นิรมล วรสิษฐ. Decolorisation of Rice Bran Oil by Kaolinite. Doctoral Degree(Biochemical Technology). King Mongkut's University of Technology Thonburi. KMUTT Library. : King Mongkut's University of Technology Thonburi, 2010.
Abstract:
Acid activation is the traditional method of choice for improving the adsorption
efficiency of clay minerals used for decolorisation of vegetable oils. However, with
kaolin samples, simple acid activation treatment was ineffective, and this project has
focused on the determination of suitable activation procedures for application to the
Ranong kaolin for decolorisation of rice bran oil. The results show that modification of
the kaolin by combined physical and chemical treatments can produce material with
improved adsorption properties, but it was necessary first to destroy the ordered
structure of the mineral by physical treatment before acid activation. Physical
modification was achieved by grinding using a planetary ball mill (300 rpm for 1 h),
and this was followed by activation with various strengths of sulfuric or oxalic acid.
Optimum decolorisation was achieved by using 2 M H2S04 at 90?C for 4 h. With
H2C204, the best results were obtained with 0.7 M solution, but these were inferior to
those obtained with 2 M H2S04 acid. This treatment produced an increase in the specific
surface area of the resulting product from ~13 cm2/g to -244 cm2/g, and the total pore
volume from 0.06470 cm3/g to 0.4280 cm3/g. The pore size distribution curves show
that most pores are in the mesoporous region with their diameters of 3.0-4.5 run, and are
thus suitable for adsorption of pigment molecules that are present in rice bran oil. The
adsorption process could be described by both the Freundlich and Langmuir isotherm
models, and FTIR spectroscopy showed that adsorption of pigment molecules involved
acidic sites on the clay surface. Desorption and spectroscopic studies suggest that both
electrostatic and chemical processes are involved in the interaction between pigments
and active sites on the clay surface.
Various physical and analytical techniques (X-ray diffraction (XRD), X-ray
fluorescence (XRF), Scanning electron microscope( SEM), Fourier transform infrared
spectroscopy( FTIR), Electron paramagnetic resonance( EPR) and (Brunauer Emmett
Teller(BET) method) were used to characterise the structural changes in Ranong kaolin
that were induced by the chemical and/or physical modifications. Finally, the EPR
technique was used to study the rice bran oil before and after bleaching with modified
kaolin. The results showed that in addition to removing the material that contained a
stable free radical in the original oil, new free radicals were formed during the bleaching
processes. The EPR spectra of these free radicals resemble those of products
formed by oxidation of a-tocopherol and related tocopherols. However, unlike in
biological systems, these radicals were quite stable and persisted for several weeks,
indicating the presence of antioxidant molecules in the bleached oil that prevented their
further oxidation. The rice bran oil after bleaching by modified kaolin was slightly
yellow in color, the peroxide value decreased from 18.8 meq/kg to 5.3 meq/kg, but free
fatty acid remained unchanged at 0.14%.