SYNERGISTIC EFFECT OF K2O PROMOTER AND CAO:ZNO RATIO ON

K2O/CAO-ZNO CATALYST FOR TRANSESTERIFICATION PROCESS

I. Istadi*, Rahmatika Luthfiani Safitri, Louis Claudia Marpaung

Department of Chemical Engineering, Faculty of Engineering, Diponegoro University,
Jl. Prof. Soedarto, SH, Kampus Undip Tembalang, Semarang, Indonesia 50275

Abstract

Production of biodiesel from transesterification reaction between soybean oil and methanol has been done in this
research. The reaction using base catalyst of solid metal mixture 5%K2O/CaO-ZnO with mol ratio variables 1:1, 1:1.5,
1:2, 1:3, and 3:1 for increased the reaction rate. Preparation of the catalyst started by coprecipitation of CaO-ZnO
using solution of Na2CO3 upon the hotplate with heating temperature 60 oC which last for one night. The result of
coprecipitation process which has been filtered, then dried by oven and calcinated by furnace within temperature 800 oC
for 3 hours. The catalyst then impregnated by 5%K2O promotor using solution of KNO3, furthermore it dried and
calcinated again in temperature 300oC for 5 hours. Additional variables of promotor percentage 1%, 3%, and 7% has
been done on 3:1 CaO-ZnO catayst. The crystalinity of ctalyst 5%K2O/CaO-ZnO then characterized by XRD method
and its basicity tested by basicity test using benzene-titration method. The quality of catalyst is also tested by
transesterification process for producing biodiesel from soybean oil with molar ratio oil methanol 1:15, in 60 oC
temperature, for 4 hours, using mass catalyst 5% weight of oil. The result of biodiesel then tested by GCMS method and
poduce 75,289% for the highest %FAME. The highest yield FAME obtained from catalyst with CaO:ZnO molar ratio
1:2. Basicity test showed that 5%K2O/CaO-ZnO with mole ratioCaO:ZnO 3:1 has the highest basicity. On the other
hand, variable of %K2O shows that catalyst 7%K2O/CaO:ZnO with mol ratioCaO:ZnO 3:1 has the highest basicity.

Key words: K2O/CaO-ZnO, biodiesel, soybean oil, mol ratio, transesterification.

1. Introduction contamination and slower reaction rate, and higher

Biodiesel is a renewable alternative fuel made
from vegetable oils or animal fats. The biodiesel which
is a mixture of fatty acid methyl esters (FAMEs) has
lower emissions than petroleum diesel (Chen et al.,
2011). Biodiesel can be made from fatty acid such as
palm kernel oil, sunflower seed oil (Granados et al.,
2007), soybean oil (Kouzu et al., 2008), few seed oil
(Gryglewicz, 1999) and others. Process of making the
biodiesel was depends on the amount and kind of free
fatty acid (FFA). To get the high FAME of biodiesel,
vegetable oil with low FFA was needed.
Transesterification process occurred on low FFA
amount while the esterification and transesterification
process occur on high FFA amount ( up to 20%) (Abdul
& Achmad, 2014).
. In this research heterogeneous catalyst was
developed because the catalyst can be separated from
the liquid products easily and can be designed to give
higher activity, selectivity and has a longer life time
(Boey et al., 2009; Dehkhoda dkk., 2010; Lee et al.,
2009). However, the use of alkaline solid catalyst is
limited by free fatty acid usually contained in low
quality feedstock, metal oxide leaching caused by
deactivation of the active sites and resulted in product
reaction temperature required (Taufiq, 2011).
In the pioneering works (Istadi et al., 2014), solid
base catalyst with CaO as the active site has been made.
Catalyst was combined with ZnO to increase the surface
area and promoted with K2O to increase the basicity .
After some tests, the CaO-ZnO catalyst showed the high
surface area but indicated a lower catalytic activity than
the K2O/CaO-ZnO catalyst. These tests proved that
addition of K2O brought the higher amount of base sites
on the 2 wt.% K2O/CaO-ZnO catalyst. The catalyst
showed the higher catalytic activity with 81.08 % of
FAME yield various K2O contents (Azis et al., 2014).
However, the proper composition of metal oxides
(CaO, K2O, and ZnO) on transesterification reaction of
vegetable oils to produce biodiesel should be
investigated in detail. The study should be focused on
maintaining the basic active sites and the basicity of
catalyst by synergistic effect of CaO and K2O
components. Synergistic effect of CaO and ZnO is also
important to maintain the good surface area and
performance of the catalyst. Therefore, this research was
purposed to study the synergistic effect of K2O, CaO,
and ZnO components on the maintaining good catalyst
in supporting transesterification reaction of vegetable
oils to produce biodiesel and increasing the surface area.

Copyright 2014, TEKNIK, ISSN 0852-1697


2. Materials and Method
In this research, soybean oil (Mamasuka) and
methanol (99.9%, Merck), were used as raw materials.
The following chemicals, i.e. Zn(NO3)2.4H2O (98.5%,
Merck), Ca(NO3)2.4H2O (99%, Merck), KNO3 (99%,
Merck), and Na2CO3(99%, Merck), NaOH (99%,
Merck), were used as precursors for catalysts
preparation. The K2O/CaO-ZnO catalyst was prepared
according to the coprecipitation and impregnation
methods.
This research used a three-neck flask which acts
as a reactor in which the transesterification reaction
occurs. The three-neck flask equipped with a stirrer
which is driven by the motor, reflux condenser, elbow,
shell and thermometer. That strain is placed on the
Heating mantle (M-Top Heating Mantle MS-E), which
is on the order portable. Thereafter, the circuit is
equipped with a clamp and stand. The top and bottom of
reflux condenser connected to a hose in which the hose t
pumped the water as a coolant that will come out
through the tube at the upper of the reflux condenser.
. equipped with motor. After that the reaction was
Figure 1. Arrangement of transesterification instrument
(1) three-neck flask, (2) heating mantle, (3)
thermometer, (4) motor, (5) controller, (6) condenser
reflux, (7) elbow, (8) stirrer, (9)stand and clamp, (10)
shell , dan (11) portable frame
The preparation of catalyst was started by
making CaO-ZnO catalyst using coprecipitation
method. The mixture of metal oxides of CaO:ZnO (1:1,
1:1.5, 1:2, 1:3, 3:1) were prepared by dissolving
Calcium nitrate (Ca(NO3)2) 1 M and Zinc nitrate
(Zn(NO3)2) 1 M, into aquadest separately. Then, blend
both mixture (Zn(NO3)2) 1 M and (Ca(NO3)2) 1 M into a
beaker glass. Solution of Na2CO3 2 M was added slowly
into the mixed solution with vigorously stirred. pH of
the solution was adjusted to 10 by adding NaOH 1 M
solution. The obtained precipitate was aged for 24 h at
temperature of 60 0C while stirring. The CaO-ZnO
catalyst was made with Na 2CO3 as coprecipitation
agent. The solid product was filtered, washed by
deionized water until alkaline free, and dried at 110 0C
for overnight in an oven (Memmert). The dried solid
catalyst was calcined at 800 0C for 3 h in a box furnace
(Ney Vulcan) and resulting the CaO-ZaO solid catalyst.
Thereafter, the solid catalyst was impregnated to the
solution of KNO3 1 M for 1 h while stirring and was
dried in an oven (Memmert) at 110 0C overnight. The
K2O/CaO-ZaO catalyst were obtained after calcination
at 300 0C for 5 h in a box furnace (Ney Vulcan).
On the transesterification process, mole ratio of
methanol to soybean oil was kept at 15:1, while the
catalyst loading was 4 wt.% of total solution. The
soybean oil was weighed and heated to 60 C on a
heater separately. Both catalyst and methanol were
weighed and heated to 60 0C in a 500 mL three-necked
flask. Thus, the heated soybean oil was added and the
transesterification reactions were performed at 60 0C
for 4 h in a 500 mL three necked reaction flask round
bottom equipped with a water cooled reflux condenser,
a thermometer, a heating mantle, and an impeller
stopped and cooling down the reactor to room
temperature. The products were placed in a separatory
funnel overnight to ensure that the phase of FAME
(Fatty Acid Methyl Ester), glycerol, and catalyst were
separated completely. The concentration of methyl
esters then was determined by using Gas
Chromatography-Mass Spectrometry (GC-MS)
To determine the effect of mol ratio of CaO-ZnO
and addition of K2O on basicity of K2O/CaO-ZnO
catalyst, the basicity analysis of the catalyst was
needed. The basicity analysis used here is the titrimetric
method to determine the basicity of catalyst (Tanabe,
1964). First of all 0.5 gr catalyst was dissolved in 20 ml
benzene. Then 3 drops of bromotymol blue was added.
The solution was stirred for 30 minutes and then titrated
with 0.1 N benzoic acid. The titration will stop when the
color of solution change from blue to faded green.
Basicity can be calculated by the equation
Basicity =
3. Results and Discussion
3.1. Catalyst Structure Characterization by XRD
Method
Characterization of catalyst by XRD method aims to
study the structure and the crystallinity of a catalyst as
depicted in figure 1. Diffractogram of CaO content
shows intensity and peak at 2 angle of: 17.2 , 28.7 ,
50.5 , and 52.7 (JCPDS File No. 37-1497) (Taufiq-
yap et al. 2010). Meanwhile, XRD patterns of ZnO
 content was visible at 2 angle of: 31.84 , 34.51 ,
36.33 , 47.62 , 56.66 , 62.92 , 66.41 , 68 , 69.13 ,
76.98 and 89.67 (JCPDS File No. 36-1451)
(Software Mach! 3). Then, impregnation result of
5%weight K2O component on the CaO-ZnO catalyst
gives additional peak intensity at 2 angle of: 23.88 ,
39.49 , 46.67 , 48.88 and 64.57 (NBS Monograph
16, 1972).
Inte
nsit
y
(au)
2 teta (degree)
Figure 2. XRD pattern of the 5%K2O/CaO-ZnO
catalyst
Diffraction for CaO and ZnO of all catalysts showed
a similar pattern, but different the peaks intensity due to
different CaO or ZnO content on the catalyst (Mutreja et
al. 2014). From the XRD pattern, it is showed that the
structure and crystallinity of the catalyst with CaO:ZnO
ratio of 1: 3 provides the highest intensity of ZnO due to
high content of ZnO. While the the highest intensity of
CaO owned by catalysts with CaO-ZnO ratio 3: 1 due to
high content of CaO. However, the K2O diffraction
showed small intensity in the XRD pattern due to
inadequate dispersion of low K2O content (Istadi,
2015).
3.2. Effect of CaO:ZnO Mole Ratios on The Catalyst
Basicity
Basicity test method for the catalyst was done using
titration by benzoic acid and benzene as the solvent,
using bromotymol blue (BTB) (Tanabe, 1964). The
catalyst basicity the results on the various CaO:ZnO
mole ratios were presented in Table 1.
Table 1. Catalyst basicity at various CaO:ZnO mole
ratio
CaO:ZnO Basicity (mmol/g)
mole ratio of Before K2O After K2O
catalyst impregnation impregnation
1:1 0.344 0.504
1:1.5 0.260 0.316
1:2 0.164 0.280
1:3 0.088 0.230
3:1 0.662 1.090
From the basicity test results reported in Table 1, it
is showed that the impregnation of K2O content on the
CaO-ZnO catalyst could increase the basicity of
catalyst. The K2O could also has function as binding
agent without reduce the basicity of catalyst. Without
this binding agent, the CaO-ZnO catalyst has lower
mechanical strength and easy to be broken by pressure.
Based on Table 1, the rise of CaO content in the 5%
K2O/CaO-ZnO catalyst led to increase basicity.
Conversely, an increase of ZnO content in the catalyst
led to decrease the catalyst basicity. That is because
ZnO is a component in the catalyst support (Istadi,
2011). ZnO is support of a catalyst which is aims to
increase the surface area, porosity, mechanical
properties, and also stability of the catalyst (Istadi,
2011). Thus, the increase of ZnO contribute to the rise
of surface area, not the increase of active site.
On the other hand, the strength base of CaO content
is greater than ZnO leads to increase the catalyst
basicity. Strength base of alkaline earth metal oxides
was parallel by the size of alkaline earth metal atom
(Samik, 2015).
3.3. Effect of K2O Impregnation As Binding Agent
on The Catalyst Basicity
The variations of K2O impregnation on the CaO-
ZnO catalysts were aimed to determine whether the
addition of a K2O content or binding agent could
maintain or even increase the catalyst basicity. This
were added in CaO-ZnO catalyst with ranges of 1%, 3%
and 7%. The basicity increase due to the K2O addition
on the CaO-ZnO catalyst was depicted in Figure 2.
Ba
sici
ty
(m
mo
l/gr
am
)
Figure 3. Effect of K2O promoter on the catalyst
basicity test
 From Figure 3 shows that the higher of catalyst
percentage of K2O as a binding agent in the catalyst 1:1 97.96
will increase its basicity. The K2O component acts as a 1:1.5 88.86
promoter which is designed to assist active components 1:2 98.98
as well as function as a binding agent (Istadi, 2011). The 1:3 94.53
promoter aims to bind the CaO-ZnO catalyst in order to 3:1 97.88
increase its mechanical strength, togenerate activity,
selectivity and stability of catalyst (Istadi, 2011). Amount of methyl esters in biodiesel (FAME yield
Earlier, in Table 1 shows a contrast between and biodiesel yield) is the most important result in the
active component (CaO) and catalyst support (ZnO). transesterification process. The value of FAME yield in
Table 1 shows that the increase of CaO contet will led biodiesel indicates the presence of fatty acid methyl
the rise of catalyst basicity, but the increase of ZnO will ester. Based on SNI requirements, biodiesel is a
cause the decrease of catalyst basicity. Reffered to the substance which is contain 96.5% or more of %FAME
research of Nugroho and Sebastianus (2014) and also (SNI 7182:2015).
Mabruro and Kalimantini (2015) the surface area of FAME yield is biodiesel result which is only
catalyst with 2%K2O impregnation and variation mole measures the %FAME of product towards the soybean
ratio is as follow : oil feed. Whereas, yield of biodiesel is only measures
the total production of biodiesel (including %FAME)
Table 2. Surface area of catalyst based on CaO:ZnO towards the soybean oil feed. The formulas to measure
mole ratio the FAME yield and biodiesel yield are as follow :
CaO:ZnO Surface Area References FAME yield :
mole ratio (m2/g)
of catalyst
1:3 28 Nugroho and Biodiesel yield :
Sebastianus (2014)
3:1 3.094 Mabruro and
Kalimantini (2015) The FAME yield and biodiesel yield results can be
Zno only 5.71 Nugroho and seen in Table 4.
Sebastianus (2014)
Table 4. FAME yield and biodesel yield of
The research which showed by Table 2 tells us that transesterification products
the increase of CaO moles will cause the surface area of CaO:ZnO mole FAME Yield Biodiesel Yield
catalyst decrease, although the basicity increase (Table ratio of catalyst (%) (%)
1). While, the surface area of pure ZnO catalyst shows a 1:1 45.038 45.976
high result. Thus, can be conclude that a higher contet 1:1.5 63.856 71.861
of ZnO can increase the surface area of catalyst, despite 1:2 75.289 76.065
of its reduction of basicity. Therefore, impregnation of 1:3 49.858 52.743
K2O on the catalyst should be done to maintain the 3:1 41.327 42.222
basicity. In this case, impregnation of K2O is not only
acts as the binding agent but also as a promoter which Determination of the best CaO:ZnO mole ratio of
could increase basicity of catalyst. the catalyst can be assessed based on the highest FAME
yield (Puspitaningati et al, 2013). The greater FAME
3.4. The K2O/CaO-ZnO Catalyst Testing on the yield, the higher quality of biodiesel will be obtained.
Transesterification of Soybean Oil with Biodiesel quality requirements such as density,
Methanol to Produce Biodiesel viscosity, and acid number must agree with the
This catalyst testing used the following fixed Indonesian National Standard (SNI 7182:2015). The
parameters: soybean oil to methanol mole ratio of 1:15, SNI standards of biodiesel including kinematic viscosity
5% weight of catalyst loading relative to weight, batch 2.3 to 6 mm2 / s by ASTM D 445 method, density 850-
time of 4 hour, reaction temperature of 60oC, and at 890 kg / m3 by ASTM D 1298 method, and the acid
constant stirring of 240 rpm. number <0.5 mgKOH / g sample by ASTM D 664
The biodiesel was then tested its viscosity, density, method. The quality of biodiesel products are as follow:
acid number, and FAME yield. The result of FAME
percentage in the biodiesel product can be seen in Table Table 5. The quality of biodisel products
3. CaO:ZnO Kinematic Acid number
Density
Table 3. FAME precentage results of biodiesel products mole ratio viscosity (mg KOH/gr
(kg/m3)
CaO:ZnO mole ratio %FAME of catalyst (mm2/s) sampel)
 1:1 3.996 872.4 0.2468 While reaction (3) pointed out that tetrahedral ion take
1:1.5 2.612 861.2 0.2468 H+ ion from the surface of O-Ca-O-Zn-O-K- catalyst.
1:2 4.797 866 0.2468 On reaction (4) tetrahedral ion also reacted with
1:3 2.964 864 0.1234 methanol to produce metoxide anion (Ma and Hanna,
3:1 3.996 872.4 0.4937 1999). The last reaction (5) was a tetahedral ion
SNI breaking reaction that formed biodiesel and alcohol.
2.3-6 850-890 <0.5
Biodiesel
4. Conclusion
Based on the data obtained in Table 4 and Table 5, The 5%K2O/CaO-ZnO catalyst with variation of
biodiesel production which using the 5% K2O/CaO- CaO:ZnO mole ratio of 1:1, 1:1.5, 1:2 and 1:3 has been
ZnO catalyst with CaO:ZnO mole ratio of 1:2 shows prepared and also has been tested by transesterifiction
the highest FAME yield. Its viscosity, density, and acid reaction to produce biodiesel from soybean oil. Mol
number are also meets SNI requirements. It is ratio of CaO:ZnO shows that a higher CaO ratio will
concluded that the 5%K2O/CaO-ZnO catalyst with increase the catalyst basicity, but it decrease the surface
CaO:ZnO mole ratio of 1: 2 is the most promising area of catalyst. Otherwise, a high ratio of ZnO will
catalyst. decrease the catalyst basicity, but it increase the surface
A good performance of catalyst is also depend on its area of catalyst. Those were because CaO has a high
basicity. That was because a higher basicity will bring a strength of base and included to the active site of
high rate of reaction (Yan et al., 2009). But, a too high catayst. That cause the CaO will support the rate and
basicity not always gives a high result of FAME yield. direction of the catalyst through its basicity. While, ZnO
Based on Nugroho and Sebastianus (2014) experiment, is included to the catalyst support which support the
2%K2O/CaO-ZnO catalyst has 81.08% FAME yield but catalyst stability, mechanical strength, and surface area.
5%K2O/CaO-ZnO catalyst has 74.52% FAME yield. That brings the addition of ZnO will incline the rise of
Thus, catalyst basicity must be maintain to obtain the catalyst surface area. Thus, the addition of K2O content
best strength of base. One of the way to get the best is needed, and those give a result that a high contain of
basicity of catalyst is by settle the suitable mole ratio K2O will led an increase of catalyst basicity. The most
and the promoter content. A prediction of reaction promising catalyst which has a highest result of FAME
mechanism of transesterification using K2O/CaO-ZnO yield is 5%K2O/CaO-ZnO catalyst with CaO:ZnO mole
are as folow: ratio of 1:2. While the highest basicity of catalyst is
found at 5%K2O/CaO-ZnO catalyst with CaO:ZnO
mole ratio is 3:1. The best result of catalyst
(1) 5%K2O/CaO(1)-ZnO(2) also produce biodiesel with
spesification that meets the SNI quality requirements.
(2)
Acknowledgment
The authors woud like to express appreciation for
(3) the support given by lecturer supervisor Dr. Istadi, ST.,
MT. Gratitude to the Chemical Engineering Department
for the permission to used the equipments and materials
(4) in the Process Engineering Laboratory.

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Figure 4. Mechanism prediction of transesterification
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