, the % yield also increased. The longest needs to be improved by adding a plasticizer. The
extraction time is 6 hours which has yield clove bud’s cardboard started to degrade by
percentage around 7.04%. Both of clove oil which heating at 286.58oC.
collected from experiment and commercially
available have similar characteristic of their ACKNOWLEDGMENTS
constituents. Two major components of clove oil
are eugenol and eugenyl acetate, which have % This study was supported financially by
area around 80 % and 12 %, respectively. By Kementerian Riset, Teknologi, dan Pendidikan

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Tinggi Republik Indonesia (Kemenristek DIKTI)) Salmonella Enterica. Journal of Food

2018. Protection. 65(10): 1545-1560.
Frohlich, P. C., Santos, K. A., Palu, F., Cardozo-
AUTHOR’S CONTRIBUTIONS FIlho, L., da Silva, C., da Silva, E. A.
Paramita Jaya Ratri and Meri Ayurini 2019. Evaluation of the effects of
equally contributed of the presented idea, temperature and pressure on the
developed the theory, verified the analytical extraction of eugenol from clove
methods, wrote the manuscript. Khabib (Syzygium aromaticum) leaves using
Khumaini supervised the project. Azka supercritical CO2. The Journal of
Rohbiya carried out the experiment. All authors Supercritical Fluids. 143: 313-320.
discussed the results and contributed to the final Guan, W., Li, S., Yan, R., Shaokun, T., Quan, C.
manuscript. 2007. Comparison of essential oils of
clove buds extracted with supercritical
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