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Energy Procedia 9 (2011) 515 – 521

9th Eco-Energy and Materials Science and Engineering Symposium

The effect of catalyst types and starting materials on furan

production in hot compressed water
Pornlada Daorattanachai a, Pongtanawat Khemthong b, Nawin Viriya-empikul b,
Navadol Laosiripojana a and Kajornsak Faungnawakij b*
a
The Joint Graduate School of Energy and Environment (JGSEE), King Mongkut’s University of Technology Thonburi,
Bangkok 10140, Thailand
b
National Nanotechnology Center (NANOTEC), National Science and Technology Development Agency (NSTDA),
Pathumthani 12120, Thailand

Abstract

The catalytic conversion of sugars (glucose and fructose) to furan compounds (HMF and furfural) was
studied under hot compressed water (HCW) conditions. The effect of catalyst types (homogeneous acid
(H3PO4) and base (NaOH)), and starting materials (monosaccharide and cellulose) on furan yields was
investigated. It was found that at 200 qC, phosphoric acid showed great catalytic activity on the
production yield of HMF from dehydration of the sugars, when compared with NaOH. Cellulose is
composed of glucose units, and would first be hydrolyzed and then dehydrated to furans. The optimum
condition for hydrolysis/dehydration was observed under the acid-catalyzed conditions with the reaction
temperature of 230 qC and reaction time of 5 minutes, at which the yields of sugar and furan compounds
were achieved at 23.0 and 7.5%, respectively.
© 2011 Published by Elsevier Ltd. Open access under CC BY-NC-ND license.
Selection and/or peer-review under responsibility of CEO of Sustainable Energy System,
Rajamangala University of Technology Thanyaburi (RMUTT).
Keywords: Hot compressed water; HMF; sugar; cellulose; phosphoric acid

1. Introduction

Nowadays, the shortage of fossil fuels is a serious concern around the globe. Moreover, pollutant
emission during their combustion has influenced on the climate change and environmental problems.
Utilization of renewable energy from biomass will be one of the solutions to cut-off these problems.
Lignocellulosic biomass is one kind of biomasses which refer to plant biomass consisted of biopolymer
such as cellulose (40-60%), hemicellulose (20-40%), and lignin (10-24%) [1]. Degradation of the
polysaccharide constituents, i.e. cellulose and hemicelluloses results in formation of sugars, e.g. hexose

* Corresponding author. Tel.: +66 2 564 7100; fax: +66 2 564 6981.
E-mail address: kajornsak@nanotec.or.th

1876-6102 © 2011 Published by Elsevier Ltd. Selection and/or peer-review under responsibility of CEO of Sustainable Energy System, Rajamangala
University of Technology Thanyaburi (RMUTT). Open access under CC BY-NC-ND license.
doi:10.1016/j.egypro.2011.09.059
516 Pornlada Daorattanachai et al. / Energy Procedia 9 (2011) 515 – 521

and pentose which could be used as versatile starting materials for producing a variety of value-added
products.
In considering the biomass conversion method, hot compressed water (HCW) is an attractive one for
processing of sugars and lignocellulosic feedstocks due to its advantages on environmental friendliness
and potential on reaction control through the use of water density [2]. Chemical reactions in HCW can be
enhanced by water which acts as solvent, reactant, and catalyst in the systems. HCW has typically been
developed for production of various chemicals. Specifically, furan derivatives such as 5-
hydroxymethylfurfural (HMF) and furfural, obtained by dehydration of carbohydrates, have been
described as key substances that bridge carbohydrate chemistry and petroleum-based industrial chemistry
because the wide range of chemical intermediates and end-products can be produced from these
compounds. Interestingly, furan compounds can be subsequently converted into diesel fuel additives, bio-
polymers, and industrial solvents [3]. This versatile chemical platform is considered to play a significant
role in biorefinery industry.
In the present work, we aimed at the study of effects of catalyst types on hydration of sugars and the
integrative hydrolysis/dehydration of cellulose to produce HMF, furfural, and/or sugars under hot
compressed water. Moreover, the influence of reaction temperature and time was investigated to optimize
furan yields.

2. Experimental

Glucose, fructose, and sodium hydroxide were commercially obtained from Carlo Erba, whilst
cellulose was from Sigma Aldrich. Phosphoric acid was obtained from Ajax Finechem. All are of
analytical grade.
The reactions were carried out in an SS316 stainless steel tube reactor with the inner volume of 10 cm3.
A typical reaction procedure was as follows: sugar or cellulose (0.1 g) and water (1 cm3) were introduced
into the reactor along with 0.1 M H3PO4 or 0.1 M NaOH to adjust pH to 2 and 11, respectively. Nitrogen
was loaded to raise the reactor pressure to 2.5 MPa. Then, the reactor was heated at desired temperature
with a heating rate of 20 qC/min. After reaching the reaction time required, the reaction was stopped
instantly by quenching the reactor in an ice-cooling bath.
The samples taken from the reactor were filtered and washed with a portion of deionized water to
recover the liquid products. The amount of products in the liquid samples was quantitatively analyzed by
a high-performance liquid chromatography (HPLC) after appropriate dilution with pure water. A Shodex
RSpak KC811 column with UV detector was employed to detect HMF and furfural compounds. Gel
permeation chromatography (GPC) coupled with a Shodex Sugar SP810 column with reflective index
(RI) detector was employed to detect the glucose, fructose, and 1,6-anhydroglucose (AHG). The amount
of each compound in the liquid products was determined using calibration curves obtained by analyzing
standard solutions with known amounts. The HMF or furfural yield, conversion of sugar, and sugar yield
were calculated using the following equations:

HMF or furfural yield (%) = gram of HMF or furfural in product x 100 (1)
gram of feedstock

Conversion of sugar (%) = (initial sugar mass – last sugar mass) x 100 (2)
initial sugar mass

Sugar yield (%) = gram of sugar in product x 100 (3)

gram of initial biomass
 Pornlada Daorattanachai et al. / Energy Procedia 9 (2011) 515 – 521 517

3. Result and discussion

3.1 Effect of catalyst type

The effect of catalyst types on dehydration of sugars (glucose and fructose) and hydrolysis/dehydration
of cellulose was investigated in detail under HCW condition. Sodium hydroxide and phosphoric acid
were chosen as representative base and acid catalysts in these experiments for activity comparison. The
results obtained in the absence and presence of the catalysts are shown in Fig.1. As shown in Fig.1A, the
conversion of glucose was slightly promoted by adding sodium hydroxide and phosphoric acid when
compared with blank test without catalyst. However, the HMF yield from glucose dehydration in the
presence of phosphoric acid and sodium hydroxide was two times higher than that without catalyst. This
result revealed that both base and acid catalysts can effectively enhance glucose dehydration.

(A) HMF Furfural Conversion

5 100

4 80
Product yield (%)

Conversion (%)
3 60

2 40

1 20

0 0
No catalyst Phosphoric acid Sodium hydroxide

(B) HMF Furfural Conversion

50 100

40 80
Product yield (%)

Conversion (%)

30 60

20 40

10 20

0 0

No catalyst Phosphoric acid Sodium hydroxide

(C) HMF Furfural Glucose

15
Product yield (%)

12

0
No catalyst Phosphoric acid Sodium hydroxide

Fig. 1. Effect of catalyst type on the conversion and product yield from dehydration of glucose (A) and fructose (B), and
hydrolysis/dehydration of cellulose (C) at 200 qC for 5 min.
518 Pornlada Daorattanachai et al. / Energy Procedia 9 (2011) 515 – 521

With or without catalysts, the fructose conversion was nearly comparable at 82-92%. Under the present
condition studied, fructose could be rapidly dehydrated to furans, and therefore the addition of sodium
hydroxide and phosphoric acid provided a small effect on the fructose conversion. Nonetheless, the HMF
yield was highest at 29% over phosphoric acid. The results showed that dehydration reaction of fructose
was much easier proceed than that of glucose catalyzed by both sodium hydroxide and phosphoric acid.
For glucose transformation, selectivity to furans was highly enhanced with the use of the catalysts. This
behavior could be ascribable to their structural change during the reaction. Glucose forms a very stable
ring structure, so that the fraction of open chain formed in the solution, and the enolisation rates were
consequently slow. On the other hand, less stable ring structures of fructose gave rise to higher open
chains, and so the enolisation rates were comparatively high. Strictly speaking, glucose undergoes
polymerization to fructose and subsequently fructose is transformed to HMF via dehydration step [4]. The
ring-opening step would have a high energy barrier, especially when no catalyst was used, and was
presumably considered a rate-determining step in overall glucose transformation to HMF. Using the
catalyst would suppress the activation energy required. HMF yield was consequently higher with the use
of the catalysts and/or with fructose as the starting material.
Cellulose is polysaccharide which is hydrolyzed and dehydrated to produce sugar and furans,
respectively. Glucose, HMF, and furfural, as three main products from cellulose conversion, are depicted
in Fig.1C. The catalytic effect of phosphoric acid was much higher than that of without catalyst, and with
sodium hydroxide in enhancing the formation of glucose, HMF, and furfural, with a total yield of 10% at
200 qC for 5 min. As it turned out, only phosphoric acid is capable of effective hydrolysis of cellulose,
and dehydration of the resultant sugar.

3.2 Effect of reaction temperature

To obtain the highest product yield, it is necessary to optimize the reaction conditions by varying the
reaction temperature and time. The reaction tests were implemented at varied temperatures (200-270 °C)
in the presence of phosphoric acid.
Fig.2 shows the values of conversion of glucose, fructose, and cellulose, and their product yields. It was
clear that temperature had a dramatic effect on the hydrolysis and/or dehydration of glucose, fructose, and
cellulose. Glucose conversion was elevated from 43 to 92% when the temperature increased from 200 to
270 qC. HMF yield was gradually incremented as temperature increased, and the yield of ca. 10% was
peaked at 220 and 230 qC. At temperature higher than 230 qC, HMF yield gave the opposite results,
though the glucose conversion kept slightly increasing. In Fig.2B, fructose conversion showed high
values (>85%) for all temperatures studied. HMF yield decreased sharply from 29 to 0% when the
temperature increased from 200 to 270 °C, and large amounts of brown insoluble products were formed,
presumably to be humins.
The hydrolysis of cellulose is strongly dependent on the temperature (see in Fig.2C). The high
temperatures can enhance the transformation of cellulose to glucose. However, degradative side-reactions
of glucose could also take place and speed up with the increase of temperature. By increasing the
temperature, products yields from cellulose hydrolysis/dehydration were enhanced, reaching a maximum
at 230 qC. When the reaction temperature rose above 230 qC, the yield of HMF began to fall, and
intermediates such as glucose were not detected. These results were in line with the conversion behaviors
of glucose and fructose described above. The higher temperatures thus could accelerate the chemical
reactions, meanwhile unwanted side-reactions also appeared at the same time. Under the present
conditions investigated, it was found that humins occurred during the reaction at higher temperature. In
addition, carboxylic acids and aldehydes were partially detected as confirmed by qualitative analysis of
GS-MS.
 Pornlada Daorattanachai et al. / Energy Procedia 9 (2011) 515 – 521 519

(A) HMF Furfural Conversion

12 100

9 75

Conversion (%)
Product yield (%)

6 50

3 25

0 0
200 °C 210 °C 220 °C 230 °C 240 °C 270 °C

(B) HMF Furfural Conversion

40 100

30 75
Product yield (%)

Conversion (%)
20 50

10 25

0 0
200 °C 210 °C 220 °C 230 °C 240 °C 270 °C

(C) HMF Furfural Glucose

40

30
Product yield (%)

20

10

0
200 °C 210 °C 220 °C 230 °C 240 °C 270 °C

Fig. 2. Effect of temperature on the conversion and product yield from dehydration of glucose (A) and fructose (B), and
hydrolysis/dehydration of cellulose (C) catalyzed by H3PO4 at 200-270 qC for 5 min.

3.3 Effect of reaction time

The effect of reaction time on the hydrolysis and/or dehydration of glucose, fructose and cellulose in
the presence of phosphoric acid was studied under hot compressed water conditions at 220, 200, and 230
qC, respectively. As shown in Fig.3A, glucose conversion monotonously increased with increasing
reaction time, and was greater than 90% at 30 min. However, HMF production decreased at prolonged
time, due to the consecutive decomposition to formic and levulinic acids as confirmed by GC-MS
analysis. Fructose conversion showed high values (>90%) at 0-30 min (see in Fig.3B). The HMF yield
increased with the prolongation of time from 0 (26%) to 5 min (29%). The yield reached a maximum at 5
min, and then decreased greatly afterward.
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Fig.3C shows the product yields of HMF, furfural, and glucose from hydrolysis/dehydration of
cellulose implemented at reaction temperature of 230 qC for 0-10 min. The total yield from
hydrolysis/dehydration of cellulose increased from 24 to 31 % when the reaction time increased from 0 to
5 min, respectively. Then it decreased to 16.7 % at a reaction time of 10 min. These results suggested that
the increase in the reaction time improved not only the formation of products but also at the same time
their decomposition rate. Glucose formation decreased from 23.0 to 6.6 % with increasing reaction time
from 5 to 10 min. Sasaki et al (1998) [5] concluded that the glucose decomposition rate is much faster
than the hydrolysis rate of cellulose. Thus, even if the hydrolysis products, such as glucose or oligomers,
are formed, their further decomposition rapidly takes place and thus a high yield of hydrolysis products
cannot be obtained.

(A) HMF Furfural Conversion

12 100

9 75
Product yield (%)

Conversion (%)
6 50

3 25

0 0
200°C,0 min 200°C,5 min 200°C,10 min 200°C,20 min 200°C,30 min

(B) HMF Furfural Conversion

32 100

24 75
Product yield (%)

Conversion (%)

16 50

8 25

0 0
200°C,0 min 200°C,5 min 200°C,10 min 200°C,20 min 200°C,30 min

(C) HMF Furfural Glucose

40

30
Product yield (%)

20

10

0
230°C,0 min 230°C,5 min 230°C,10 min

Fig. 3. Effect of reaction time on the conversion and product yield from dehydration of glucose (A) and fructose (B), and
hydrolysis/dehydration of cellulose (C) catalyzed by H3PO4.
 Pornlada Daorattanachai et al. / Energy Procedia 9 (2011) 515 – 521 521

According to the results in Fig.3C, cellulose was first hydrolyzed into glucose and then dehydrated to
furans. The amount of formation of glucose from hydrolysis was more than decomposition of glucose to
HMF at initial time of reaction. Then, when glucose was generated more, the HMF yield increased
because glucose decomposition rate is much faster than the hydrolysis rate of cellulose (from 3.6 to 7.5%
with reaction time at 0 to 5 min, respectively). Moreover, even hydrolysis products at 10 min were
formed in higher yield, the amount of glucose decreased because glucose converted to HMF and then
HMF could be decomposed to degraded products such as acids or aldehydes.

4. Conclusions

We have studied the effect of catalyst types, reaction temperature, and reaction time on the catalytic
conversion of cellulose and sugar to furan compounds in hot compressed water. It was observed that
catalyst types, temperature, and reaction time have a great effect on the hydrolysis and dehydration of
glucose, fructose, and cellulose. Phosphoric acid shows great catalytic activity for dehydration of glucose
and fructose. Moreover, phosphoric acid can promote hydrolysis of cellulose in producing glucose in high
yield. Sodium hydroxide as a base catalyst can promote dehydration of glucose in HMF yield, comparable
to phosphoric acid. However, sodium hydroxide could not catalyze the cellulose conversion, and there
was no significant difference with the HCW without catalyst.
The best reaction condition of glucose, fructose, and cellulose was found at 200-230 qC and 5 min.
HMF yield from dehydration of glucose and fructose was 9.6 and 29%, respectively. Sugar and furan
compounds from hydrolysis and dehydration of cellulose were achieved at 23.0 and 7.5%, respectively.

Acknowledgements

The authors acknowledge financial supports from Thailand Graduate Institute of Science and
Technology (TGIST) and Discovery Based Development Grant (DD Grant) from National Science and
Technology Development Agency.

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