Asian Journal of Chemistry; Vol. 29, No. 8 (2017), 1705-1708
ASIAN JOURNAL OF CHEMISTRY
Isomerization Reaction of α-Pinene Using Zirconia/Natural Zeolite Catalysts
*
N. WIJAYATI , T. HANDAYANI and SUPARTONO
Department of Chemistry, Universitas Negeri Semarang, Sekaran, Gunungpati, Semarang, Indonesia
*Corresponding author: Fax: +62 24 8508035; Tel: +62 81575579586; E-mail: nanikanang@gmail.com; nanikanang@mail.unnes.ac.id
Received: 30 January 2017;
Accepted: 12 April 2017;
Published online: 12 June 2017;
AJC-18426
The isomerization reaction of α-pinene from turpentine oil using heterogeneous catalysts (Zr4+/natural zeolite) produces monocyclic and
bicyclic compounds and other products. The purpose of this study is to investigate the effects of time, concentration of Zr4+ and temperature
on the activity and selectivity of the catalyst. Catalyzed reactions in heterogeneous phases were performed. In heterogeneous reaction,
catalyst Zr4+/natural zeolite at several temperatures were used. Results indicate that the modification of the catalyst by cation Zr4+ increases
the acidity from 2.76 to 6.64 mmol/g. It can be observed that conversions and selectivities have been explained in terms of surface acidity,
structural and textural features of the modified natural zeolite determined by using X-ray diffraction and N2 adsorption at 77 K. FT-IR
spectra of adsorbed pyridine on catalysts Zr4+/natural zeolite show the presence of Lewis and Brönsted acid sites.
Keywords: Natural zeolite, Isomerization, α-Pinene.
formation of monocyclic compounds. Yadav et al. [7] studied
INTRODUCTION
the reaction catalyzed by a montmorillonite pre-treated with
sulfuric acid, the results obtained α-pinene conversions of 96 %
with selectivity for camphene ranging 39-49 %.
Turpentine oil is a product widely used in the cosmetic
industry as pharmaceutical raw materials, perfumes, solvents,
resins and polymers [1]. Turpentine oil contains about 57-86 %
α-pinene, 8-12 % 3-carene and other groups of monoterpene.
The structure of α-pinene having a skeleton of bicyclo[3.3.1]-
heptene, in the presence of acids, easily participates in cycle
opening reactions to derivatives of p-menthane and molecular
Grzona et al. [9] using sulfated Zirconia as a catalyst prefor-
mance α-pinene isomerization reaction to produce α-pinene
conversion of 17-90 %. In the present work, Zr4+/ZA catalyst
was selected to study the isomerization of α-pinene. The method
used in dropped Zr against natural zeolite is a method of impreg-
rearrangement reactions to derivatives of bornane or fenchane
nation.
[2-4]. Complex mixture are obtained resulting from isomeri-
zation.
EXPERIMENTAL
The isomerization reaction is developed in presence of
strong acid catalysts. Homogeneous catalysts have been used
by most of the industry and have a negative impact in the form
of hazardous acid waste, also has short comings because it is
difficult to separate from product. Heterogeneous catalysts can
be used as an alternative with positive opportunities related to
increased yields and selectivity of the process through the
α-pinene isomerization reaction. Clay, zeolites and different
oxide have been used for the catalysts of isomerization of
α-pinene [5-7].
GC Hawllett Packard 5890 Series II, GC-MS Shimadzu
QP 5000, SAA Quantachrome ASiQwin 1:11, Philips XRD
Expert, PANalytical XRF MiniPal 4 and FT-IR spectrophoto-
meter Shimadzu FT-IR 8201 PC.
Natural zeolite has been activated, calcined at 400 °C for
4 h in a calcining furnace with nitrogen gas 10 mL/min.
Furthermore, natural zeolite impregnated with a Zr4+ metal
ion. Characterization of calcinated zirconia/zeolite was carried
out as the same step in the activation of zeolite, which the test
catalyst’s acidity using ammonia and pyridine.
Isomerization of α-pinene can produce bicyclic compound,
monocyclic or other products. Severino et al. [8] conducted
α-pinene isomerization reaction using zeolite as a catalyst and
they state that Lewis acid sites on the catalyst (weaker than
Brønsted sites) are beneficial for the formation of bicyclic
compounds, while Brønsted sites are responsible for the
The isomerization of α-pinene was carried out at atmospheric
pressure at 90, 120 and 150 °C in a batch reactor using three-
necked 100 mL flask with magnetic stirring, a thermometer and
reflux condenser.A mixture of 10 mL α-pinene and 0.5 g catalyst
was added the flask. After reacting for 60, 90, 120, 150 and 180
min, the product were analyzed by the GC-MS and FT-IR.