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Derek T. A. Lamport
MSU-DOE Plant Research Laboratory, Michigan State University, East Lansing,
Michigan 48824, USA
(Received 8 June 1987; revised version received 8 September 1987;
accepted 11 September 1987)
ABSTRA CT
INTRODUCTION
EXPERIMENTAL
Materials
Procedure
through the test tube by an inlet/outlet tube tapped through the stopper.
The batch reactor was immersed in a thermostatted paraffin oil bath pre-
heated to the desired reaction temperature (95C to 140C). The batch
reaction was allowed to proceed for a given reaction time (0"5 h to 15 h).
The reactor was then removed from the oil bath. Immediately thereafter,
5.0 ml of distilled water at room temperature was added to the reaction
mixture and briskly stirred to quench the reaction and dissolve the
water-soluble reaction products away from the L Z Y catalyst powder and
insoluble carbonaceous residue. The product solution was then filtered
and frozen for storage.
Product analysis
RESULTS
Solid D-fructose crystals were heated with and without LZY zeolite
powder in order to demonstrate the existence of catalytic activity. Since
the melting point of D-fructose is 103C to 105C a reaction temperature
of 95C (10C below the melting point) was selected to exclude the pos-
sibility of thermal decomposition. When solid D-fructose crystals without
catalyst were heated to 95C, no reaction occurred after 1 h, and the D-
fructose crystals remained white. However, when solid D-fructose
crystals were mixed with L Z Y zeolite powder and heated to 95C, after
Catalytic dehydration olD-fructose 189
Solid D-fructose crystals were mixed with LZY zeolite powder and
heated to 140C. At this temperature the o-fructose crystals melted
around the LZY zeolite powder. Soon after, the reaction mixture turned
yellow then yellow-brown. The water-soluble reaction products were
yellow, and the insoluble reaction products were brown. The formation
of carbonaceous, water-insoluble residue at 140C was probably due to
two processes: thermal decomposition of o-fructose, and acid-catalyzed
decomposition of HMF and levulinic acid to 'humin', a carbonaceous
hydrocarbon identified by Kuster & Van Der Baan 7 during hydronium-
ion-catalyzed o-fructose dehydration.
The kinetics of levulinic acid and by-product formation are given in
Table 1 and Fig. 1. Evidently, LZY zeolite dehydrated o-fructose to
levulinic acid with high yield and selectivity relative to H M E Levulinic
acid was the predominant water-soluble reaction product. The
maximum theoretical yield of levulinic acid from D-fructose is 64"5 % of
the original weight of the o-fructose. The maximum levulinic acid
attained in this study was 0.432 g levulinic acid per 1.00 g of the original
TABLE 1
Product Distribution of o-Fructose Dehydration over LZY-Zeolite Catalyst at 140C:
Initial o-fructose to catalyst ratio was 1 : 1 by weight
100.0 H D-Fructose
90.0 1 H HMF
80.0 ~ Levulinic Acid
; -: D-Glucose
~" 70.0
60.0
o.ol
'o.o1
l--1/.2'-.-
.............. . . . . . . . . _ . ,
DISCUSSION
On the basis of the reaction product distribution data presented here, the
reaction scheme for molten D-fructose dehydration of H M F and
levulinic acid over L Z Y zeolite powder is consistent with the reaction
scheme for hydronium-ion catalyzed D-fructose dehydration proposed
by Kuster & Van Der Baan, 7 as shown in Fig. 2. This conclusion is not
surprising, since the alumina/silica support of the LZY zeolite acts as a
strong Lewis acid.
The LZY zeolite catalyst effectively dehydrated D-fructose to levulinic
acid, as demonstrated in Table 1 and Fig. 1. Two unique properties of the
LZY zeolite are responsible for this catalytic activity: the strong Lewis-
acid function of the alumina/silica support, and the molecular-sieving
capability of the Y-type zeolite (Faujasite) pore matrix. In all previous
studies of acid-catalyzed D-fructose dehydration, H M F was the primary
dehydration product, or at least appeared in significant concentration
before being further dehydrated to levulinic acid. However, in this study
the H M F intermediate was not detected until the reaction had
Catalytic dehydration of o-fructose 191
.
CH3-C-CH,,-CH2-C-OH
HIH~OMoH H+ >HOH2C C-H H+ II ~ II
k., o./1 0 0
HO'~ l ~ "CH2OH -I-
OH H
+
Formic Acid
+ H-C-OH
II
D-Glucose 0
humin +
CH2OH
..J;-\o. c,.2 .,.o H2O
. O~/IH
H OH
+
humin
C1.4H1.0
proceeded for nearly 2 h at 140C and even then appeared in only minor
amounts relative to levulinic acid. Evidently, the hexose ring of the D-
fructose molecule was first opened over a Lewis acid site on the
alumina/silica support. The resulting acyclic hexose (1, 2-enediol) then
diffused through the zeolite pore matrix and into a 'cage' joining pores
within the zeolite pore matrix. Here, the 1, 2-enediol was dehydrated to
HMF over Lewis acid site on the alumina/silica support within the cage.
However, the cyclic, 0.82 nm diameter HMF molecule was too large to
exit the cage through the 0"75 nm Y-type zeolite pore, and so remained
trapped within the zeolite cage until it was catalytically dehydrated to the
linear molecule levulinic acid, which was now small enough to exit the
cage by threading its long axis through the pore opening.
The model just presented suggests that HMF would not be detected in
the product phase. However, small amounts of HMF were detected later
in the reaction. It is likely that the levulinic acid product catalyzed the
homogeneous dehydration of unreacted D-fructose to HMF in the
product phase outside of the LZY zeolite particle. This reaction can be
considered autocatalytic, since levulinic acid is first formed by catalytic
dehydration of D-fructose within the LZY zeolite pellet.
Apparently, a high yield of levulinic acid is possible, although at
140C the thermal decomposition of D-fructose and the acid-catalyzed
decomposition of HMF and levulinic acid to the carbonaceous residue
'humin' lowered the maximum attainable levulinic acid yield. 'Humin'
192 J. Jow, G. L. Rorrer, M. C. Hawley, D. T. A. Lamport
CONCLUSIONS
REFERENCES