ISSN: 0970-020 X

ORIENTAL JOURNAL OF CHEMISTRY CODEN: OJCHEG

An International Open Free Access, Peer Reviewed Research Journal
2018, Vol. 34, No.(2):
Pg. 750-756
www.orientjchem.org

Synthesis and Characterization of Natural Ca(OH)2/KF

Superbase Catalyst for Biodiesel Production from Palm Oil
I F NURCAHYO1,2*, KARNA WIJAYA1, TRIYONO1, ARIEF BUDIMAN3 and
YUN HIN TAUFIQ-YAP4,5

1
Department of Chemistry, Faculty of Mathematics and Natural Sciences, Gadjah Mada University,
Sekip Utara BLS 21, Bulaksumur, Sleman, Daerah Istimewa Yogyakarta 55281, Indonesia.
2
Department of Chemistry, Faculty of Mathematics and Natural Sciences, Sebelas Maret University,
Jl. Ir. A. Sutami 36A, Kentingan, Surakarta 57126, Indonesia.
3
Department of Chemical Engineering, Faculty of Engineering, Gadjah Mada University,
Jl. Grafika No. 2 Yogyakarta 55281, Indonesia.
4
Department of Chemistry, Faculty of Science, Universiti Putra Malaysia, 43400, UPM Serdang,
Selangor, Malaysia.
5
Catalysis Science and Technology Research Centre (PutraCAT), Faculty of Science,
University Putra Malaysia, 43400, UPM Serdang, Selangor, Malaysia.
*Corresponding author E-mail: ifnurcahyo@staff.uns.ac.id

http://dx.doi.org/10.13005/ojc/340218

(Received: November 12, 2017; Accepted: February 10, 2018)

ABSTRACT

The natural Ca(OH)2/KF superbase catalyst was synthesized by grinding and calcinations
with a rapid thermal annealing method. It was applied to transesterification of palm oil into biodiesel.
The effect of molar ratio Ca(OH)2 to KF and calcinations temperature on the catalyst character
and the catalytic activity was investigated. The catalysts were characterized by XRD, FTIR,
CO2-TPD, surface area, and TGA. The results indicated that natural Ca(OH)2 reacted to KF in
forming monoclinic and orthorhombic KCAF3. The monoclinic KCF3 was produced by reaction
between Ca(OH)2 and KF, whereas the orthorhombic KCaF3 was produced by reaction between
CaCO3 impurities and KF. The best catalyst was natural Ca(OH)2/KF with molar ratio of Ca(OH)2
to KF 0.8:1 and calcinations at 500 oC. The catalyst was able to convert 97.6 % oil into biodiesel
within 1 min. at 5 % catalyst, molar ratio oil/methanol of 1/12, reaction temperature of 65 oC.

Keyword: Natural Ca(OH)2/KF, Superbase, Biodiesel, Palm oil.

INTRODUCTION 3relative order of effectiveness to catalyze

Among the studied heterogeneous transesterification was BaO ~ SrO > NaOH >> CaO
catalysts, there was alkaline earth basic oxide such ~ MgO. The SrO catalyst was further examined due

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4.0 International License (https://creativecommons.org/licenses/by-nc-sa/4.0/ ), which permits unrestricted
NonCommercial use, distribution and reproduction in any medium, provided the original work is properly cited.
 NURCAHYO et al., Orient. J. Chem., Vol. 34(2), 750-756 (2018) 751

to toxicity concerning with BaO4. Calcium-based enhanced by loading potassium fluoride. The
heterogeneous catalysts were very intriguing to loading will produce superbase catalyst KCaF35-11.
develop. It is due to natural calcium abounds in the Some data concerning a state of transesterification
CaCO3 phase. The CaCO3 can be converted to CaO and catalyst preparation for various catalysts of CaO
and Ca(OH) 2 . Their catalyst activity can be and Ca(OH)2 loaded KF are shown on Table 1.

Table 1: Literature of transesterification on CaO/KF

Catalyst CaO to KF Calcinations Transesterification

or Ca(OH)2 to KF T t Catalyst Oil to T t Methylester
(mol/mol) (oC) (h) weight Methanol (oC) (min.) yield
(%) (mol/mol) (%)

KF/CaO5 4.14/1 600 4 4 12-Jan 65 150 96.8

CaO/KF11 1/1.036 500 5 2.1 12-Jan 65 20 99.9
ZnO/Ca(OH)2/KF9 1-Jan 400 6 3 12-Jan 65 90 97.6
Na2SiO3/CaO/KF10 1/1.5 400 4 3 10-Jan 65 30 97.1

The data in Table 1 indicate that the CaO/ possibility of using Ca(OH)2 was more effective than
KF is a good catalyst for transesterification. Both CaO in formation of KCaF3. The Ca(OH)2/KF catalyst
molar ratio of CaO/KF and calcinations temperature was prepared by simple grinding, thus it was
have an effect on this catalyst activity. The best of calcined with rapid thermal annealing method. The
the molar ratio of CaO/KF is around 1-1.5. On the
catalyst was characterized by X–ray diffraction
best molar ratio, transesterification of triglyceride
(XRD), FTIR, CO2-TPD, TGA, and Surface Area
was almost complete. The good calcinations
Analyzer. It is applied to transesterification of palm
temperature in order to prepare this catalyst is about
400-500 oC. Catalyst of CaO/KF without other oxides oil and the resulting biodiesel was detected by
has higher activity than the catalyst plus other oxides. H-NMR.
The catalysts were calcined using normal heating
about 400-600 oC for 4-6 hours. The calcination MATERIALS AND METHODS
was just wasteful of energy. In order to save energy,
Natural Ca(OH)2 was obtained from home
calcination with other methods shall be attempted.
One such method is rapid thermal annealing (RTA). industry in Klaten, Indonesia. Reagent grade
This method allows calcination process performed potassium flouride and methanol were purchased
in a short time and rapid heating rate. The RTA from Merck & Co. Chemical. Sample of palm oil
method for calcination is superior to the CFA was purchased from local store on Indonesia.
(conventional furnace annealing) method for
reducing calcination timing budget and yielding Preparation and characterization of Ca(OH)2/KF
relatively high specific surface areas of tin oxide Amount of natural Ca(OH)2 mixed KF with
powders 12. Calcination using the RTA method molar ratio of Ca(OH)2 to KF was 0.8:1. The mixture
produced a smaller crystalline size of the oxide than
was ground by mortar until evenly for 15 minutes.
those produced using the CFA method at the same
The homogenous mixture was added by 3 mL of
temperature12.
distilled water then it was pulverized by mortar for
In this study, Ca(OH)2 was obtained from 15 minutes. The resulted sludge was dried up at
natural CaCO3 in Indonesia. The authors chose 120 oC for 6 hours. The dried sludge were crushed
Ca(OH)2 and did not opt for CaO as its precursor. and filtered with 100-mesh sieve. The amount of
This selection is based on consideration that 7 g powder was calcined at 400, 500, and 600 oC
CaO/KF is prepared by adding water. If CaO was for 10 min. by heating rate of 200 oC/min. on rapid
added by water, it will produce Ca(OH) 2. The thermal annealing (RTA) furnace (Figure 1).
752 NURCAHYO et al., Orient. J. Chem., Vol. 34(2), 750-756 (2018)

30 second. The methyl esters were investigated at

various reaction times. The investigation used
Agilent of 400 MHz H-NMR Spectrometer.
Conversion of palm oil to biodiesel can be
measured based on Knothe’s method 13 from
integration values of glyceridic and methyl ester
protons in H-NMR.

Fig. 1. RTA furnace

Powder XRD patterns were recorded on a

Shimadzu XRD 6000 diffractometer using CuKα
radiation (λ= 1.5418 A) at 40 kV and 30 mA. An
FTIR spectrum of the catalyst was detected by using
Shimadzu IR Prestige 21 spectrophotometer. Basic
strength of catalyst was detected by CO2-TPD on
Thermo Scientific TPDRO 1100. Thermal
decomposition of catalyst was investigated by TGA
on Linseis STA PT1600. The surface area was
detected by Quantachrome Nova 1200. The best Fig. 2. Transesterification reactor
character was chosen for variation of Ca(OH)2 to
RESULTS AND DISCUSSION
KF mol ratio. The variations were 0.8:0.5, 0.8:1, and
0.8:1.5. They were characterized by XRD, FTIR,
Characterization of Catalyst
CO2-TPD, TGA, and surface area analyzes. The
X-ray Diffraction, Fig. 3 depicts the profiles
obtained catalyst is abbreviated in Table 2.
of natural Ca(OH)2 and dried natural Ca(OH)2-KF
Table 2: Abbreviation of catalyst mixture. Fig. 3a represents natural Ca(OH) 2
containing CaCO 3 impurities. Concentration of
Mol Mol KF Calcination Abbreviation Ca(OH)2 and CaCO3 in natural Ca(OH)2 will be
Ca(OH)2 temperature discussed on TGA session. The XRD profile of the
dried Ca(OH)2-KF mixture is shown in Fig. 3b. This
0.8 0.5 500 CaK-A-500 reflects that KCaF3 has been formed on this stage
0.8 1 500 CaK-B-500 in small quantities. The KCaF3 formed in 2 phases
0.8 1.5 500 CaK-C-500 was monoclinic and orthorhombic. KCaF3 crystals
0.8 1 400 CaK-B-400 are very clear when the mixture is calcined. At
0.8 1 600 CaK-B-600 calcination of 500 oC, CaK-A-500 and CaK-C-500
indicates an imperfect reaction (Fig. 4). On the XRD
Transesterification of palm oil profile, the peaks of Ca(OH)2 and CaCO3 apparently
The transesterifications were conducted remains to have high intensity. The imperfection of
at 65 oC. Experiments were carried out in a 50 mL reaction on CaK-A-500 was caused by deficiency
of three-necked flasks (Fig. 2). Catalysts and of K atoms. Another case in CaK-C-500, the
methanol were mixed in advance at room possibility of this imperfection due to hygroscopic
temperature for 15 minutes. Then the mixture was catalyst was fairly high. The best catalyst was CaK-
heated at 65 oC. In a separate container, palm oil B-500 in its XRD profile, the peaks of Ca(OH)2 and
was heated at temperature of 65 oC. This reaction CaCO 3 were low, but the one with KCaF3 was
set up by mixing all the reactants and catalysts at elevated. The monoclinic KCaF3 peaks appear at
65 oC. The molar ratio of palm oil to methanol was 2è 20.08, 28.6, 40.93, 51.01, and 59.54 degrees14.
maintained at 1:12.The catalyst used was 5 % by The orthorhombic KCaF3 peaks come out at 2è
weight of oil. After each reaction, the catalyst was 35.54, 37.17, 48.10, and 68.23 degrees15. KCaF3
separated by using a centrifuge at 15,000 rpm for monoclinic formation was also reported by Fan9 in
 NURCAHYO et al., Orient. J. Chem., Vol. 34(2), 750-756 (2018) 753

a conventionally calcined Ca(OH)2-KF reaction.

Furthermore, the CaK-B-500 catalyst was selected
for variations of calcination temperature. Profile of
XRD in Fig. 5 indicates that monoclinic and
orthorhombic KCaF3 peaks turn up. The higher the
calcination temperature was, the peak intensity of
Ca(OH) 2 d101 (2θ 33.8 deg) was dropped off. A
decrease of intensity also occurred in CaCO3. It can
be confirmed by TGA (Fig. 8) and FTIR (Fig. 6). This
phenomenon proves that KF is not only reactive to
Ca(OH)2 but KF is also reactive to CaCO3. Thus this
is the first paper postulated that KF can be reactive
to CaCO 3 . Reaction between KF and CaCO 3
produces orthorhombic KCaF3. The equation of the
reaction is written as follows:
Ca(OH)2 + 3 KF KCaF3 (monoclinic) + 2 KOH9
Fig. 5. XRD profile of catalysts at various
heat calcination temperatures
2 KOH K2O + H2O11

CaCO3 + 3 KF KCaF3 (orthorhombic) + K2O + CO2

Fig. 6. FTIR Spectra of catalyst, a) KF, b) natural

Ca(OH)2, c) dried mixture of Ca(OH)2-KF(CaK-B-500 oC
before calcination), d) CaK-A-500, e) CaK-C-500, f)
Fig. 3. Diffractogram a) natural Ca(OH)2, b) mixture CaK-B-400, g) CaK-B-500, h) CaK-B-600
of Ca(OH)2-KF
Fourier Transform Infrared (FTIR)
Figure 6 depicted FTIR spectra for KF,
natural Ca(OH)2, dried natural Ca(OH)2-KF mixture,
and catalysts after calcinations. Fig. 6a is a spectrum
of KF. The KF spectrum is similar to pure water
spectrum. It indicates that KF does not absorb IR
rays and KF is highly hygroscopic. On Fig. 6a-6h,
broadband at 2600-3600 cm-1 is vibration of O-H in
water and 1640 cm-1 corresponding to bending
mode of H2O16. Vibration band at 3644 cm-1 was
corresponded to O-H bond of Ca(OH)217. Peak height
at 3644 cm -1 was corresponded to Ca(OH) 2
concentration. The study of Ca(OH)2 concentration
will be discussed at TGA session. The vibration band
Fig. 4. XRD profile of catalysts at various molar 1465, 1389, 873, 713 cm-1 correspond to vibration
ratios of Ca(OH)2 to KF modes on CaCO317-19.
754 NURCAHYO et al., Orient. J. Chem., Vol. 34(2), 750-756 (2018)

Surface area and CO2- TPD, Based on the strength. It has two CO2-TPD peaks on 900 and
data from nitrogen adsorption isotherms (Table 3), 950 o C. Having compared with KF/CaO that
the catalysts were micro-porous material. The best synthesized by Lin20, the CaK-B-500 seems more
of surface area catalyst was CaK-B-500 with surface superior. Basic strength of KF/CaO that synthesized
area of 21.81 m2/g and pore diameter 1.18 nm. by Lin was 600-700 oC. The high of the catalyst
basic strength is derived from KCaF35 and K2O21
Character of CO2 desorption for all synthesized
compounds. At Table 3, the catalyst has almost the
catalyst have superbase sites. On the data
same base.Therefore, the basic strength is very influential
CO 2-TPD (Fig. 7), CO 2 desorption was occurred
on catalytic ability. In this case, the CO2 detected by the
on 550 – 950oC. The order of basic strength is TPD instrument comes from the base sites and
CaK-B-500 > CaK-B-600 = CaK-B-400 > CaK-C- decomposition of CaCO3, but desorption of CO2 from
500 > CaK-A-500. The CaK-B-500 is the best basic the decomposition was very small.
Table 3: Absorption isotherm and basicity of the catalyst

Catalyst Surface area Pore diameter CO2 from decomposition Basic strength
(m2/g) (nm) CaCO3 (mmol /g)a (mmol/g)b

Natural Ca(OH)2 1.86 Not investigated

CaK-A-500 15.19 1.19 0.56 2285.18
CaK-B-500 21.81 1.18 0.19 2125.77
CaK-C-500 16.79 1.19 0.02 2381.20
CaK-B-400 12.48 1.19 0.18 2095.40
CaK-B-600 14.88 1.19 undetected 1902.47

a
Data from TGA
b
Data from CO2-TPD
Thermogravimetry analysis. Based on
XRD data, the natural Ca(OH)2 contains Ca(OH)2
and CaCO3. Based on XRD data, natural Ca(OH)2
contains Ca(OH)2 and CaCO3. The Ca(OH)2 and
CaCO3 concentrations can be measured based on
TGA data. Fig 8, weight loss at temperature of 380-
500 oC indicates decomposition of Ca(OH)2 to CaO
and H2O. The weight loss at 590-750 oC represents
decomposition of CaCO3 to CaO and CO 2. The
decomposition of Ca(OH) 2 and CaCO 3 at this
approaching temperature were also reported in
other paper22-26. Concentration of Ca(OH)2 and
Fig. 7. Desorption of CO2 from the catalyst CaCO3 were represented on Fig. 9 and Fig.10. In
Fig. 9, the higher the calcination temperature, the
concentration of Ca(OH)2 and CaCO3 dropped off.
This fact indicates that the higher temperature leads
to an increase in reaction rate. The decrease of
Ca(OH) 2 and CaCO 3 proves that both can be
reactive to KF. In Fig. 10, an increase in KF
concentration results in a decrease in Ca(OH)2 and
CaCO3 concentrations. It means that an increase
in concentration of the reactants will speed up the
reaction rate. This phenomenon fits the law of the
reaction rate. These data fit with XRD and FTIR
Fig. 8. Thermogravimetry analysis of the catalyst data.
 NURCAHYO et al., Orient. J. Chem., Vol. 34(2), 750-756 (2018) 755

Fig. 11. Transesterification of palm oil used catalyst

CaK-B. Mol ratio oil to methanol 1 : 12, temperature
reaction 65 oC, weight of catalyst 5 % from weight
Fig. 9. The decrease of Ca(OH)2 and CaCO3 on of oil
CaK-B catalyst based on TGA

Fig. 12. Transesterification of palm oil use catalyst

CaK-A-500, CaK-B-500, and CaK-C-500 . Mol ratio
oil to methanol 1 : 12, temperature reaction of 65 oC,
weight of catalyst of 5 % from weight of oil
Fig. 10. The decrease of Ca(OH)2 and CaCO3 on
CONCLUSION
CaK catalyst at 500 oC based on TGA
A natural Ca(OH) 2 containing CaCO 3
Transesterification of palm oil. Fig. 11, palm impurities can be reactive to KF in order to create
oil has been widely converted in 1 minute. The monoclinic and orthorhombic KCaF 3 . The
activity of catalyst CaK-B-500 is better than the one Monoclinic KCaF3 is formed from reaction between
with CaK-B-400 and CaK-B-600 catalyst. In 1 min. Ca(OH)2 and KF. The orthorhombic KCaF3 is formed
CaK-B-500 catalyst can convert palm oil to methyl from the reaction between CaCO3 and KF. The
natural Ca(OH)2/KF catalyst can be used as an
ester by 97.6 %. In Fig. 12, activity of CaK-B-500
effective catalyst for transesterification of soybean
catalyst is better than the one with CaK-A-500 and oil and methanol. Under optimum conditions,
CaK-C-500 catalyst. This phenomenon suits natural Ca(OH)2/KF catalyst can convert 97.6 % of
perfectly with the data of the surface area and basic palm oil into biodiesel.
strength. The CaK-B-500 catalyst has the best
ACKNOWLEDGEMENT
surface area and strength characteristics. When
CaK-B-500 catalysts are compared with a The authors wish to thank Sebelas Maret
University for the financial support for this work under
homogeneous catalyst for transesterification27-29, the
the Grant of University Research Committee
CaK-B-500 catalyst activity is superior. So the (“Hibah Penelitian Disertasi dan Doktor Baru” PNBP
catalyst is potential to be used in the flow reactor. UNS, 2016).
756 NURCAHYO et al., Orient. J. Chem., Vol. 34(2), 750-756 (2018)

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