Effect of Demineralization On The Physiochemical Structure and Thermal Degradation of Acid Treated Indigenous Rice Husk
Effect of Demineralization On The Physiochemical Structure and Thermal Degradation of Acid Treated Indigenous Rice Husk
Effect of Demineralization On The Physiochemical Structure and Thermal Degradation of Acid Treated Indigenous Rice Husk
Pol. J. Chem.
10.1515/pjct-2016-0057
Tech., Vol. 18, No. 3, 2016 117
Energy generation from biomass presents some serious problems like slagging, fouling and corrosion of boilers.
To address these problems, demineralization of biomass is performed using different leaching agents. This study is
focused on determining the influence of leaching agents and leaching time on the physiochemical structure of rice
husk during demineralization. Dilute (5% wt) solutions of HCl and H2SO4 were used for the demineralization of
rice husk separately with leaching time of 15, 60 and 120 minutes. It is shown that H2SO4 exhibited higher removal
of alkali and alkaline earth metals (AAEM) comparatively as depicted by the 34.2% decrease in ash content along
with an increase of 7.10% in the heating value. The acid has been seen to induce more notable changes in physi-
ochemical structure as depicted by the FTIR spectra and SEM micrographs. The thermal degradation behavior
of the demineralized rice husk has also been reported.
Keywords: demineralization, leaching agent, physiochemical structure, alkali and alkaline earth metals,
thermal degradation.
approached to neutral. After washing, treated samples The sample was placed in the furnace of SDT Q600 TA
were dried in an oven at 80oC for 24 h and then were instrument. It was initially heated up to 100oC in N2
stored in air tight bags for further analysis. The identi- environment. Then temperature was raised to 500oC in
fication of each sample and actions performed on them N2 environment. At the end, the sample was burned by
are shown in Table 1. increasing the temperature to 950oC in O2 environment.
The heating rate was set at 10oC/min.
Scanning electron microscopy (SEM)
In order to investigate leaching efficiency and structural Ash percentage and heating value
changes, the surface morphology and shape, all samples The ash percentage was calculated by using ASTM 3174
were observed by SEM (JEOL JSM-6490 LV) operating and heating value was calculated by using ASTM D5865.
at low vacuum and 5 kV accelerating voltage. Conductive
coating was applied to prepare the samples for analysis. RESULTS AND DISCUSSION
Fourier transform infrared (FTIR) Spectroscopy
SEM
FTIR spectroscopy was performed using ASTM E1252
in order to observe the structural changes after demi- Figure 1 shows the SEM images of raw and treated
neralization of rice husk qualitatively. rice husk. Raw sample has clear structure and plant
epidermis and stomata are not damaged (shown in
Thermogravimetric Analysis Fig. 1a). While fuzziness and erosion can be observed
Thermal degradation behavior was studied based on in treated samples (shown in Fig. 1b–1g). Raw sample
the thermal behavior of the samples using a Thermo- has less porosity than the treated samples especially in
gravimetric Analyzer (TGA) SDT Q600 from TA In- case of Figures 1f (R5) and 1g (R6) which means H2SO4
struments. 10mg sample was taken in platinum crucible. as leaching agent has more significant effect on biomass
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Figure 1. SEM images of raw and treated samples Download Date | 10/13/16 2:23 PM
Pol. J. Chem. Tech., Vol. 18, No. 3, 2016 119
Table 1. Identification and actions performed on each sample vibration of –CH2 and –CH3 functional groups. A slight
change in both bands can be observed after acid treat-
ment specially for samples R3, R5 and R6 and it is in
agreement to with the studies done by Jiang et al.17 and
Asadieraghi et al.15. The peak at 1730 cm–1 corresponds
to C=O stretching vibration of free carbonyl group
therefore it is a typical hemicellulose component. The
next peaks from 1650–1510 cm–1 shows C=C stretching
vibrations of aromatics and generally considered as lignin
component. A slight change in intensity of bands around
1730 cm–1 and 1650 cm–1 of samples R3 and R6 can be
structure by dissolving cellulose and hemicellulose11, 14.
observed which is probably due to the high removal of
Increased porosity also indicates that some material was
inorganics comparatively. The spectrum around 1400–600
leached away by dilute acid solutions. The removed par-
cm–1 is very complex to analyze. However, in this region
ticles from biomass might be extractives and minerals15.
vibrations related to lignin components can be detected
The removal of minerals and extractives and dissolution
as at 1240 cm–1 (C=O stretching), 850–750 cm–1 (C-H
of hemicellulose and cellulose may result in the higher
bending). The band between 1440–1400 cm–1 contains
availability of surface area and pore volume16.
O-H bending which are related to hemicellulose and
FTIR spectroscopy cellulose. A band intensity change in this region can be
observed in case of sample R6. All above band variations
Chemical structure evaluation of biomass is frequently
indicate that some changes have occurred in cross linking
studied using infrared spectroscopy. In this study, FTIR
between different functional groups and thus represents
technique was used to investigate the impacts of acid
the acid treatment effects. More significant changes can
treatment on the biomass chemical structure. Figure
be observed in case of sample R6.
2 shows the various FTIR spectra of HCl (Fig. 2) and
H2SO4 (Fig. 3) treated biomass samples. Thermogravimetric analysis
In the spectra, the first broad band at 3700–3000 cm–1
Figure 4 shows the TG curves (percentage weight
can be observed and it is related to O-H stretching
loss vs temperature) and Figure 5 shows DTG curves
vibrations of hydroxyl functional groups which may be
(differential weight loss vs temperature) for raw and
present in phenolic, alcoholic and carboxylic structures.
treated samples. Three regions in all the curves can be
The band at 2800–3000 cm–1is attributed to C-H stretching
observed. The first region from 0oC to 100oC is assi-
gned to water evaporation. The second region between
250–400oC is attributed to decomposition of cellulose
and hemicellulose. The third region between 450–500oC
shows the degradation of lignin17. In the second region,
two peaks can be observed. The first peak represents
the decomposition of thermally unstable hemicellulose
while second peak is showing the degradation of cellu-
lose. It can also be observed that the peaks of treated
samples have slightly shifted towards right side showing
an increase in temperature presented in Table 3. This
can be explained by the reason that AAEM, which act
as catalyst during decomposition, have been removed
through acid treatment and cellulose and hemicellulose
are now more resistant towards thermal degradation18.
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Figure 3. FTIR spectra of raw and H2SO4 treated samples Figure 4. Mass loss (TG) curves of
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Date and untreated
| 10/13/16 2:23 PM samples
120 Pol. J. Chem. Tech., Vol. 18, No. 3, 2016
Figure 5. Derivative mass loss (DTG) curves of treated and untreated samples
Ash percentage and heating value shifting of peaks of treated samples towards high tem-
Table 2 shows the ash percentage and heating value of perature in TG and DTG curves showed that treated
all the samples. A maximum decrease of 34.2% in ash sample are more resistant towards thermal degradation
content of sample R6 was observed while a maximum due to the elimination of catalytic role of AAEM. An
increase of 7.10% in heating value was observed also for increase of 7.10% in heating value was also shown by
R6. These results are consistent with Carrillo et al.19. R6 validating the reciprocal relation between ash content
While for R1, R2, R3, R4 and R5 percentage decrease and heating value.
in ash content was 15.6, 17.4, 33, 16.60 and 18.04 re-
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Pol. J. Chem. Tech., Vol. 18, No. 3, 2016 121
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