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Waste Biomass Valor

DOI 10.1007/s12649-010-9045-3

ORIGINAL PAPER

Production of Solid Biofuel from Agricultural Wastes of the Palm


Oil Industry by Hydrothermal Treatment
Ahmad T. Yuliansyah • Tsuyoshi Hirajima •

Satoshi Kumagai • Keiko Sasaki

Received: 24 April 2010 / Accepted: 25 September 2010


Ó Springer Science+Business Media B.V. 2010

Abstract In this study, upgrading of agricultural waste, Introduction


in the form of oil palm fronds and trunks, into solid biofuel
was investigated using hydrothermal treatment. A slurry of The rapid increase in energy consumption within the last
300 mL of water and 30 g of material was treated in a few years, combined with the steady depletion of fossil fuel
500-mL batch autoclave equipped with stirrer, thermo- reserves, has prompted a global search for alternative
meter, and pressure sensor. Experiments were conducted in energy resources. Biomass is a promising alternative owing
the temperature range 200–350°C at an initial pressure of to its sustainability and environmental friendliness. Various
2.0 MPa. The slurry was gradually heated to the target types of biomass products are available in large quantities
temperature and held for a further 30 min. Approximately and have potential for further utilization.
35–65% of the original material was recovered as a solid One potential biomass source that is abundant in most
product with favorable solid fuel characteristics. The gross tropical countries is oil palm waste. This waste can be
calorific value ranged from 19.9 to 29.7 MJ/kg and the categorized into two types: waste from harvesting and
equilibrium moisture content was 7.6–4.5 wt%. The carbon replanting activity in plantation fields and waste from the
content varied from 51.4 to 78.5 wt% and the oxygen milling process to obtain palm oil. Numerous studies on
content was 42.1–16.1 wt% after upgrading. Changes in the utilization of milling waste (oil palm fiber, shell, and
solid composition and carbon functional groups following empty fruit bunches) have been conducted for energy
upgrading were identified by FTIR and 13C NMR. In applications [1–3], pulp and papermaking [4–6], bio-
addition, analyses on the liquid product (by GC–MS) and adsorbents [7–10], construction materials [11, 12], and
the gas product (by GC) were carried out to clarify the biocomposites [13–15]. However, most of the milling
decomposition behavior of material. waste is fully utilized by the palm oil industry either as an
additional energy source (oil palm fiber and shell) or as
Keywords Upgrading  Agricultural waste  Biomass  fertilizer (empty fruit bunches). By contrast, only a few
Hydrothermal treatment  Solid biofuel studies have considered the utilization of harvesting
waste. Currently, most of this waste is used convention-
ally as an organic fertilizer in plantation fields. However,
A. T. Yuliansyah—On leave from Department of Chemical unpleasant smells coupled with a slow release of CO2 and
Engineering, Gadjah Mada University, Indonesia. CH4 gas on decomposition, which can last for up to
1 year, are common problems. Nevertheless, oil palm
A. T. Yuliansyah  T. Hirajima (&)  K. Sasaki
fronds and trunks have great potential. In 2005, approxi-
Department of Earth Resources Engineering, Faculty of
Engineering, Kyushu University, 744 Motooka, Nishi-ku, mately 43.05 million ton of frond and 13.94 million ton
Fukuoka 819-0395, Japan of trunk wastes were generated in Indonesia, the largest
e-mail: hirajima@mine.kyushu-u.ac.jp crude palm oil producer in the world. This amount will
continue increase with the rapid growth in the Indonesian
S. Kumagai
Research and Education Center of Carbon Resources, Kyushu palm oil industry. Thus, a better method to manage such
University, 744 Motooka, Nishiku, Fukuoka 819-0395, Japan wastes is highly desired.

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Waste Biomass Valor

Various treatment methods for several agricultural pretreatment step in bio-ethanol production [26–29]. Few
wastes have been reviewed in several papers [16–19]. For studies have considered benefits of the resulting solid. The
energy application purposes, the methods can be simply focus of the present study was upgrading of solid material
divided into thermo-chemical and biological processes [20, into solid biofuel by hydrothermal treatment. Therefore, we
21]. Hydrothermal treatment is one of thermo-chemical evaluated the feasibility of upgrading oil palm fronds and
processes have attracted much attention recently. In this trunks and investigated their decomposition behavior dur-
process, biomass is treated in hot compressed water ing hydrothermal treatment.
yielding in gases, aqueous organics and upgraded solid [22,
23]. After filtered and dried, the obtained solid can be used
for solid fuel due to its high calorific value. Compared to
Experimental
other thermo-chemical conversion methods such as pyro-
lysis and gasification, the temperature for hydrothermal
Materials
treatment is much lower (200–350°C for hydrothermal,
compared with 450–550°C for pyrolysis and 900–1200°C
Oil palm waste in the form of fronds and trunks was col-
for gasification) [16, 24]. In addition, biomass conversion
lected from an oil palm plantation in southern Sumatra,
takes place in a wet environment so high moisture content
Indonesia. Both raw fronds and trunks were chipped into
of feed biomass is not an issue. The role of water in the
pieces of approximately 2 cm in width of slabs. Prior to
treatment is not only as a medium, but also a chemical
use, the chips were ground using a cutting mill to form
reactant on decomposition. Therefore, such method is
powder with a maximum particle size of 1 mm. The
suitable for treating biomass with high moisture content,
composition of the waste material is listed in Table 1.
such as agricultural wastes which contain more than 50 wt. %
of moisture in fresh condition. A contrast situation is found
on pyrolysis and gasification which have a limitation on Apparatus and Experimental Procedure
moisture content of the feed [24, 25].
Many studies using hydrothermal treatment have been Experiments were carried out in a 500-mL batch-type auto-
conducted, but most of these used the method as a biomass clave (Taiatsu Techno MA 22) equipped with a stirrer and an
automatic temperature controller (Fig. 1). The autoclave had
a maximum temperature of 400°C and a maximum pressure
Table 1 Composition of the raw materials
of 30 MPa. A slurry of 300 mL of water and 30 g of waste
Component Frond Trunk material was loaded into the autoclave. A stream of N2 gas
Cellulose (wt. %, d.b) 31.0 39.9 was used to purge air from the autoclave and to maintain an
Hemicellulose (wt. %, d.b) 17.1 21.2
initial internal pressure of 2.0 MPa. With stirring at 200 rpm,
Klason lignin (wt. %, d.b) 22.9 22.6
the autoclave was heated to the target temperature at an
average rate of 6.6°C/min. The target temperature, ranging
Wax (wt. %, d.b) 2.0 3.1
from 200 to 350°C, was automatically adjusted. Once the
Ash (wt. %, d.b) 2.8 1.9
target temperature was reached, the sample was held for a
Others 24.2 11.3
further 30 min before the autoclave was cooled to ambient

Fig. 1 Schematic diagram of


the experimental apparatus

Cooling water out Cooling water in


PS
TS

N2
Control Board

Vessel

PS = Pressure Sensor
TS = Temperature Sensor

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Waste Biomass Valor

300) with the following conditions: 10,000 scans; contact


time, 2 ms; spinning speed,[12 kHz; pulse repetition time,
7 s. The spectrum was calibrated using hexamethyl ben-
zene. Curve fitting analysis of the spectrum was performed
using Grams/AI 32 ver. 8.0 software. Composition of the
liquid products were analyzed by gas chromatography—
mass spectrophotometer (GC–MS) Agilent 6890 N equip-
ped with Jeol JMS-Q1000GC(A) system. Additionally, total
organic carbon content of liquid was determined on a Shi-
madzu TOC-5000A instrument. Solid yield, energy densi-
fication ratio, and energy yield are three important
parameters in this study which are defined as [31]:
Solid yield ¼ mass of dried solid product=
Fig. 2 Pressure and temperature profile for experiments (1 200°C; 
2 240°C; 3 270°C; 4 300°C; 5 330°C; 6 350°C) mass of dried feed material  100%
Energy densification ratio ¼ GCV of product=
conditions. Pressure and temperature profile for the experi- GCV of feed material
ments was described in Fig. 2.
After cooling, the gas products were fed into a gasometer Energy yield ¼ solid yield  energy densification ratio
(Shinagawa DC-1) to measure the volume. The gas was
sampled using a microsyringe (ITO MS-GANX00) and its .
composition was determined by gas chromatography with
thermal conductivity detection (Shimadzu GC-4C). The
remaining slurry was filtered using an ADVANTEC 5C Results and Discussion
filter and a water aspirator. The solid part was dried in an
oven at 105°C to yield the final solid product. Product Distribution

Analysis Hydrothermal treatment led to thermal degradation of the


feed material. Physical and chemical bonds in the material
The solid products were characterized using several tech- were broken, so that large long-chain compounds such as
niques. The elemental composition was measured using cellulose, hemicellulose and lignin were broken down into
Yanaco CHN Corder MT-5 and MT-6 elemental analyzer. smaller and simpler molecules. Furthermore, some of the
The cellulose, hemicellulose, and lignin contents were molecules were dissolved into liquid part and some others
measured using a procedure recommended by the US were degraded to gases. The remainder of feed material
National Renewable Energy Laboratory [30] that is sub- was recovered as a solid residue. Filtration and drying
stantially similar to ASTM E1758-01. The mineral com- yielded a solid product from this residue.
position in ash was determined using X-ray fluorescence Figure 3 shows the distribution of organic compounds,
(XRF) on Rigaku ZSX Primus II equipment. In addition, represented by percentage carbon, in the gas, liquid, and
proximate, total sulfur and gross calorific value (GCV) solid phases. However, a small amount of material was not
analyses were carried out according to JIS M 8812, JIS M recovered during filtration and drying. The results indicate
8819, and JIS M 8814, respectively. The equilibrium that most of the carbon remained in the solid phase and that
moisture content (EMC) of raw frond and trunk and the the relative amount gradually decreased as the temperature
corresponding solid products was determined according to increased. Conversely, the proportion of carbon in the gas
JIS M 8811. An aliquot of the sample was placed in a phase steadily increased with temperature. For the liquid
desiccator containing saturated salt solution at a constant phase, a unique characteristic was observed. The relative
relative humidity (75% RH). After equilibrium was reached, amount of carbon increased with temperature to a maxi-
the moisture content of the solid was quickly measured mum at *270°C and then decreased owing to polymeri-
using a Sartorius MA 150 analyzer. Identification of the zation of soluble compounds to produce solid precipitates.
chemical structure and functional groups was performed on
a Fourier transform infrared (FTIR) spectrometer (JASCO Solid products
670 Plus) using the KBr disk technique. Cross polarization/
magic angle spinning (CP/MAS) 13C NMR spectra were The properties of solid products for different temperature
measured on a solid-state spectrophotometer (JEOL CMX- treatments are described in Table 2. Reaction temperature

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Waste Biomass Valor

The calorific value is correlated with the elemental


composition of a solid. The data in Table 2 show that an
increase in calorific value is correlated with an increase in
carbon content and a decrease in oxygen content. Com-
pared to the raw material, the solid produced at 350°C has
*59% higher carbon content and *58% lower oxygen
content. These results suggest that components degraded
and removed from the material were mainly oxygen-rich
compounds. Dramatic changes in the calorific value and
elemental composition took place in the temperature range
200–270°C.
Due to thermal degradation, the content of cellulose,
hemicellulose, and lignin in the solid decreased. Table 3
shows the percentage of these components in the solid
products after treatment at 200–300°C. The data suggest
that hemicellulose and cellulose were relatively easier to
degrade than lignin. The treatment significantly degraded
both hemicellulose and cellulose to produce a more lig-
neous solid. Slightly different behavior was observed for
hemicellulose decomposition between frond and trunk
material. The frond solid produced at 200°C still had a
small amount of hemicellulose, which completely vanished
on treatment at 240°C. On the other hand, no hemicellulose
was found for the trunk products, even for treatment
200°C. This suggests that hemicellulose decomposition
started at temperatures \200°C. By contrast, cellulose was
gradually degraded at higher temperature and \0.5 wt%
(on a solid product basis) remained after treatment at
270°C. This behavior is in agreement with previous reports
Fig. 3 Distribution of carbon in the hydrothermal product a frond;
[22, 32].
b trunk
The obtained solids contained a small amount of ash
had a significant effect to the solid yield, energy densifi- ranging from 0.7 to 2.2 wt% (Table 2). The use of these
cation ratio and energy yield of the solid products. low-ash products as fuel will be beneficial because it will
Increasing temperature led to a decrease in solid yield and reduce potential for solid deposition on burner equipment
energy yield, while energy densification ratio increased. that commonly found on combustion of high-ash fuel.
For the same reaction temperature, the solid product of Table 4 shows ash analysis of frond and trunk solid prod-
trunk had a higher solid yield and energy yield than frond. ucts. As can be seen from this table, CaO and SiO2 were
However, the differences were smaller at higher tempera- two major oxides accounted for 28.80–51.30 and
ture. At 200°C, the solid yields were 58.3 and 67.8 wt%, 16.40–39.10 wt% for frond, and 15.20–27.30 and
while the energy yields were 63.5 and 71.7%, for frond and 22.80–44.30 wt% for trunk, respectively. The data in
trunk, respectively. The solid yield reduced to 35.1 and table 4 also indicates that some minerals such as CaO,
35.3 wt%, while the energy yield decreased to 55.4 and MgO and K2O were selectively leached from material
55.7% at 350°C treatment. during treatment.
Like other biomass materials, both fronds and trunks
have very high volatile content of 82.5 and 83.9 wt%, in Coal Band
contrast to the low fixed carbon of 17.5 and 16.1 wt%,
respectively. Progressive decomposition reactions occurred Under hydrothermal treatment, frond and trunk materials
at higher temperature, leading to an increase in fixed carbon undergo a coalification-like process, as demonstrated in the
content and a decrease in volatile content. Treatment at Van Krevelen diagram in Fig. 4. The raw materials have
350°C increased the fixed carbon content to 54.8 and high atomic H/C and O/C ratios, which both gradually
55.0 wt% and decreased the volatile content to 45.2 and decreased during treatment. The slope of the trajectories
45.0 wt% for fronds and trunks, respectively. This led to an suggests that the O content decreased in proportion to the H
increase in gross calorific value of the solid product. content, probably due to dehydration. It is clear that the

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Table 2 Properties of the raw materials and the solid products


Properties Raw Treated temperature (°C)
200 240 270 300 330 350

(a) Frond
Proximate analysis (wt.%)
Fixed carbon (d.a.f) 17.5 20.5 29.7 45.9 48.1 52.3 54.8
Volatile matter (d.a.f) 82.5 79.5 70.3 54.1 51.9 47.7 45.2
Ash (d.b) 1.8 1.3 1.3 1.2 1.0 0.7 0.8
Equilibrium moisture 14.7 7.6 6.4 5.5 5.2 5.0 5.2
Ultimate analysis (wt.%) (d.a.f)
C 47.2 53.6 58.6 69.4 71.1 73.9 75.1
H 5.9 5.7 5.4 4.9 4.9 4.9 4.8
N 0.2 0.2 0.3 0.4 0.4 0.4 0.4
O (diff) 46.6 40.4 35.7 25.3 23.5 20.7 19.5
S 0.1 0.1 0.1 0.1 0.1 0.1 0.1
Yield of solid product (wt.%) (d.b) 58.3 52.0 42.5 38.4 36.7 35.1
Gross calorific value (MJ/kg) (d.a.f) 18.8 20.5 23.0 26.7 27.3 29.0 29.7
Energy densification ratio 1.09 1.22 1.42 1.45 1.54 1.58
Energy yield (%) 63.5 63.6 60.3 55.9 56.5 55.4
(b) Trunk
Proximate analysis (wt.%)
Fixed carbon (d.a.f) 16.1 16.2 26.6 45.1 48.8 52.8 55.0
Volatile matter (d.a.f) 83.9 83.8 73.4 54.9 51.2 47.2 45.0
Ash (d.b) 2.2 1.8 1.8 2.2 2.1 1.9 2.1
Equilibrium moisture 13.6 7.5 6.5 5.1 4.8 4.6 4.5
Ultimate analysis (wt.%) (d.a.f)
C 47.5 51.4 57.5 69.3 71.4 73.4 75.3
H 5.9 5.9 5.6 5.1 5.0 4.9 4.9
N 0.5 0.4 0.6 0.8 0.8 1.0 1.0
O (diff) 45.9 42.1 36.2 24.6 22.6 20.6 18.6
S 0.1 0.1 0.1 0.1 0.1 0.1 0.2
Yield of solid product (wt.%) (d.b) 67.8 56.9 41.7 38.7 36.9 35.3
Gross calorific value (MJ/kg) (d.a.f) 18.8 19.9 22.6 27.0 28.0 29.4 29.7
Energy densification ratio 1.06 1.20 1.44 1.49 1.57 1.58
Energy yield (%) 71.7 68.3 60.0 57.8 57.9 55.7
d.b dry basis, d.a.f dry ash free basis, diff. differences

Table 3 Percent component in the solid products decrease in O and H content occurred mainly in the range
200–270°C. Less significant changes were observed at
Product Cellulose Hemicellulose Lignin & other
higher temperature. The solids resulting from higher tem-
Frond perature treatment had comparable compositions with
200°C 55.1 3.2 41.7 typical solid fuels such as sub-bituminous coal. Although
240°C 42.3 0.0 57.7 fronds and trunks have different raw compositions, the
270°C 0.2 0.0 99.8 products after treatment at C300°C had almost identical
300°C 0.0 0.0 100.0 compositions.
Trunk
200°C 62.9 0.0 37.1
Fourier Transform Infrared (FTIR) Analysis
240°C 44.8 0.0 55.1
270°C 0.4 0.0 99.6
To understand changes in functional groups during
300°C 0.0 0.0 100.0
hydrothermal treatment, FTIR analysis of the products was

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Table 4 Mineral composition of ash in the raw materials and the solid products
Solid products Oxide (wt.%)
CaO SiO2 MgO K2O Fe2O3 Al2O3 ZnO SO3 P2O5 Others

(a) Frond
Raw 52.70 12.20 16.00 8.29 0.39 0.21 0.05 7.21 2.43 0.52
200°C 51.30 28.70 6.04 3.66 1.41 0.79 0.06 5.78 1.10 1.16
240°C 39.50 32.90 7.52 4.36 1.97 1.49 0.07 8.31 2.54 1.34
270°C 28.80 39.10 7.60 4.64 1.22 1.61 0.05 12.40 2.95 1.63
300°C 30.80 29.60 6.95 5.50 2.19 2.17 0.05 15.20 5.36 2.18
330°C 37.10 16.60 8.49 6.03 2.54 2.62 0.07 16.30 8.14 2.11
350°C 36.50 16.40 8.51 5.71 2.96 2.67 0.08 16.00 7.83 3.34
(b) Trunk
Raw 23.50 14.90 15.60 24.50 0.71 0.25 0.12 10.70 8.71 1.00
200°C 18.80 39.80 8.37 13.20 1.14 0.67 0.11 9.54 7.27 1.10
240°C 15.20 44.30 5.83 9.21 1.43 0.76 0.10 9.23 13.10 0.84
270°C 16.40 44.00 4.64 7.38 1.21 0.83 0.06 9.95 14.80 0.73
300°C 18.20 41.40 4.64 5.38 1.69 1.49 0.06 7.97 18.20 0.97
330°C 27.30 22.80 5.05 6.76 2.57 1.22 0.15 9.64 23.00 1.51
350°C 22.10 22.80 11.80 5.16 3.13 0.76 0.12 9.33 18.40 6.41

represents carbonyl (C=O) stretching vibrations. The peak


at *1515 cm-1 reveals to aromatic skeletal vibration
derived from lignin. The peak at *1050 cm-1 attributed to
glycosidic bonds, indicating the presence of cellulose,
steadily weakened and completely disappeared for tem-
peratures [270°C, indicating that cellulose was totally
degraded at this temperature. The decrease in intensity for
C–O–C aryl–alkyl ether linkages at *1230 cm-1 suggests
lignin decomposition. Conversely, solids derived from
polymerization of intermediate compounds in the liquid
phase increased the aromatic content, particularly at tem-
peratures [300°C, as indicated by the increase in intensity
for the peak at 1600 cm-1 attributed to aromatic skeletal
vibrations and CO stretching.
Fig. 4 Van Krevelen diagram for the solid products obtained at
different temperatures in comparison with other solid fuel (1 raw
13
material; 2 200°C; 3 240°C; 4 270°C; 5 300°C; 6 330°C; 7 350°C; C Nuclear Magnetic Resonance (NMR) Results
a frond; b trunk)
13
C NMR measurements were conducted to complement
performed. Peaks were assigned based on literature data [3, FTIR in characterizing the molecular structure of the solid
33]. Figure 5 shows spectra of the raw materials and the products. NMR is useful for making comparisons without the
corresponding solid products. The spectra for frond and need for peak ratios. Each resonance peak can be measured
trunk materials were similar. The intensity of the peak relative to the total resonance intensity to give the relative
*3500 cm-1 attributed to –OH groups decreased at ele- amount of individual molecular groups. Typical 13C NMR
vated temperature, indicating that water molecules within spectra for raw biomass with peak assignment can be found
the solids were gradually expelled. In other words, dehy- in the literature [34–36]. In brief, resonance peaks in spectra
dration of the feed material occurred. The peak at for raw frond and trunk material were assigned to CH3 in
*2900 cm-1 attributed to aliphatic CHn groups also acetyl groups (21 ppm), methoxyl groups in lignin
weakened, indicating that several long aliphatic chains were (56 ppm), C-6 carbon atoms in cellulose (62–65 ppm), C-2/
broken down. More distinctive peaks were observed in the C-3/C-5 atoms in cellulose (72–75 ppm), C-4 atoms in cel-
region below 2000 cm-1. The peak at *1700–1740 cm-1 lulose (84–89 ppm), C-1 atoms in hemicellulose (102 ppm),

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Fig. 6 13C NMR spectra with curve fitting for raw frond and products
obtained at different temperatures

aromatic content, which correlates with the lignin content,


consistently increased in the range 200–270°C, whereas the
carbohydrate content (hemicellulose and cellulose)
Fig. 5 FTIR spectra for the raw materials and the corresponding decreased. This is in good agreement with the component
products a frond; b trunk analysis, which suggested that lignin was the predominant
component for treatment at C270°C (Table 3).

C-1 atoms in cellulose (105 ppm), unsubstituted olefinic or Equilibrium Moisture Content (EMC) Analysis
aromatic carbon atoms (110–127 ppm), quaternary olefinic
or aromatic carbon atoms (127–143 ppm), olefinic or aro- Hydrothermal treatment greatly reduced the EMC of
matic carbon atoms with OH or OR substituents materials. Treatment at 200°C reduced the EMC from 14.7
(143–167 ppm), esters and carboxylic acids (169–195 ppm) to 7.6 wt% for fronds and from 13.6 to 7.5 wt% for trunks.
including acetyl groups in hemicellulose (173 ppm), and Further treatment at 350°C led to EMC as low as 5.2 and
carbonyl groups in lignin (195–225 ppm). Despite the vari- 4.5 wt% for fronds and trunks, respectively. However, the
ous resonance peaks observed, for semi-quantitative analysis decrease in EMC mainly occurred in the range 200–270°C,
the spectra can be simply classified into aliphatic with only small changes observed at higher temperatures.
(0–59 ppm), carbohydrate (59–110 ppm), aromatic These results are in agreement with the changes in solid
(110–160 ppm), carboxyl (160–188 ppm), and carbonyl components shown in Fig. 3.
regions (188–225 ppm) [35, 36]. Based on the component characteristic on water
Data for raw and treated fronds reveal that the peak adsorption, hemicellulose exhibits the strongest water
resonance for hemicellulose and cellulose progressively adsorption, followed by cellulose and lignin [37]. Since
decreased (Fig. 6). A similar pattern was observed for hemicellulose was removed first from the solid at low
trunk spectra (Fig. 7). Products resulting from treatment at temperature, it is reasonable that the EMC of the material
200 to 240°C exhibited identical spectra to that of the raw dramatically decreased in this range. By contrast, solids
material. However, treatment at 270°C led to extreme with high lignin content adsorb only a small amount of
spectral changes to a more aromatic nature. The relative moisture. The EMC results were confirmed by NMR

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Fig. 8 Relationship between percentage aromatic carbon and equi-


librium moisture content

Fig. 7 13C NMR spectra with curve fitting for raw trunk and products
obtained at different temperatures

results demonstrating an increase in aromatic content in the


solid material. The presence of aromatic compounds,
which are hydrophobic, results in resistance to humidity
and water adsorption from air. Therefore, a higher aromatic
content is correlated with lower EMC. The relationship
between the relative amount of aromatic carbon and the
EMC is presented in Fig. 8.
EMC and calorific value are two important properties of
solid fuels. When material is burned, some of the energy
released by combustion is consumed to vaporize the water
contained in the material. Material with a higher EMC will
require more energy for moisture evaporation. Thus, a
good solid fuel should have a high calorific value and a low
EMC. Our experiments demonstrated that both properties
were improved by hydrothermal treatment.
Although combustion of the solid fuel products totally
produces less energy than that of raw materials, the fuels
offer other benefits. They are more resistant to undesired
biological decomposition when they are kept in storage. In
addition, as solid fuel which may be transported from one
location to other, their higher energy density will affect on
reduction of storage cost, as well as transportation cost.
Fig. 9 GC-MS spectrogram for the liquid products obtained at
various temperatures a frond; b trunk
Liquid Product
chromatogram of the liquid product of frond and trunk,
Under hydrothermal treatment, materials were degraded respectively. As indicated by those chromatograms,
into numerous low-molecular weight compounds that hydrothermal liquid product contained various organic
subsequently leached into liquid. Figure 9 shows GC–MS compounds. Table 5 lists peaks for several major

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Table 5 Peak for identified


No. Retention time Compounds Chemical Molecular
compounds in GC-MS
Peak (min) formula weight
chromatograms
1 00:04:50 Methanol CH4O 32
2 00:05:45 Ethanol C2H6O 46
3 00:06:16 Aceton C3H6O 58
4 00:09:24 Acetic acid C2H4O2 60
5 00:10:21 1-hydroxy 2-propanon C3H6O2 74
6 00:10:59 Propanoic acid C3H6O2 74
7 00:12:11 Cyclopentanone C5H8O 84
8 00:12:57 Furfural C5H4O2 96
9 00:13:00 2-cyclopenten-1-one C5H6O 82
10 00:13:55 2-cyclopenten-1-one, 2-methyl C6H8O 96
11 00:14:25 4-oxopentanethioic acid C5H8O2S 132
12 00:15:25 Phenol C6H6O 94
13 00:16:16 2-methoxy phenol C7H8O2 124
14 00:17:15 3-pyridinol C5H5NO 95
15 00:18:20 1,2 benzenediol C6H6O2 110
16 00:18:21 5-HMF C6H6O3 126
17 00:19:04 2,6-dimethoxy phenol C8H10O3 154
18 00:19:43 2-methyl 1,3-benzenediol C7H8O2 124
19 00:20:03 4-methoxy-3-(methoxymethyl) C9H12O3 168
phenol

compounds identified on GC/MS chromatogram. The


chromatograms show that acetic acid and furfural were two
predominant organics obtained at 200°C, followed by 5-
HMF, phenol, and 1-hydroxy 2-propanone. The intensity of
acetic acid and phenol tended to increase at elevated
temperature. However, peaks revealed furfural and 5-HMF,
secondary decomposition products of hemicellulose and
cellulose, were present only at 200–270°C. These data
confirmed the results of chemical analysis and 13C NMR of
solid that suggest a progressive decomposition of hemi-
cellulose and cellulose took place within 200–270°C. On
the other hand, phenol and other phenolic compounds such
as 2,6-dimethoxy phenol and 1,2 benzenediol, indicating
decomposition of lignin, were observed along the temper-
ature range of 200–350°C. Due to their composition which Fig. 10 Gas produced form hydrothermal treatment at various
mainly contained organic acids and phenolic compounds, temperatures
the liquid product could be considered for disinfectant and
organic preservatives. However, such applications need a
in Fig. 10, the gas proportion strongly depended on the
further investigation.
temperature. At 200°C, only CO2 was produced. The per-
centage of CO2 gradually decreased, accompanied by
Gas Product increases in CO and H2 at elevated temperature. A slight
amount of CH4, indicating a methanation, was found at
Hydrothermal reactions involve the formation of gases 350°C. The gas formed at this temperature comprised
derived from degradation of water-soluble compounds [38, 5.3–5.5 vol.% H2, 3.5–5.3 vol.% CO, 83.5–85.2 vol.% CO2
39]. A small amount of gas was produced at low temper- and 5.6–6.0 vol.% CH4. Application of this gas product
ature and steadily increased as the temperature was seems less essential. Although the gas product contained
increased. However, CO2 was the predominant gas H2 and CH4, clean and high calorific gases, presence of
observed (C80 vol.%), followed by CO and H2. As shown very high of CO2 makes its application for fuel gas

123
Waste Biomass Valor

inappropriate. On the other hand, its utilization for high Acknowledgments The authors are grateful for support of this
purity CO2 source will be costly since an additional sepa- research by a Grant-in-Aid for Scientific Research No. 21246135
from the Japan Society for the Promotion of Science (JSPS) and the
ration process is needed. Meanwhile, conversion into the Global COE program (Novel Carbon Resources Sciences, Kyushu
gas products is less than 10%, as shown in the carbon University).
balance (Fig. 3).

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