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Procedia Earth and Planetary Science 6 (2013) 441 – 447

International Symposium on Earth Science and Technology, CINEST 2012

Production of 5-hydroxymethyl Furfural from Sugarcane


BagasseUnder Hot Compressed Water
Dewi Agustina Iryania,c, Satoshi Kumagaib, Moriyasu Nonakaa, Keiko Sasakia and
Tsuyoshi Hirajimaa,a*
a
Department of Earth Resources Engineering, Faculty of Engineering
b
Research & Education Center of Carbon Resources, Kyushu University, Fukuoka 819-0395, Japan
c
Department of Chemical Engineering, Lampung University, Indonesia

Abstract

5-hydroxymethyl furfural (5-HMF) is an important organic compound for production of renewable plastics, fine chemicals and
fuel. Nowadays, the manufacturing of 5-HMF is mainly derived from edible glucose and fructose. In order to replace the use of
food crops such as glucose and fructose as a feed stock, experiment were conducted by using sugarcane bagasse as a raw
material. These experiments were performed in a batch-type reactor containing slurry of 10 ml of water and 1.2 g of solids. Effect
of temperature (200°C and 300°C) and reaction times (3 to 30 min) on 5-HMF yield was studied. The highest yield of 5-HMF
was found at 270°C (10 min). Moreover, at temperature (>300°C) and long reaction time, 5-HMF production yield decreased,
this is mainly because of the heightened decomposition and polymerization of 5-HMF to formic acid and char,respectively. This
study reveal that, condition for production of 5-HMF achieved at medium range of temperature and reaction time.

Keywords:

1. Introduction

Among several biomass conversion methods, the hot compressed water(HCW) is one of thermochemical
methods has generated a widespread interest in recent years for conversion of biomass (Sasaki et al., 2003; Hirajima
et al., 2003; Yuliansyah et al., 2010, Kumagai et al. 2012). An advantage of converting lignocellulosic biomass from
agricultural waste via HCW treatment is that, the raw material is not necessary to be dried. Hence, wet biomass can
be directly applied and energy for the drying process can be saved. Moreover, the HCW is typically environmental
friendly and a promising method for obtaining certain chemicals such as sugars and furans.
Recently, Yin et al. (2011) conducted an experiment for production 5-HMF by using cellulose as a raw material.
They reported that, 5-HMF and furfural produced by using hydrothermal treatment at neutral condition (water only)
was highly pure comparing with those produced by hydrothermal treatment under acid or alkaline conditions. This

* Corresponding author. Tel.: +0-000-000-0000 ; fax: +0-000-000-0000 .


E-mail address: hirajima@mine.kyushu-u.ac.jp.

1878-5220 © 2013 The Authors. Published by Elsevier B.V.


Selection and/or peer review under responsibilty of Institut Teknologi Bandung and Kyushu University.
doi:10.1016/j.proeps.2013.01.058
442 Dewi Agustina Iryani et al. / Procedia Earth and Planetary Science 6 (2013) 441 – 447

study showed that the material based on cellulose can be used for substitute fructose and glucose which is
commonly used for 5-HMF production.
Based on several advantages of HCW treatment, this study focuses on 5-HMF production from agricultural waste
such as sugarcane bagasse. Sugarcane bagasse is considered as raw material resources, due to its composition and its
abundantly. In addition, utilization of the low-cost agricultural waste as a raw material has a double consequence
such as elimination of the waste and the regeneration of value-added product thus increasing the economy of the
process.
Normally, several parameters such as temperature, retention time and the composition of medium are affecting on
the conversion of lignocellulosic biomass in HCW treatment, due to differences of their chemical structure and
compositions. Therefore, in order to optimize the conversion method, in this study, by using the simple batch-type
reactor, the influence of the HCW condition such as temperature and reaction time were examined. The effects of
treatment on cellulose from sugarcane bagassewere determined to describe the time course of cellulose degradation
into 5-HMF and the composition of liquid product.

2. Materials and Methods

2.1. Materials

Sugarcane bagasse provided bythe sugar industry was ground using a cutting mill to form powder with a
maximum particle size of 1.0 mm. The powder was then dried in an oven at 60°C for 24h before commencing
treatment. The compositions of sugarcane bagasse were determined using procedure recommended by US National
Renewable Energy Laboratory (NREL㹒㹦) (Sluiter et al., 2005).

2.2. Methods

The HCW experiments were conducted in a batch-type reactor (SUS 316, 14 ml) and equipped with K-
thermocouple to measure temperature of reaction. Slurry consisting of 10 ml water and 1.2 g sugarcane bagasse was
placed in the reactor. A stream of N2 gas was used to replace air in the reactor and to regulate initial internal
pressure of 0.5 MPa. The reactor was immersed into a preheated salt bath at the desired temperature and a given
reaction time. The reactor was then removed from the salt bath and the reaction was quickly quenched by immersion
of the reactor into a water bath to room temperature. The temperature range was from 200 to 300 °C and reaction
time from 3 to 30 min. At the end of the treatment, the treated slurry was collected and filtered using GP 16 glass
filter under vacuum to separate the solid and liquid fractions for further analysis.
Compositions of liquid products were analyzed by gas chromatography-mass spectrophotometer (GC–MS)
Agilent 6890 N which is equippedwith Jeol JMS-Q1000GC (A) system andhigh-performance liquid
chromatography (HPLC). The HPLC chromatograph was equipped with a KC-811 column (JASCO) and refractive
index (RI) detector (RI-2031, JASCO). The HPLC operated under the following conditions: oven temperature 50°C,
using 2 mM HClO4 as the mobile phase, delivered at a flow rate of 0.7 ml/min. At the same time, solid fraction was
dried at 105 °C until constant weight to yield the solid final product. Further, the solid fraction was subjected to
measure their content in cellulose, hemicelluloses and lignin using same methods as for raw material analysis.

3. Results and Discussion

The compositions obtained for the sugarcane bagasse are as follows: cellulose 43.4 wt%, hemicelluloses 21.7
wt%, lignin 20.3 wt%, wax 2.3 wt% and ash 5.6 wt% on a dry base, respectively.

3.1. The Liquid Products Analysis by Using GC-MS

Under HCW treatment, the lignocellulosic polymers from sugarcane bagasse were degradedinto numerous low-
molecular weight compounds thatsubsequently dissolve into liquid.As indicated by those chromatograms, HCW
liquid product contained various organiccompounds. Thechromatograms show that furfural wasthe predominant
organic, followed by acetic acid, 5-HMF, and phenol. However, peaks revealed furfural and 5-HMFas secondary
Dewi Agustina Iryani et al. / Procedia Earth and Planetary Science 6 (2013) 441 – 447 443

decomposition products of hemicellulose andcellulose were present only at 200–270°C. These dataconfirmed the
results of chemical analysis ofsolid product suggested a progressive decomposition of hemicellulosesand cellulose
took place within 200–270°C.
In the other hand, the intensity of acetic acid tends to rise with increasing the treatment temperature and reaction
time. Yoshida et al. (2005) reported that the production of acetic acid is generated by sugar decomposition reactions,
and also by detachment of the acetyl group from hemicellulose. Onthe other hand, phenol and other phenolic
compounds suchas 2,6-dimethoxy phenol were observed along the temperaturerange of 200–300°C. The increase of
phenol intensity indicates that the decomposition of lignin occurs along of the temperaturerange of 200–300°C.

Acetone
GCMS data 10 min

Furfural
Intensity a.u

Acetic acid 5-HMF


Ethanol Phenol 300 RC

270 RC

240 RC

200 RC

00:05:00 00:10:00 00:15:00 00:20:00 00:25:00

Retention time (min)

Acetone GCMS data 20 min

Ethanol

Phenol
Intensity a.u

Acetic acid Phenol 2,6-dimethoxy


300 RC
Furfural
5-HMF 270 RC

240 RC

200 RC

00:05:00 00:10:00 00:15:00 00:20:00 00:25:00

Retention time (min)

Figure 1 GC-MS spectrogram for the liquid productsobtained at various HCW condition.

3.2. The Liquid Products Analysis by Using GC-MS

Effect of temperature on 5-HMF yield


For determining the effect of treatment conditions on 5-HMF and other chemical products from HCW treatment,
the HPLCanalysis was carried out. The effects of temperature on HMF yield are shown in Figure 2 at 10 and 20
minute (data for other treatment conditions omitted here). The data showed that the yield of solid product gradually
declined with the increasing of treatment temperature. At temperature 270°C and 300°C only a few amount of solid
residue was recovered.
HCW treatment is leading to thermal degradation of the raw material. When, the raw material which consistsof
polymer such as cellulose, hemicelluloses and lignin heated to high temperature, the physical and chemical bonds of
polymerwere broken.The large long-chain compounds such ascellulose, hemicellulose and lignin were broken down
444 Dewi Agustina Iryani et al. / Procedia Earth and Planetary Science 6 (2013) 441 – 447

intosmaller and simpler molecules. Furthermore, some of the molecules were dissolved into liquid part and some
others degraded to gases.
Allen et al. (1996) reported that the breaking of the chemical bonds may be enhanced by increased
disproportionation of water at elevated temperatures. At elevated temperature, hot compressed water has unique
properties of density, dielectric constant, ion product, viscosity, diffusivity, electric conductance, and solvent ability.
HCW has an ion product (Kw) about three orders of magnitude higher than that of ambient liquid water; in this
condition, water acts as an acid-base catalyst precursor (Kruse andDinjus, 2007). For example at 220°C the ion
product of liquid water is 10-11, thus the pH of water at this temperature is 5.5, as compared to 7.0 at 25°C (Allen et
al., 1996). Thus, the HCW is able to hydrolyze woody biomass component to saccharides without any acids or
solvents.
At low treatment temperature such as 200°C,hemicellulose already decomposes. The decomposition of
hemicellulose began at 200°C (3 min) and completely decomposed at 200°C (20 min). Thus, it makes the solid
residue mainly dominated by cellulose and lignin. However, in the range of temperature270-300°C the yield of
cellulose gradually decreased. Cellulose started to decompose at 240°C (5 min) and was completely degraded at
270°C (20 min) and at 300°C (10 min), no cellulose weredetected in the solid residue products after treatment at
those conditions.
At the elevated temperatures, long chains of cellulose arebroken down to shorter groups of molecules and glucose
was released. The highest glucose yield was 1.887 wt% at 270°C (3 min). Hereafter, the yield of glucose gradually
decreased with increased time and temperature. The reduction of glucose yield occurs due to glucose dehydration
into 5-HMF.

Figure 2 Effect of temperature on conversion of sugarcane bagasse into solid product, cellulose, glucose, 5 -HMF and formic acid.

5-HMF was obtained as glucose yield decreased. The yield of 5-HMF tend to increase with increasing of
temperature. The increase in the HMF yield occurred when the temperature increased from 200°C to 270°C with the
highest yield of 5-HMF was 3.09 wt% obtained at 270°C (10 min).However, when temperature increased from 270-
Dewi Agustina Iryani et al. / Procedia Earth and Planetary Science 6 (2013) 441 – 447 445

300°C, the yield of 5-HMF decreased and was undetected at 300°C (> 10 min). Thesedata suggests that high
temperatures have negative effects on 5-HMF production, mainly because of the heightened rehydration and
polymerization of 5-HMF to organic acids and char, respectively (Yin et al. 2011).
Formic acid is one of organic acids which is produced from rehydration and polymerization of 5-HMF and
furfural. The highest yield of formic acid was detected at 240°C (10 min), then decreased with extended treatment
temperature and was undetected beyond 300°C (20 min). According to Yu et al. (1998), formicacid readily
decomposes at elevated temperature into CO2 and H2.
Alongside of formic acid, levulinic acid was also produced from rehydration and polymerization reaction of 5-
HMF. Asghari and Yoshida (2006) reported that more levulinic acid produced as the HMF yield decreased.
Effect of reaction time on 5-HMF yield
The effect of reaction time on 5-HMF yield is shown in Figure 3. It showed that yield of 5-HMF tends to
decrease with the increase of reaction time. The peak of 5-HMF yield was obtained in range of reaction 5 to 30 min
at low temperature;however, the 5-HMF yield decreased in the range of reaction time 10 to 30 min at temperature
300°C. The decrease of 5-HMF yield mainly with reaction time was caused by formation of organic acids and char.

Figure 3 Effect of reaction time on conversion of sugarcane bagasse into solid product, cellulose, glucose, 5-HMF and formic acid.

As can be seen in the figure, the yield of solid product tends to increase with the increase of reaction time. The
solid product yield increased to 54.55 wt% (240°C) and 37.74 wt% (300°C) at reaction time 30 min, respectively. In
this study, the recovered solid product at short reaction time and low temperature had yellow color, indicating that
the solid product was mainly dominated by cellulose. However, when the yield of cellulose decreased with reaction
time, the solid product color changed into dark-color, indicating that char formation was performed. Based on these
results, a short reaction time is recommended for 5-HMF production in order to minimize the formation of organic
acid and char from depolymerization of 5-HMF.
To summarize the conversion mechanism ofdecomposition sugarcane bagasse in HCW treatment, the simplified
pathway is presented in Figure 4.
446 Dewi Agustina Iryani et al. / Procedia Earth and Planetary Science 6 (2013) 441 – 447

Figure 4 The simplified pathway of HCW conversion of sugarcane bagasse into 5-HMF and other chemicals

4. Conclusions

Based on the analytical results of HCW treatment of sugarcane bagasse, it was concluded that the conversion of
sugarcane bagasse into 5-HMF and other chemical compounds was influenced by treatment temperature andreaction
time. Degradation of cellulose is started at 240°C (5 min) and was completely degraded after 20 minutes at 270°C,
and after 10 minutes at 300°C. Cellulose decomposed to form glucose, which further decomposed to form 5-HMF
and organic acids. The yield of 5-HMF reached its maximum when the temperature increased from 200°C to 270°C
with the highest yield of 5-HMF was 3.09 wt% obtained at 270°C (10 min). As there was an increase in temperature
(> 300°C) and in reaction time (>20 min), the yield of 5-HMF decreased, mainly because of the decomposition and
the polymerization of 5-HMF into formic acid and char,respectively.
The HCW treatment is a promising technique for the hydrolysis and dissolution of lignocellulosic biomass in
water. This method not only shows the possibility for the hydrolysis of lignocellulosic biomass into water-soluble
saccharides, but also showed commercially attractive yields of HMF and furfural from the agricultural waste.

Acknowledgements

The authors are grateful for the financial support of this research to The Global COE program (Novel Carbon
Resources Sciences, Kyushu University) and Grant-in-Aid for Scientific Research No. 21246135 and 24246149.

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