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Preparation and application of heterogeneous catalyst based on KOH

impregnated activated carbon from rubber seed kernel for biodiesel synthesis

Article in IOP Conference Series Earth and Environmental Science · December 2022
DOI: 10.1088/1755-1315/1115/1/012081

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4th International Conference on Natural Resources and Technology IOP Publishing
IOP Conf. Series: Earth and Environmental Science 1115 (2022) 012081 doi:10.1088/1755-1315/1115/1/012081

Preparation and application of heterogeneous catalyst based on

KOH impregnated activated carbon from rubber seed kernel
for biodiesel synthesis

Iriany, Taslim*, O Bani, A Aldi and S Rahmadani

Department of Chemical Engineering, Faculty of Engineering
Universitas Sumatera Utara, Medan 20155, North Sumatera, Indonesia

*Email: [email protected]

Abstract. Research to explore the potential of rubber seeds kernel as a carbon source for the
preparation of heterogeneous catalysts has been carried out. This study aimed to characterize
rubber seed kernel carbon, impregnate it with KOH, and apply it as a heterogeneous catalyst in
biodiesel synthesis. In this research, rubber seed kernel was powdered then carbonized in a
furnace for 4 h at 500℃, followed by activation with HCl for 1 h and dried. The resulting
activated carbon was impregnated with KOH solution for 3 h at 80℃. After pre-drying, it was
calcined at 500℃ for 3 h. The rubber seed kernel powder, activated carbon, and KOH
impregnated carbon were characterized using SEM-EDX and FTIR. KOH impregnated carbon
was used as a heterogeneous catalyst in coconut oil transesterification for biodiesel synthesis.
The parameters studied were catalyst load (2 - 4%) and reaction temperature (55 - 65℃). Molar
ratio of oil to methanol and time were set at 1:9 and 2 h, respectively. The highest yield (96.43%)
was obtained at 3% catalyst load and reaction temperature of 60℃.

1. Introduction
Indonesia is one of the countries with enormous rubber plantation. Rubber plantation area in Indonesia
is reaching 3.683 million hectares, but it mainly produces latex as raw material for rubber industry.
Aside of latex, rubber plantations also produce rubber seeds, up to 1 kg/m2. Rubber seed contains 40 –
50 %wt. oil composed of palmitic acid (13.11%), stearic acid (12.66%), arachidic acid (0.54%), oleic
acid (39.45%), linoleic acid (33.12%) and other fatty acids. Meanwhile, rubber seed kernels are currently
underutilized and only become plantation waste. Rubber seed kernel ash contains carbon (64.45%),
hydrogen (8.23%), nitrogen (3.63%) and sulphur (0.32%) [1]. The high carbon content of rubber seed
kernel enables its use as raw material for activated carbon.
Activated carbon has low alkalinity. As such, it cannot be directly employed as catalyst for biodiesel
production. For such usage, activated carbon needs to be modified through alkaline impregnation.
Alkaline, such as KOH, are easily attached on the surface of activated carbon because there are many
micropores. The bond on activated carbon is inert and the surface is easy to modify. Thus, it is suitable
as a catalyst support [2].
Preparation of carbon-based catalyst usually goes through several stages, namely carbonization,
activation, impregnation, and calcination. Carbonization is usually affected by temperature and depends
on the type of raw material used [3]. Activated carbon can be made from lignocellulosic-biomass

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Published under licence by IOP Publishing Ltd 1
4th International Conference on Natural Resources and Technology IOP Publishing
IOP Conf. Series: Earth and Environmental Science 1115 (2022) 012081 doi:10.1088/1755-1315/1115/1/012081

through thermal decomposition or carbonization. During the process, decomposition of volatile matters
in material will trigger pores formation.
Carbon activation is carried out using HCl solution. Metals and other impurities dissolve in HCl,
resulting in increased number of pores. In addition, the volume and diameter of the pores also increase.
KOH impregnation aims to bind potassium ions to activated carbon surface and can shift the activated
carbon surface morphology [4]. The time required for impregnation varies depending on the carbon
source and the type of metal ion used. Additionally, it also depends on carbonization temperature and
the concentration of KOH used [2]. KOH impregnated carbon can act as heterogeneous catalyst for
biodiesel production. Some advantages of such catalyst are it is easy to obtain, cheap, easy to separate
from liquid phase products, has high activity and selectivity, and can be reused [5].
Catalyst supports based on biomass for biodiesel production have been published in literatures, such
as shea nutshell [2], candlenut shell [4], flamboyant pods [6,] nipa palm shell [7], palm shell [8] and
coconut shell [9]. So far, the utilization of carbon from the rubber seed kernel (RSK) as catalyst support
for transesterification has not been carried out. Therefore, this study aimed to investigate RSK as carbon
source, impregnate it with KOH, and examine it as heterogeneous catalyst in biodiesel
transesterification.

2. Materials and Methods

2.1. Materials
Coconut oil was obtained from vegetable oil shop in Medan. Rubber seed kernel (RSK) was obtained
from Labuan Batu Utara, Sumatera Utara. KOH and methanol were supplied from local market.

2.2. Catalyst preparation

Rubber seed kernel (RSK) is cleaned of dissolved impurities through washing with water. Then it was
dried at 130oC for 2 h in an oven followed by milling and sieved to 100 mesh to produce rubber seed
kernel powder (RSKP). A furnace operated for 4 h at 500oC was used to carbonize RSKP [4]. The
residual carbon was leached with 0.1 N HCl at a ratio of 1:6 (w/v) and neutralized with deionized water.
The activated carbon formed was dried for 2 h at 120oC in an oven. Ten g activated carbon was
impregnated with 50 g KOH dissolved in 150 mL water for 24 h at ambient temperature and agitation
speed of 250 rpm. KOH impregnated carbon was filtered and dried in an oven and calcined in a furnace
at 500oC for 3 h. SEM-EDX and FTIR were used to characterize the resulting carbon which was ready
to be used as catalyst in biodiesel synthesis.

2.3. Transesterification
Fifty g oil was added into a flask fitted with a thermometer and condenser. Methanol was mixed with
catalysts in a glass beaker for 60 min. Then, this mixture was added into the flask and heated to 55 –
65oC under constant stirring speed of 350 rpm for 120 min [4]. The amount of methanol was adjusted
to molar ratio of oil to methanol (MROM) 1:9 and catalyst load was varied from 2 – 4wt.% of the oil.
After transesterification, mixture was separated by filtration and purified by washing. The purified final
product was examined for methyl ester content, density and viscosity, and values were compared to
available standards.

3. Results and Discussion

3.1. SEM-EDX analysis
Figure 1 depicts RSK, RSKP, and carbon from RSKP. RSK and RSKP is light brown, while the carbon
was black.

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4th International Conference on Natural Resources and Technology IOP Publishing
IOP Conf. Series: Earth and Environmental Science 1115 (2022) 012081 doi:10.1088/1755-1315/1115/1/012081

(a) (b) (c)

Figure 1. (a) RSK, (b) RSKP and (c) carbon from RSKP

Figure 2 depicts surface morphology of RSKP before and after carbonization using SEM. In
Figure 2(a), RSKP surface was irregular and has empty spaces or cavities between solid particles and
the pores are not clearly visible. In Figure 2(b), activated carbon from RSKP, carbonized at 500oC for
4 h and activated with HCl solution, formed very clear pores compared to pre-carbonized RSKP. HCl
solution can dissolve impurities on the carbon surface, enlarging pore surface which is important as
attachment sites for potassium during KOH treatment [4].

(a) (b) (c)

Figure 2. SEM analysis of (a) RSKP, (b) activated carbon from RSKP and (c) the KOH
impregnated carbon

In Figure 2(c), KOH impregnated carbon had reduced surface area because the pores are occupied
by potassium. During impregnation, potassium ion diffuses into the carbon pores. It is then calcined or
thermally activated to remove moisture and aid potassium adherence to catalyst surface.
EDX results of RSKP, activated carbon from RSKP, and the KOH impregnated carbon are in Table 1.
In Table 1, the constituent of RSKP and activated carbon from RSKP are mainly C and O, and several
other elements in trace amounts such as Cu, Zr and K. Carbon composition increased after carbonation
from 59.31 to 88.02%. During carbonization, volatile matters are thermally degraded thus pores are
formed and carbon surface area is increased. In addition, the fused carbon will produce more stable
bonds while the other components are degraded or vaporized [10]. After impregnation treatment with
KOH, carbon composition decreased from 88.02 to 53.20% because it reacted with KOH to form K2O
and K2CO3 [11]. Both compounds formed, K2O and K2CO3, are active components that catalyze the
transesterification reaction.
C + KOH → K2O + K2CO3 + 2H2
C + K2O → 2K + CO
2C + K2CO3 → 2K + 3CO

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4th International Conference on Natural Resources and Technology IOP Publishing
IOP Conf. Series: Earth and Environmental Science 1115 (2022) 012081 doi:10.1088/1755-1315/1115/1/012081

In Table 1, potassium content of the activated carbon increased after impregnation with KOH. This
confirms that potassium has been well dispersed on the activated carbon surface. This phenomenon has
also been reported in several literatures [8,12]. Potassium composition in RSKP was initially negligible
but increased to 1.18% after carbonization and increased to 17.93% after impregnation with KOH.
Table 1. Elemental composition of RSKP, the activated carbon and the impregnated carbon
Composition (%)
Element
RSKP Activated carbon Impregnated carbon
C 59.31 88.02 53.20
O 39.94 10.04 24.36
Cu 0.31 0.40 0.78
Mg - 0.06 0.12
Al - - 0.15
Si - - 2.96
Zn - 0.31 0.50
K - 1.18 17.93
Zr 0.43 - -

3.2. FTIR analysis

Figure 3 shows FTIR results of carbon from RSKP before impregnation in the black spectrum and
carbon after KOH impregnation in the red spectrum. Carbon before KOH impregnation had lower peak
intensity than the activated carbon after impregnation. The appearance of a peak at wave number
1353 cm-1 in the red spectrum indicates the formation of a carbonate group (-CO3). Potassium carbonate,
K2CO3 is the carbonate compound formed on activated carbon after impregnation with KOH [13].
Modification of activated carbon with KOH, can neutralize the carbon surface [11]. In addition, there is
also a K-O bond indicating that there is K2O at wave number of 649 cm-1 [14].

K-O

-CO3

Figure 3. FTIR analysis

3.3. Transesterification
In order to study the effect of catalyst load on biodiesel yield, the catalyst load was varied in the range
of 2-4% at MROM 1:9, 120 min and 60oC. In Figure 4, biodiesel yield maximized at 3% catalyst load.
More active sites are available as catalyst amount is increased, leading to better contact with the reactant
and resulting in higher yield. However, further increase in catalyst amount renders the reaction mixture
viscous and difficult to stir, increasing mass transfer resistance which reduce yield [15-17]. The use of

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4th International Conference on Natural Resources and Technology IOP Publishing
IOP Conf. Series: Earth and Environmental Science 1115 (2022) 012081 doi:10.1088/1755-1315/1115/1/012081

3% catalyst load was the optimum condition with 96.43% yield. This biodiesel yield is close to that
using carbon catalyst from candlenut shell which yielded 96.65% [4] but superior to that using carbon
catalyst from flamboyant pods at 89.81% [6].

Figure 4. Biodiesel yields at various catalyst loads

Several runs were carried out to examine the effect of temperature on biodiesel yield. Observations
were made by adjusting the reaction temperature from 55 – 65oC at 3% catalyst load, reaction time of
120 min, and MROM 1:9. In Figure 5, as reaction temperature increased from 55 to 60oC, the biodiesel
yield also increased due to higher collision rate between reactant molecules. In addition, the oil viscosity
decreases which lower mass transfer resistance, thus accelerating reaction and increasing yield.
However, at 65oC yield decreased due to methanol vaporization. The same incident was also reported
by other researchers [9,18]. The highest yielding temperature in this research was 60oC with a yield of
96.43%. Some researchers also proposed that highest yielding temperature was 60oC [9,14].

Figure 5. Biodiesel yields at various temperatures

3.4. Biodiesel Properties

Some of the biodiesel properties were analyzed and were found to meet the European standard (EU
14214) as in the following Table.

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 4th International Conference on Natural Resources and Technology IOP Publishing
IOP Conf. Series: Earth and Environmental Science 1115 (2022) 012081 doi:10.1088/1755-1315/1115/1/012081

Table 2. Biodiesel properties

Properties This study EN 14214
Methyl ester content % 99.17 ≥ 96.5
Density kg/m3 872 860-900
Kinematic viscosity mm2/s 4.79 3.5-5.0

4. Conclusion
RSK can be used as a carbon source via carbonization. After calcination and KOH impregnation, the
carbon catalyst contains K2O and K2CO3 as active compounds which catalyze biodiesel
transesterification. Highest yield of 96.43% was achieved at 3% catalyst load, MROM 1:9, 60oC and
120 min. The biodiesel obtained has also met the European standard.

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