The 4th TIChE International Conference 2014

"Changes: Cleaner Energy, Leaner Processes, Better Living"

Chiang Mai, Thailand, December 18-19, 2014

Characterization and Catalytic Activity Studies of Neodymium Oxide

Catalyst for Biodiesel Production
Teerapong Ajpakdee, and Dussadee Rattanaphra*
Research and Development Division, Thailand Institute of Nuclear Technology,
Phathumtani, 12120, Thailand
*Corresponding author: E-mail drattanapra@yahoo.com

Abstract The neodymium-EDTA solution obtained

from decomposition of Thai monazite ore by alkali
method and using ion exchange technique as
purification process was used as raw material to
prepare neodymium oxide (Nd2O3) catalyst. The
catalyst was synthesized by oxalate precipitation
method. Effect of calcination temperature (500, 600,
800, 900 and 1000 oC) on structure and properties of
Nd2O3 catalyst was studied. The obtained catalyst was
characterized by X-ray diffraction (XRD), BrunauerEmmett-Teller (BET) method, Thermogravimetric
analysis (TGA) and Scanning electron microscope
(SEM). The result showed that the prepared catalyst
was very fine. The average crystallite size of Nd2O3
catalyst was about 46.77 nm. The catalyst was used to
catalyze the transesterification of palm oil with
methanol to biodiesel production. It was found that the
high fatty acid methyl ester (biodiesel) content of
97.2% was obtained under the conditions: molar ratio
of methanol to oil of 30:1, catalyst loading of 10 wt%,
reaction temperature of 200 oC, reaction pressure of 39
bar and stirring rate of 600 rpm for 5 h.
Keywords: neodymium oxide catalyst, characterization,
catalytic activity, and biodiesel.
I.

INTRODUCTION

Due to the increasing of conventional diesel

consumption, the running out of fossil fuel and the rising
of environmental concerns, an alternative diesel fuel is
becoming more popular. Biodiesel is a viable and
attractive alternative fuel [1-2]. It can be derived from
various renewable sources including vegetable oils, animal
fats and recycled cooking oils. Biodiesel is obtained
through transesterification reaction of vegetable oils and
low molecular weight alcohol (usually methanol) in the
presence of a catalyst [3]. Biodiesel shows clear advantage
over conventional diesel. It is biodegradable and naturally
non-toxic [4]. One of the most advantages of biodiesel is

that it reduces the emission profile including carbon

monoxide (44%), sulfur oxide (100%), unburned
hydrocarbons (68%), particulate matter (40%) and
polycyclic aromatic hydrocarbons (PAHs) (80-90%) [5].
Moreover, biodiesel is safer to handle and store than
petroleum diesel fuel because it is higher flash point (over
150 oC) than petroleum diesel fuel (77 oC) [6].
The catalyst used to produce biodiesel can be divided
into two main types: homogeneous and heterogeneous.
Homogeneous catalysts such as NaOH and KOH are
favored to catalyze biodiesel reaction due to its high
activity, its selectivity and its mild reaction conditions (at
low reaction temperature and atmospheric pressure) [7].
However, the use of homogeneous catalysts cause
undesired soap formation through the hydrolysis of esters,
which reduces the biodiesel yield and causes significant
difficultly in the separation of ester and glycerol. Besides,
the removal of the catalyst after reaction is technically
difficult and the huge amount of wastewater is generated
in order to separate and clean the products [8]. These
limitations can be overcome by using a heterogeneous
catalyst. Heterogeneous catalysts have several advantages
over homogeneous catalyst: simple catalyst recovery,
catalyst reusability, simple production purification and a
simple glycerol recover. Moreover, it requires less energy
and water consumption that lead to safer, cheaper and
more environmental friendly approach [7].
Neodymium oxide (Nd2O3) has various applications in
numerous scientific and industrial fields. It is used as
luminescent materials, protective coatings, catalysts or
catalyst modifiers and components for advanced ceramic
materials [9-10]. The applications of Nd2O3 based catalysts
include dehydrogenation, hydrogenation and esterification
[11]. In addition, it has been used as a catalyst for
biodiesel production [12-14].
In this work, pure Nd2O3 catalyst was prepared by
oxalate precipitation method. The catalyst calcined at

The 4th TIChE International Conference 2014

"Changes: Cleaner Energy, Leaner Processes, Better Living"
Chiang Mai, Thailand, December 18-19, 2014

different temperatures was characterized using XRD,

TGA, BET and SEM. The catalytic activity of pure Nd2O3
catalyst in transesterification of palm oil with methanol
was investigated.

II.

MATERIALS AND MATHODS

1. Preparation of Nd2O3 catalyst by oxalate precipitation

method
A solution of 10 wt% of oxalic acid was added
dropwise to1400 ml of Nd in EDTA solution as obtained
from the decomposition of monazite ore process under
constant stirring until a pH of 3-4. After complete
precipitation, a white precipitate of neodymium oxalates
were filtrated and then washed with distilled water several
times as well as were dried at 110 oC for 12 h. Finally, the
samples were calcined at different temperatures (500, 600,
800, 900 and 1000 oC) for 3 h.
2. Sample Charecterization
Powder X-ray diffraction (XRD) patterns were recorded
on a Panalytical, XPert PRO equipped with Cu K
radiation ( = 1.5406 ) operating at 45 kV and 40 mA.
The measurements were performed in the 2 range of 2090o. The TGA analysis was performed on a Mettler Toledo,
TG/SDTA 851e in the range of 25-1100 oC and the heating
ramp of 20 oC/min. The specific surface area and total pore
volume were measured by BET surface area and BJH
method using surface area analyzer (Autosorb-1,
Quantachrome). The surface morphology was observed by
scanning electron microscopy, SEM (S-3400N, HITACHI).

4. Analysis of biodiesel
The fatty acid methyl ester contents (FAME) in the
samples were quantified by using a GC-MS (Algilent,
6890) equipped with a HP-5 capillary column (30 m x 0.25
mm x 0.25 m). Helium was used as a carrier gas. The
oven temperature was programmed from 120 oC to 180 oC
at 20 oC/min and then to 280 oC at 5 oC/min, and held for 3
min. The injector and interface temperature was 280 oC.
The IE ionic source temperature was 230 oC. The
compounds were identified by mass spectrometry in both
SCAN and SIM mode. Spectra of the compounds was
obtained and compared with those in library.

III.

RESULTS AND DISCUSSION

Figure 1 shows the XRD patterns of Nd2O3 calcined at

different temperatures. A monoclinic structure of
Nd2O2CO3 was observed when the calcined temperature
was at 500 and 600 oC, according to JCPDS card No. 230421 and 37-0806 respectively. At the calcined temperature
higher than 800 oC, the crystal structure of Nd2O3 was
observed. A sharp diffraction peak was observed at around
2 = 26.89, 29.83, 30.81, 40.55, 47.47 and 53.53. All of the
diffraction peaks can be indexed to a hexagonal structure,
which matched well with the standard data (JCPDS card
No. 00-041-1089). All the sharp peaks of the powder
indicated that the crystallization was perfectly achieved.

3. Synthesis of biodiesel
Synthesis of biodiesel was investigated using a 600 ml
Parr stirred batch reactor (model 4568) equipped with a
magnetic stirrer drive, a four-blade impeller and a
temperature controller. Initially, 100 g of palm oil and
catalyst were charged into a reactor. After the reactor was
closed, nitrogen was purged to remove the air from the
reactor. When the reactant and catalyst were heated to the
desired reaction temperature, with constant stirring rate of
600 rpm, nitrogen was introduced to pressurize the system
to ensure that the reactants were forced to be liquid. The
reaction was started when methanol was added into the
reactor vessel. After the reaction completion, the sample
was separated from catalyst and glycerol by centrifuge.
The final product was obtained after removal of excessive
methanol.

Figure 1 XRD patterns of Nd2O3 calcined at different

The average crystallite size of Nd2O3 powder was
estimated by the Scherrer equation as follows:
(1)

The 4th TIChE International Conference 2014

"Changes: Cleaner Energy, Leaner Processes, Better Living"
Chiang Mai, Thailand, December 18-19, 2014

where
is the average crystallite size of Nd2O3, =
0.154 nm is the X-ray wavelength of Cu K, is the fullwidth of the peak measured at half maximum intensity
(FWHM) and
is the Braggs angle of the peak, was
about 46.77 nm.
TGA curve of neodymium oxalate (Nd2(C2O4)3.H2O) is
illustrated in Figure 2. The thermal decomposition of
Nd2(C2O4)3..H2O occurred via a three stages process. The
first stage was the dehydration process in the temperature
range of 40-300 oC with weight loss of 24.67%. The
second step located approximately between 300-605 oC
with weight loss about 27.69%, which can be assigned to
the decomposition of Nd2(C2O4)3 to the intermediate
Nd2O2CO3. The third stage beginning at 605 oC and
completing at 752 oC with weight loss 3.54% can be
attributed to the decomposition of Nd2O2CO3 to Nd2O3.
This result was in good agreement with the XRD data.
However, the calcination temperature up to 850 oC is
necessary to convert the remaining Nd2O2CO3 to pure
Nd2O3 [14].

Table 1 shows the BET surface area of Nd compound

calcined at different temperatures. It can be seen that the
BET surface area of Nd2O3 decreased from 8.09 to 4.79
m2/g with the increasing of calcination temperature from
800 to 1000 oC.
SEM images of Nd2O3 calcained at 900 oC are shown
in Figure 3. The SEM photograph of Nd2O3 showed non
uniform sizes and shapes. However, the sizes of most
particles were very fine.

Figure 3 SEM images of Nd2O3 calcined at 900 oC

Pure Nd2O3 catalyst calcined at 900 oC was used to
catalyze transesterification of palm oil and methanol. This
catalyst showed high activity with fatty acid methyl ester
content of 97.2% under the conditions: molar ratio of
methanol to oil of 30:1, catalyst loading of 10 wt%,
reaction temperature of 200 oC, reaction pressure of 39 bar
and stirring rate of 600 rpm for 5 h.

IV.
Figure 2 TGA plot of neodymium oxalate
Nd2(C2O4)3..H2O.

Table 1 BET surface area Nd compound calcined at

different temperatures

CONCLUSIONS

Pure neodymium oxide prepared by oxalate

precipitation presented a promising potential as catalyst in
transesterification of palm oil with methanol to produce
biodiesel. Under the conditions as follows: molar ratio of
methanol to oil of 30:1, a catalyst loading of 10 wt%, a
reaction temperature of 200 oC, a reaction pressure of 39
bar and a stirring rate of 600 rpm for 5 h. The high fatty
acid methyl ester content of 97.2% was obtained.

Calcination
temperature (C)

Nd compound

BET surface
area (m2/g)

500

Nd2O2CO3

14.09

ACKNOWLEDGMENT(S)

600

Nd2O2CO3

8.09

800

Nd2O3

8.04

Financial support from Thailand Institute of Nuclear

Technology is gratefully acknowledged.

900

Nd2O3

6.16

1000

Nd2O3

4.79

The 4th TIChE International Conference 2014

"Changes: Cleaner Energy, Leaner Processes, Better Living"
Chiang Mai, Thailand, December 18-19, 2014

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