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Chang 2006
Chang 2006
Chang 2006
Abstract Lewlinic acid is a kind of new green platform chemical with wide application. The kinetics of levulinic acid
formation from glucose decomposition at high temperature was investigated. Glucose containing 1%, 3% or 5% H2S04
was treated at 170°C or 190°C.For the various experimental conditions assayed, the time-courses of glucose and glucose
degradation products (including 5-hydmxymethylfurfural and levulinic acid) were established. These variables were cor-
related with the reaction time based on the equations derived from a pseudo-homogeneous, fmt-order kinetic model,
which provided a satisfactory interpretation of the experimental results. The set of kinetic parameters from regression of
experimental data provided useful information for understanding the levulinic acid formation mechanism.
Keywords levulinic acid, kinetics, decomposition, platform chemical
0'25 5
0.20
I, o.20t
0 10 20 30 40 50 60
t, min 1, min
(a) 1% H,SO, (a) 1% H$O,
0.20
0'25 5
0 10 20 30 40 50 60
t, min 1, min
(b) 3% H,SO, (b) 3% HISO,
0.20 1
I -.
7
I I I
0 10 20 - min
I,
30 & 60 0 10 20 30
t, min
40 50 60
(c) 5% H,SO,
(c) 5% H,SO,
Figure 1 Experimental and predicted concentrationsof Figure 2 Experimental and predicted concentrationsof
the products generated during the hydrolysis of 1% ,3% or the products generated during the hydrolysis of 1%,3% or
5% &SO4 at 170C and different time 5% H2S04at 190C and different time
+
glucose; W 5-HMF; A LA +glucose; W 5-HMF; A LA
be seen that the glucose decomposition rate constant k
5-HMF formation from glucose is very complicated,
increases as the acid concentration and temperature
increases, and the values of kl with different acid con- many unidentified intermediates can be formed during
glucose decomp~sition"~~. Neglecting the formation
centration are smaller than the values of k, indicating
of intermediates, the formation of 5-HMF can be
that only part of glucose can decomposes into 5-HMF
and the yield of LA can not reach its theoretical yield. modeled as consecutive reactions, and Figs.1 and 2
exhibited the change of 5-HMF concentration with
3.2 5-HMF formation time displayed typical behavior of a consecutive
As the precursor of LA, the mechanism of first-order pathway with a maximum concentration.
October, 2006
Kinetics of Lewlinic Acid Formation from Glucose Decompositionat High Temperature 711
Table 2 Generalized models for predicting kinetic pa- value of activation energy for glucose decomposition
rameters as a function of sulphuric acid concentration was greater than that of 5-HMF decomposition. Tara-
Models ? banko et al. reported the kinetics of LA formation
from glucose at 98"C, revealing the rate of LA for-
k, = 4.597 x 109 C0.427 exD( -86.33 X lo3 ) 0.994 mation from lucose depends slightly on the acid
c~ncentration'~? But, different results were obtained at
k, -56.95~10~
higher temperature conditions. The rate of LA forma-
=4.318x107c0.973
exp( RT ) 0.958 tion increases sharply with the increase of the acid
concentrations.
k3 = 1 . 2 01023C0.119
~ exp( 209i;103] 0.940
The acid-catalyzed conversion of glucose into LA
can also be carried out in concentrated solutions of
acids at lower temperature, thus high consumption of
the acid and longer reaction time were required[211.
Table 1 shows that with the increases of tem- Although high yield of LA can be attained at low
perature and acid concentration, 5-HMF formation temperature, the disadvantages of long reaction time,
rate constant kl also increased. But the relative rate of corrosion to equipment and the difficulty of acid re-
5-HMF formation with respect to glucose decomposi- covery limit its further use in industry. Contrarily, the
tion had not the same rules as rate constant kl. In- consumption of the acid and reaction time can be de-
creasing acid concentration from 1% to 5% did not creased sharply under high temperature conditions,
enhance the formation rate of 5-HMF relative to over- which was helpful to decrease the side products"".
all glucose decomposition obviously as indicated by High temperature hydrolysis with dilute acid appears
kl/k ratio. The values of kllk at 190°C are lower than to be in the best position from economic viewpoint.
those at 170"C, suggesting that the overall glucose Especially, when using biomass as raw materials to
decomposition rate k increases more quickly than the product LA, high tem erature can promote the LA
5-HMF formation rate kl, and higher temperature will production effectively'.pI. But, too high temperature
promote glucose decomposition. (>250"C) may also cause further decomposition of LA,
and different materials have different optimal condi-
3.3 Levulinic acid formation tions. In this study, the highest LA yield can reach up
LA is the product of 5-HMF decomposition'201. to 80.7% (molar percent) of theoretical yield under
As shown in Figs.1 and 2, concentration of LA in- 170°C and 5% acid conditions.
creased quickly at the initial stage, and then it reached
to a certain value. Based on the model and experi- NOMENCLATURE
mental data, the calculated rate constant of LA forma- a constant in model
tion increased with the increases of temperature and C sulfuric acid mass concentration, % (by mass)
cglu glucose concentration, mo1.L-I
acid concentration. It can be observed that the forma- CJ."~F 5-HMF concentration, mo1.L-I
tion rate of LA relative to overall glucose decomposi- cLA LA concentration, mo1.L-I
tion can be enhanced by increasing acid concentration E activation energy, kT.mo1-l
from 1% to 5%, as indicated by an increasing k2Ik ra- k rate constant, min-'
tio from Table 1. It is also found that values of kdk k0 pre-exponential factor, min-'
It constant in model
with same acid concentration at 190°C are smaller T temperature, K
than those of 170°C. The reason is that the average t time, min
October, 2006