Pyrolysis of Rice Husk: Analysis of its Biochar Properties

1. Introduction
The agricultural sector is one of the vital sectors in human life. The
agricultural sector has a very significant contribution to achieving the goals of the
second Sustainable Development Goals (SDG's) program, namely no hunger,
achieving food security, improving nutrition, and encouraging sustainable
agricultural cultivation. The role of the rice agricultural sector in Indonesia is also
very important because it is the second largest contributor to economic activity.
Indonesia's total rice production in 2021 will reach 54.42 Million Tons of MDG
(Milled Dry Grain) [1], During the rice milling process, the husks will separate
from the rice grains and become milling waste. The amount of rice husk waste
ranges from 20-23% of the grain [2], so that the total rice husk waste in
Indonesia's rice production in 2021 is more than 10 million tons.
Rice husk is a hard layer that covers the rice karyopsis consisting of two
interlocked parts called lemma and palea. Hard-to-weather organic materials such
as rice husks, mung bean stover, corn cobs, coconut shells, empty oil palm fruit
bunches, and so on have not been widely used as a source of soil organic matter.
Husk is categorized as a biomass that can be used for various needs such as
industrial raw materials, animal feed, energy, and fuel. Husk is composed of a
network of cellulose fibers which contain a lot of silica in the form of very hard
fibers so that the natural destruction of husks takes place slowly, and their
presence not only disturbs the surrounding environment, but also disturbs human
health. In addition, the potential of rice husk can be used as biochar, biochar from
rice husk also has a C-organic content of > 35% and a relatively high content of
macro nutrients such as N, P and K [3].
Biochar is biological charcoal from an incomplete combustion leaving
nutrients that can fertilize the land. If the combustion is complete, the biochar
turns into ashes and releases carbon, which has a lower value in terms of
environmental considerations.
In addition to reducing emissions and increasing the binding of greenhouse
gases, biochar can also increase soil fertility and agricultural crop production. In
contrast to organic fertilizers that experience decomposition, which will emit gas
in the form of methane, which causes global warming 21 times more than carbon
dioxide. Biochar biological decomposition is usually less than 20% after 5-10
years [4]. Rice husk biochar is an easily available source of organic material that
has the potential to be used to improve soil quality and increase crop yields. In
addition to increasing the pH, water holding capacity and cation exchange
 capacity, biochar addition also increased the weight of grain and straw by 30 and
40%, respectively. As a carrier material for FMA biological fertilizer, the addition
of husk charcoal into the zeolite media in the production of FMA inoculants can
improve the quality of inoculants, increase sorghum yields, and make production
costs more economical. However, the benefits of husk charcoal are not clearly
visible in a short time, charcoal and husk ash are sources of organic matter that are
difficult to decompose, due to the high lignin content. [5].
Hard-to-weathered organic matter contains high carbon, when processed using
pyrolysis techniques it can be used as a soil enhancer or biochar, one of which is to
increase the soil's ability to hold water. In addition, the use of organic matter in the
form of biochar is an action that can support soil carbon conservation [6].
In order to maximize the potential of biochar, it is necessary to vary the
temperature of pyrolysis. The yield of biochar decreases with increasing pyrolysis
temperature and is accompanied by an increase in carbon content, pH and
electrical conductivity [7]. Elements Al, Ca, Mg, Na, P, and K increase with
increasing pyrolysis temperature but there is no clear pattern for Fe and Si.
Variability of nutrients in biochar with increasing temperature is caused by the
volatility and the effect of pyrolysis temperature on both the composition and
chemical structure of biochar. In addition, the concentration of nutrients in biochar
also depends on the process of partial defraction or devolatilization of these
nutrients at high temperatures [8]. Based on this background, it is necessary to
conduct research on the effect of pyrolysis temperature on the character of rice
husk biochar.

2. Methods

3. Results and Discussion

3.1. Biochar's Chemical Properties
The X-ray Fluorescence (XRF) method was used to determine biochar's
chemical properties from rice husk. The characterization process was carried out on 4
samples of treated rice husks (250oC, 350oC, 450oC, and 550oC). The following is a
test table for each sample.
 Table 1. Chemical Properties of Rice Husk Biochar
Oxides Conc at Conc at Conc at Conc at
Compound 250oC 350oC 450oC 550oC
(%) (%) (%) (%)
SiO2 85,35 87,07 89,32 89,47
K2O 4,73 4,82 3,90 3,72
CaO 2,03 1,65 1,38 1,36
P2O5 2,43 2,16 1,86 1,79
Al2O3 1,73 1,60 1,78 1,88
Fe2O3 1,13 0,78 0,83 0,93
MgO 1,11 1,31 0,24 -
MnO 0,45 0,44 0,38 0,37
TiO2 0,17 0,12 0,11 0,13
Yields (%) 65,18 48,09 42,99 37,40
C 38,11 34,67 35,00 31,77
H 3,61 2,52 2,17 1,67
N 0,68 0,73 0,73 0,63

From table 1, information can be obtained that the results of pyrolysis of rice
husk biochar produce various oxide compounds, the dominant oxide compound
produced is a silicate compound (SiO2) with an average concentration percentage
above 85% and continues to increase linearly with the addition of pyrolysis
temperature. The concentration of silicates at 250oC is 85.35% and at the highest
pyrolysis temperature of 550oC the concentration reaches 89.47%. Pyrolysis
temperature also affects the interaction of carbon with silicon in biochar. For biomass
feedstocks that are rich in amorphous silicon, it was reported that pyrolysis in the
temperature range of 250 ~ 350 °C could cause a crack of carbon layer in the C–Si–C
structural configuration of biomass which exposes internal Si and leads to an
increasing solubility of Si in biochar [9].
Rice husk biochar samples at pyrolysis temperature changes were analyzed
for Carbon (C), Hydrogen (H), and Nitrogen (N) content. From the results of the
analysis above, information can be obtained that the carbon parameter (C) dominates
the rice husk biochar sample content with an average value above 30%, the Hydrogen
parameter (H) ranges between 1-4%, and the lowest parameter content is Nitrogen
(N) with a range of composition values below 1%. The large carbon (C) content is
because biochar is a carbon-rich product produced through a temperature pyrolysis
process from very light biomass [10]. The high carbon (C) content in biochar is
caused by a number of organic plant residues such as cellulose. The cellulose that is
still present in the biochar contains 37% carbon and 43-45% inorganic minerals.
Carbonization is characterized by the degradation of non-carbon atoms, thereby
increasing the carbon content (C) [11]. Pyrolysis temperature affects the structural
and physicochemical properties of biochar such as surface area, pore structures,
surface functional groups and elemental compositions [12]. The effect of pyrolysis
temperature on such properties can be ascribed to the release of volatiles at high
temperature [13]. Numerous studies reported that high pyrolysis temperature led to
increased biochar surface area, higher pH, %C content but lower %N content [14].
The severity of pyrolysis increases in terms of temperature, heating rate and
residence time, the initial feedstock will give place to a biochar with an increasing
aromaticity due to the formation of C complex structures while other compounds,
namely O and H, volatilize with a greater facility leading to a consequent reduction of
the H/C ratio. H/C atomic ratio seems to be a perfect mediate index for reflecting the
aromaticity of biochars and for predicting the sorption of hydrophobic organic
contaminants (HOCs) onto biochars. The H/C comparison index of rice husk biochar
due to the addition of temperature causes a decrease in the H/C index. The decrease
in the H/C ratio is associated with degree of carbonization.The lowest H/C ratio
(0.054) at 550 °C suggests that the biocharis highly carbonized, indicating higher
aromaticity at 550 °C com-pared to other employed temperature, especially at the
lowestone (250 °C). By contrast, among biochar samples, the highest H/C ratio
(0.095) found at 250 °C indicates that the biochar has con-siderable quantities of
organic materials, it can be confirmed that pyrolysis temperature is definitely the
main variable that influences both biochar yield and H/C ratio [15].
The C/N ratio index is the main indication of the preservation of collagen
protein and/or as an index of contamination by soil materials. The effect of the
addition of pyrolysis temperature on the C/N ratio index has decreased, the decrease
in the C/N ratios with temperature is associated withdehydration reactions and
resulting in less hydrophilic biochar surface [16].
A decrease in H/C and C/N atomic ratio in the biochar samples was observed
by increasing the pyrolysis temperature which can be attributed to the loss of H and
O, leading to more carbon aromaticity. The decrease in H/C and O/C atomic ratios
with increasing temperature to the removal of H- and O-containing functional groups
so that the biochar prepared at high temperature has a high aromaticity and low
polarity [16].
 Graph 1. Correlation of pyrolysis temperature to biochar yields
Graph 1 shows the biochar yield analysis for the rice husk biochar samples
produced at the different pyrolysis temperatures. It was observed that biochar yield
decreased with increasing pyrolysis temperature. Decreasing trend was observed for
the char samples produced at pyrolysis temperatures of 250 to 550 °C. This is
because at higher temperatures, there was a rapid and comprehensive decomposition
of lignocellulosic components that resulted in a reduction in biochar yield [17].
Besides that, the decrease in biochar yield was also due to the decrease in the mass of
the rice husk samples after the combustion process was carried out. This result is
consistent with the results of [18] and [3], which stated that the addition of pyrolysis
temperature would cause a decrease in the percentage of biochar yields of a material
[20].
3.2. Fourier Transform-Infrared (FT-IR) Spectroscopy

Graph 2. FTIR Spectrum from Rice Husk Biochar

Graph 2 shows the FTIR spectra for the rice husk biochars produced under
different pyrolysis temperatures. Fourier Transform Infrared (FTIR) spectroscopy
used to analyses the effect of temperature and time of heating to the surface
functional groups of biochar. The spectrum of each biochar is characterized into four
groups: The first group is the O-H functional group which is in the wave number
range of 2500-3700 cm-1, the second group is the alkyne functional group which is in
the wave number range of 2000-2500 cm-1, the third group is the inorganic functional
groups, showing that the peaks at around 1600 and 1700 cm –1 could be the presence
of C=O stretching of aromatic rings and Lignin, respectively [21]. The fourth group is
the main functional group which is characteristic of rice husk biochar (500-1500 cm -
1
), for cellulose it is shown by the presence of C-OH Bending at wave number 1095
cm-1 while for C-H Bending for alkena is present at wave number 675-995 cm-1 [22].
 The lower temperature derived biochars were less thermally stable than the
higher temperature derived biochars, because they were not fully carbonized [23].
The combustion process of pyrolysis temperature make the O-H functional groups
expand and disappear, this is because the O-H functional groups are reactive to
combustion [24]. The alkyne functional group formed from the pyrolysis process
produces a C=O bond, in a closed space where the amount of oxygen does not meet,
imperfect alkyne combustion will occur. The C-H functional group (alkene) formed
at wave number 675-995 cm-1 slightly shifted towards a higher wave number as the
pyrolysis temperature increased. Alkene are groups in the form of carbon with a high
number of purity, where there is the release of elements O and H which were
originally combined with element C [25].

3.3. X-Ray Diffraction Analysis

X-Ray diffraction analysis (XRD) is a nondestructive technique that provides
detailed information about the crystallographic structure, chemical composition, and
physical properties of a material [26]. It is based on the constructive interference of
monochromatic X-rays and a crystalline sample. X-rays are shorter wavelength
electromagnetic radiation that are generated when electrically charged particles with
sufficient energy are decelerated. In XRD, the generated X-rays are collimated and
directed to a nanomaterial sample, where the interaction of the incident rays with the
sample produces a diffracted ray, which is then detected, processed, and counted. The
intensity of the diffracted rays scattered at different angles of material are plotted to
display a diffraction pattern.
 Graph 3. XRD Analysis from Rice Husk Biochar
SiO2 is a dominant amorphous compound formed from rice husk biochar
samples. The pyrolysis process and the addition of temperature make the initially
amorphous silicates into crystals silicates. From the X-Ray Diffraction (XRD) results,
it can be seen that the amorphous biochar of rice husk decreases with increasing
pyrolysis temperature, whereas the crystallinity value of biochar increases with
increasing pyrolysis temperature. A qualitative assessment of the crystallinity of the
samples can be obtained from the intensity of the narrow reflections with the
comparation to the spectra around 2 theta (22 o) for Rice husk burned at 250-550 oC.
These results are consistent with research [27, 28, 29], which states that the addition
of pyrolysis temperature changes amorphous compounds into crystals.

3.4. Calori Metric Analysis

Caloric metric analysis was carried out to be able to see the potential for
stored heat energy from the rice husk biochar obtained. This analysis was also carried
out using the pyrolysis temperature increase parameter from 250oC to 550oC. The
following is the result of calorie analysis from rice husk biochar samples.
Table 2. Calori Metric Analysis
Sample Results Unit
250 14,4818 MJ/Kg
350 12,6014 MJ/Kg
450 12,9670 MJ/Kg
550 11,6164 MJ/Kg

From table 2 above, information can be obtained that the increase in pyrolysis
temperature to the value of the caloric content of biochar will decrease. The biochar
sample at a pyrolysis temperature of 250oC has a calorific value of 14.48 MJ/Kg and
continues to decrease at a pyrolysis temperature of 550 oC with a calorific value of
11.61 MJ/Kg. The calorific value as a main criterion in the assessment of energy
potential of raw fuel, was also more promising in the case of rice husk biochar.
Rice husk biochar which has the potential to be the best energy storage for use
as solid fuel is biochar in the low temperature pyrolysis process [30], this happens
because of the reduction in the value of biochar yields from the process of increasing
pyrolysis temperature.
4. Conclusion
The dominant oxide compound produced is a silicate compound (SiO 2) with an
average concentration percentage above 85% and continues to increase linearly with
the addition of pyrolysis temperature. In addition, the carbon composition produced
in the low temperature pyrolysis process is very high when compared to the high
temperature process, but biochar yield decreased with increasing pyrolysis
temperature, decreasing trend was observed for the char samples produced at
pyrolysis temperatures of 250 to 550 °C. From the FTIR spectra, the spectrum of each
biochar is characterized into four groups: The first group is the O-H functional group
which is in the wave number range of 2500-3700 cm -1, the second group is the alkyne
functional group which is in the wave number range of 2000-2500 cm -1, the third
group is the inorganic functional groups, showing that the peaks at around 1600 and
1700 cm–1 could be the presence of C=O stretching of aromatic rings and Lignin,
respectively. The fourth group is the main functional group which is characteristic of
rice husk biochar (500-1500 cm-1), for cellulose it is shown by the presence of C-OH
Bending at wave number 1095 cm-1. And then for the last analysis using X-Ray
diffraction analysis (XRD), it can be seen that the amorphous biochar of rice husk
decreases with increasing pyrolysis temperature, whereas the crystallinity value of
biochar increases with increasing pyrolysis temperature. In Summary, rice husk
biochar has great potential in producing silicate crystals.

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