JEMMME (Journal of Energy, Mechanical, Material, and Manufacturing Engineering)
Vol.5, No. 2, November 2020
ISSN 2541-6332 | e-ISSN 2548-4281
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Rahmawati | Kinetics Study of Acid Catalyzed Degradation of Glucose in High-… 21
Kinetics Study of Acid Catalyzed Degradation of
Glucose in High-Temperature Liquid Water
Atiqa Rahmawatia, Aulia Iin Saputrib, Ignatius Gunardic
aUniversitas Jember, a,b,cInstitut Teknologi Sepuluh Nopember, Indonesia
e-mail: tiqa054@gmail.com
Abstract
Glucose is the most abundant monosaccharide in nature, glucose obtained
from cellulose and starch, it is many used to degradation process, and for the
production of several organic compounds, one of the degradation products of
glucose is an HMF (5-hydroxymethylfurfural). HMF is a platform chemical,
which can be converted into several chemical and liquid fuels through
hydrogenation, oxidation, and esterification. The objective of this researches
has studied the kinetics of glucose degradation using acid-catalyzed (H2SO4)
in high-temperature liquid water and observe the effect of acid concentration
and temperature on degradation of glucose to HMF. In this research was used
reactor with pressure 10 atm, with variation time of reaction, sulfuric acid
concentration, and temperature of the reaction. From this research found
kinetics of glucose degradation was followed by the first-order reaction in each
variable. Activation Energy (Ea) values were 7306,593 J/mol; 6341,59 J/mol;
3988,14 J/mol and 3988,14 J/mol on the concentration sulfuric acid 0,05M;
0,1 M; 0,05M, from that result indicated that reaction rate was increase when
activation energy was decrease this was related to Arrhenius equation. The
effect of acid concentration on degradation glucose was the higher acid
concentration used, the more glucose was degraded, and more HMF was
formed. Meanwhile, the effect of temperature of reaction on degradation
glucose was the higher temperature of the reaction, more glucose was
degraded, and more HMF was formed. The highest value of HMF was in
operation condition of concentration H2SO4 0,5 M at 175°C, with a time of
reaction 120 minutes. However, the reduction rate of glucose was not equal to
the rate of formation of HMF (5-hydroxymethylfurfural), it can be indicated that
HMF (5-hydroxymethylfurfural) was not the only product of degradation of
glucose, but the others product might be formed from this operating condition.
The other product that might be formed was humin and levulinic acid.
Keywords: degradation of glucose, kinetics study, hydroxymethyl furfural
(HMF)
1. INTRODUCTION
The decreasing of fossil fuel has become a global concern; combustion of fossil fuel
have a severe impact in environments such as climate change and pollutant emission [1].
To cut-off, these problems renewable energy become one of the sustainable solution [1].
Biomass is one of the renewable resources to replace fossil fuel for the production of
organic chemicals. Some technology can provide a route to convert biomass into fuel or
chemicals [2]. Lignocellulosic biomass is a biopolymer which consists of cellulose (40 –
60%), hemicellulose (20 – 40%), and lignin (10 – 24%). Degradation of the cellulose and
hemicellulose result in formation hexose and pentose sugar, which could be used to
producing variety value-added product such as 5-Hydroxymethylfurfural and furfural [1].
HMF is a platform chemical that receives noteworthy attention as a key bio-refining
building block. Some methods used to produce HMF from biomass are hydrolysis,
isomerization, degradation methods with acidic or basic catalysts. [3]. Besides, HMF can
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JEMMME (Journal of Energy, Mechanical, Material, and Manufacturing Engineering)
Vol.5, No. 2, November 2020
Rahmawati | Kinetics Study of Acid Catalyzed Degradation of Glucose in High-… 22
be converted to promising biofuel (2,5-dimethylfuran) which produced from petroleum [3].
Attention to HMF is increasing due to the application of HMF as a substitute material for
petroleum-based building blocks. Fructose is a monosaccharide which easies to convert
over a homogenous and heterogeneous acidic catalyst in the aqueous or organic phase,
ionic liquids, and multiphase system [4]. The high price of fructose and the low availability
of fructose has led to increasing in glucose as raw materials to produce HMF using the
dehydration method [4].
Production of HMF from sugar via dehydration reaction and using variety acidic ionic
liquids as a solvent could hydrolyze cellulose to sugar and HMF. However, organic
solvents that have a high boiling point will be difficult to remove, moreover in this process
also result in adverse impacts on the environment. [1]. Water is a unique and
environmentally friendly solvent, besides being able to act as a solvent and reactant,
water can be catalyzed in pressurized water. As a green solvent that has unique
properties, water is used as an alternative solvent in biomass conversion. [1]. Besides,
using solvents such as ionic liquids that have high boiling points will result in high-cost in
the process because of the difficult separation and purification process, thus to avoid this
problem it would be preferable to use water as a solvent in the dehydration process [4]. In
the dehydration process, acid catalyst use as attractive processing option to produce
HMF from hexoses and pentoses [5]. Study of glucose degradation in Hot Compressed
Water (HCW) with catalysts or without catalysts have been shown that H2SO4 and NaOH
catalysts affect the process of glucose degradation reaction into products [1].
Pornlada et al. studied the dehydration of cellulose in hot compressed water by
using acidic and base catalysts to produce HMF. The operating conditions used was 200
– 230 ⁰C for 5 minutes. The optimum yield of HMF was 7.5% [1]. The other study using
acid catalyst in dehydration sugar mentioned that the highest product yield was obtained at
150 ⁰C and 0,55 M H2SO4 [2]. Cunshan Zhou et al. [3] had studied the conversion of glucose to
HMF in different solvent and catalyst, from that studied was obtained HMF yield in the various
solvents follows a decreasing order as DMSO > [Bmim]Cl > H2O. In the study of glucose
degradation carried out in DMSO solvents using several catalysts. It was obtained yield HMF
from low to high by using a catalyst FeCl3.6H2O, AlCl3, CrCl3.6H2O. The optimal yield of HMF
was obtained 54.4% using the CrCl3.6H2O catalyst at 403 K for 480 minutes and 52.86%
using the AlCl3 catalyst at 393 K for 240 minutes [3].
Based on previous studies, HMF can be produced from sustainable material such as
lignocellulose. However, to convert lignocellulose to HMF requires a very long process,
starting from sample preparation, lignin removal, hydrolysis process to produce glucose.
Glucose from the hydrolysis process will be converted to HMF using dehydration process.
In this study, we have examined an acid catalyst and water solvent to produce HMF. The
process to form HMF is the dehydration using acid catalysts and water solvents, and the
process will be carried out at high temperature pressured reactors.
2. MATERIALS AND METHODS
D-Glucose (≥99,5%), sulfuric acid (98%) were purchased from Sigma-Aldrich. 3,5-
dinitrosalicylic acid (DNS), natrum hydroxide, potassium sodium tartrate, sodium
metabisulphite for glucose analysis were also acquired from Sigma-Aldrich. Glucose
Solution was prepared using aquadest.
Glucose Degradation
All experiment was carried out in a batch reactor type stirred tank with stainless steel
material (volume 600 ml, height 25 cm, OD 7,5 cm) equipped with a four-blade turbine
stirrer. A solution of glucose 1% with catalyst concentration 0,5 M; 0,1M; 0,05M were fed
to the reactor system. The reactor was flow by N2 gas to expel the air inside the reactor.
The reactor was heated at 100, 125, 150, 175 ⁰C, pressure in the system was 10 atm.
The sample was taken at 0, 30, 60, 90, and 120 minutes. Reduced glucose was analyzed
using visible spectrophotometer detector (Cecil CE 1011) with a wavelength of 540 nm,
then HMF product was analyzed by HPLC Agilent 1100 series with refractive index
detector in ULFPP Airlangga University Surabaya.
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Vol.5, No. 2, November 2020
Rahmawati | Kinetics Study of Acid Catalyzed Degradation of Glucose in High-… 23
1. N2 gas
2. Valve tube gas N2
3. Heater
4. Reactor Tube N2 gas
5. Glucose and catalyst
solution
6. Stirrer
7. Reactor
8. Thermocouple tube
9. Pressure indicator
10. Gas outlet valve and
sampling valve
11. Panel control heater- reactor
Figure 1. Reactor equipment for glucose degradation
Analysis
The products present in the reaction were analyzed by HPLC Agilent 1100 series with
refractive index detector in ULFPP Airlangga University Surabaya. Reduce glucose from
the products were analyzed by visible spectrophotometer detector (Cecil CE 1011) with a
wavelength of 540 nm with DNS reagent.
Kinetic Modelling
To determine the reaction rate (k) and the order of reaction (n) in the formation of HMF
(Hydroxymethylfurfural), it is known from the equation, the relationship between t (time)
and -ln CA / CA0. The equation for the reaction is as follows:
Glucose 5-HMF (1)
The integral method was used in this kinetic model, with assumption first-orderer reaction
to glucose. The assumption was correct if the equation forms a straight line, and the
reaction order of the HMF formation from glucose occurs in the first-orderer reaction.
(2)
(3)
(4)
(5)
(6)
3. RESULTS AND DISCUSSIONS
Glucose Degradation
From this study, we use an initial concentration of glucose was 1%, then adding
several acid catalyst concentration. Product form depends on the initial glucose
concentration [6]. Fig 2 shows the effect time of reaction toward reduction of glucose
concentration in acid concentration. Increasing temperature and reaction time, the
concentration of glucose decreased. Since glucose concentration inversely proportional
JEMMME (Journal of Energy, Mechanical, Material, and Manufacturing Engineering)
Vol.5, No. 2, November 2020
Rahmawati | Kinetics Study of Acid Catalyzed Degradation of Glucose in High-… 24
to temperature and reaction time, increasing in temperature and reaction time would
result in reducing glucose concentration [7].
0,020
(m
o
l/
li
te
r)
0,018
100 C
125 C
150 C
0,016 175 C
c
o
n
c
e
n
tr
a
ti
o
n
0,014
0,012
G
lu
c
o
s
e
0,010
0,008
0 20 40 60 80 100 120
time of reaction (minutes)
100 C
0,020 125 C
150 C
175 C
0,018
(m
o
l/
li
te
r)
0,016
c
o
n
c
e
n
tr
a
ti
o
n
0,014
0,012
G
lu
c
o
s
e
0,010
0,008
0 20 40 60 80 100 120
time of reaction (minutes)
100 C
0,020 125 C
150 C
175 C
0,018
(m
o
l/
li
te
r)
0,016
c
o
n
c
e
n
tr
a
ti
o
n
0,014
0,012
G
lu
c
o
s
e
0,010
0,008
0 20 40 60 80 100 120
time of reaction (minutes)
Figure 2. Effect temperature and reaction time to glucose concentration at (a) 0,05 M H2SO4 ,
(b) 0,1 M H2SO4 , (c) 0,5 M H2SO4
HMF (Hydroxymethylfurfural) Formation
HMF (Hydroxymethylfurfural) or 5-HMF is high importance platform chemical derived
from biomass. In this study, the conversion of glucose to 5-HMF was performed in a
batch reactor of various concentration acid catalyst then analyzed by using HPLC Agilent
1100 series with a refractive index detector. Fig 3 shows effect reaction time and
temperature to HMF formation in H2SO4 concentration. From that figures show
Increasing reaction time and temperature obtained a high concentration of HMF. This is in
accordance with the other study mentioned that HMF concentration would be higher
when the temperature increase [7]. From fig 3 at 150 – 175 ⁰C at reaction time 0 – 30
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Rahmawati | Kinetics Study of Acid Catalyzed Degradation of Glucose in High-… 25
minutes HMF concentration had increased significantly, this is because HMF
concentration had increased at 160 ⁰C with reaction time 30 minutes [8]. The other study
mentioned that the formation of HMF occurred in 150 – 200 ⁰C using acid catalyst H2SO4
[2]. At reaction time 60 – 120 minutes HMF concentration tended to constant since HMF
had redehydration reaction, which forms levulinic acid and formic acid [8]. The other study
mentioned that the chemical conversion of glucose could proceed via acid-catalyzed
dehydration and obtained 5-HMF, levulinic acid, and formic acid at 150 ⁰C [9]. The
highest conversion of glucose to HMF was 18,495%, meanwhile the other study
mentioned that conversion of glucose to HMF was 91,4%, and yield of HMF was 59,8%
using Indium trichloride (InCl2) as catalyst in aqueous solution [10], Study of Qiuhe Ren
et al. mentioned that conversion of glucose was 86% and yield of HMF was 63%, this
study using metal halide (NaI dan NaBr) as catalyst [11]. Result of Yanhua wang study
was the highest yield HMF 76% using fructose as raw material, heterogeneous catalyst,
and solvent DMSO [12]. From that statement to increasing glucose conversion and yield
of HMF, we can use heterogeneous catalysts such as InCl2, NaI, NaBr, and an ionic
liquid solvent.
Figure 3. Effect reaction time and temperature to HMF formation (a) 0,05 M H2SO4 , (b) 0,1 M
H2SO4 , (c) 0,5 M H2SO4
Kinetic Modelling
Glucose degradation experiment initially used acids concentration 0,05; 0,1; 0,5 M,
and temperature at four level 100, 125, 150, 175 ⁰C. Temperature and acid concentration
were independent variables in this study. Equation 1 shows the reaction scheme for
development kinetic model for acid-catalyst degradation of glucose based on the
following consideration and assumption:
Assume all reaction rate equation using first – order reaction.
1. The desired product from glucose degradation using an acid catalyst is the
formation of HMF. However, in this degradation process obtained by-products
(levulinic acid and humin) simultaneously, which are undesirable and neglected in
the process.
2. Kinetic modeling using an integral method first-order reaction.
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Vol.5, No. 2, November 2020
Rahmawati | Kinetics Study of Acid Catalyzed Degradation of Glucose in High-… 26
In batch reactor set up with constant density and volume, ay change in the concentration
of the individual species as a function of time, maybe represented by the following
equation:
(7)
For this section, separating and integrating we obtain
(8)
(9)
A plot of ln (CA/CA0) vs. t gives a straight line through the origin for this form of rate
equation. If the straight line was obtained, the assumption was right that kinetic of glucose
degradation occurs in first-order reaction. Fig 4 shows reaction time to ln (CA/CA0) at
various acid-catalyst concentration.
Figure 4. A plot of ln (CA/CA0) to temperature at (a) 0,05 M H2SO4 , (b) 0,1 M H2SO4 , (c) 0,5 M
H2SO4
Fig 4 shows all the experimental data have a straight line which indicates the reaction
occur in first-order reaction. Others study mention that degradation glucose occurs in the
first-order reaction [7], [6].
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Vol.5, No. 2, November 2020
Rahmawati | Kinetics Study of Acid Catalyzed Degradation of Glucose in High-… 27
Table 1. Effect of temperature to reaction rate constant
H2SO4
Concentration
Temperature
(oC)
k n
100 0,00503 1
0.5 M
125 0,00543 1
150 0,00569 1
175 0,00630 1
100 0,00428 1
0.1 M
125 0,00485 1
150 0,00527 1
175 0,00610 1
100 0,00413 1
0.05 M
125 0,00474 1
150 0,00525 1
175 0,00620 1
From table 1, we can conclude that the reaction rate constant is directly proportional
to the temperature. When the temperature rises, the reaction rate constant also rises. In
the concentration acid-catalyst 0,5; 0,1; 0,05 M the reaction rate constant have been
increased with the temperature. This is in accordance with the Arrhenius equation.
k = reaction rate constant (mol/m
3
)
1-n
s
-1
,k0 = pre-exponential factor (mol/m
3
) s
-
1, Ea=
Activation energy of reaction (J/mol)
,
R = ideal gas constant. From that equation, we
could see the greater the temperature in a reaction, the constant rate of formation of HMF
(Hydroxymethylfurfural) increases, the rate of HMF formation (Hydroxymethylfurfural) also
increases. Since the temperature of a reaction raises, the reacting particles will move
faster so that the frequency of collisions is greater.
Table 2. Activation energy
Acid catalyst
concentration
Ea (J/mol)
0,5 M 3988,14
0,1 M 6341,59
0,05 M 7306,59
From table 2, we can conclude that the higher catalyst concentration, activation
energy will be decreased. This is in accordance with Levenspiel, who states that the
reaction rate and activation energy are inversely proportional so that the higher the
catalyst concentration, the rate of reaction increases and the activation energy
decreases. The activation energy has a dependency on temperature, reaction with high
activation energies are very temperature-sensitive. Reaction with low activation energies
are relatively temperature-sensitive.
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Rahmawati | Kinetics Study of Acid Catalyzed Degradation of Glucose in High-… 28
4. CONCLUSION
The value of the rate of glucose degradation is not the same as the rate of formation
of HMF, it can be indicated that HMF is not the only result of glucose degradation, but
there are other compounds formed in the process of glucose degradation. The greatest
concentration of HMF (Hydroxymethylfurfural) at operation condition 0,5 M acid-catalyst
concentration, the temperature of 175 ° C, reaction time = 120 minutes was 0.003458 mol
/ L. In this study kinetic degradation of glucose into HMF follow first-order reaction, and
the reaction rate constant proportional to rate formation of HMF. Activation Energy (Ea)
values were 7306,593 J/mol; 6341,59 J/mol; 3988,14 J/mol and 3988,14 J/mol on the
concentration sulfuric acid 0,05M; 0,1 M; 0,05M, from that result indicated that reaction
rate was increase when activation energy was decrease this was related to Arrhenius
equation. The effect of acid concentration on degradation glucose was the higher acid
concentration used, the more glucose was degraded, and more HMF was formed.
Meanwhile, the effect of temperature of reaction on degradation glucose was the higher
temperature of the reaction, more glucose was degraded, and more HMF was formed.
ACKNOWLEDGMENTS
Chemical Reaction Engineering Laboratory, Chemical Engineering Faculty, Institut
Teknologi Sepuluh Nopember Surabaya.
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