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Biomass 14(1987) 185-194

Dehydration of D-Fructose to Levulinic Acid over LZY


Zeolite Catalyst

Jinder Jow, Gregory L. Rorrer, Martin C. Hawley


Department of Chemical Engineering, Michigan State University, East Lansing,
Michigan 48824, USA

and
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

Molten D-fructose was catalytically dehydrated to HMF and levulinic acid


over solid-acid L Z Y zeolite powder within a sealed batch reactor at
140 C. Analysis of the product distribution via HPLC after various reac-
tion times (0 to 15 h) revealed that the model for the heterogeneous
dehydration of o-fructose over L Z Y zeolite catalyst was consistent with
the model for the homogeneous hydronium ion-catalyzed o-fructose
dehydration. After 15 h, the maximum yield of levulinic acid was 0"432 g
levu#nic acid per 1 "00 g of the original o-fructose, but the net yield of
HMF was only 0"044 g HMF per 1.00g of the original D-fructose. The
high yield of levulinic acid was due to the strong dehydration ability of the
Lewis acid sites on the alumina~silica support of the L Z Y zeolite. The
high selectivity was due to the molecular-sieving capability of the L Z Y
zeolite matrix, which trapped the 0"82 nm diameter HMF molecule
within a 'cage' adjoining the O"75 nm LZ Y zeolite pores.

Key words: Acid-catalyzed dehydration, zeolites, D-fructose.

INTRODUCTION

It is well established that the acid-catalyzed dehydration of D-fructose,


D-glucose, or other hexoses yields 5-hydroxymethylfurfural ( H M F ) and
185
Biomass 0144-4565/87/S03.50 - - 1987 Elsevier Applied Science Publishers Ltd.
England. Printed in Great Britain
186 J. Jow, G. L. Rorrer, M. C. Hawley, D. T. A. Lamport

levulinic acid. Levulinic acid is a particularly useful chemical inter-


mediate which can be catalytically converted to a variety of useful
chemicals and fuels, as discussed by Leonard.
The mechanism of acid-catalyzed o-fructose dehydration was
deduced by Anet 2 and Harris & Feather? They established that the
opening of the cyclic hexose ring is the first step to o-fructose dehydra-
tion. The acyclic hexose then undergoes enolization and dehydration to
yield the cyclic molecule HMF, the first stable dehydration product.
HMF can then undergo dehydration and ring cleavage under more
strongly acidic conditions to yield the linear molecule, levulinic acid.
In previous work, o-fructose, o-glucose and other sugars were cataly-
tically dehydrated first to HMF and then to levulinic acid by mineral
acids or strongly-acidic ion-exchange resins in aqueous or non-aqueous
solvent medium. Since o-fructose is dehydrated to HMF at 40 times the
rate of o-glucose,4 many investigators chose o-fructose as the model sub-
strate for acid-catalyzed hexose sugar dehydration. Rice 5 dehydrated
o-fructose with phosphoric acid in a water/ketone solvent for 48 h at
200C and attained a 65 % to 85 % yield to HMF, but no levulinic acid.
Moye & Goldsack 6 dehydrated o-fructose with sulfuric acid in boiling
tetrahydrofurfuryl alcohol for 5 s and attained a 75 % yield of HMF, but
no levulinic acid. Most notably, Kuster & Van Der Baan 7 dehydrated o-
fructose to HMF with 1-0 M hydrochloric acid at 95 C, then separately
dehydrated HMF to levulinic acid with 2.0 M hydrochloric acid at 95 C
for 48 h, and attained a 65 % yield of levulinic acid. Based on the
product distribution data, Kuster developed a kinetic model for acid-
catalyzed o-fructose dehydration.
In order to facilitate separation of the acidic catalyst from the final
product phase, several investigators used strongly acidic ion-exchange
resins to catalytically dehydrate o-fructose to HMF and levulinic acid.
Rase & Schraufnagel dehydrated sucrose (a glucose-fructose dimer)
over various Amberlyst resins in water at 100 C for 24 h. The selectivity
of levulinic acid to HMF was 83 % (defined as the moles of levulinic
acid/moles of H M F 100 %), but the yield of levulinic acid was only
24 %. Increasing the pore size in the resin decreased the selectivity of
levulinic acid to HMF. Nakamura & Morikawa 9 dehydrated o-fructose
over a Diaion resin in DMSO for 8"3 h at 88C and attained an impres-
sive yield of HMF (90%), but no levulinic acid.
The concept of heterogeneous o-fructose dehydration on a strongly
acidic particle of known pore size, as shown previously with strongly
acidic ion-exchange resins, led us to believe that o-fructose could also be
dehydrated on a solid acid zeolite catalyst of precisely known pore size
and geometry. In fact, the strong Lewis acid function of the alumina/
Catalyticdehydrationof o-fructose 187

silica zeolite support, combined with the molecular sieving capability of


the zeolite matrix, could potentially provide a high yield and selectivity
of levulinic acid by trapping HMF (the first stable dehydration product)
within a strongly acidic molecular 'cage'. The cyclic HMF molecule
could not exit the cage until it was further dehydrated to the linear mole-
cule levulinic acid, which would be small enough to exit the cage by
threading its long axis through the pore opening. We chose the Y-type
LZY zeolite (Faujasite) to carry out this molecular tailoring. The LZY
zeolite possesses a pore diameter of 0.75 nm, large enough for acyclic D-
fructose (the 1, 2 enediol formed after ring opening of D-fructose) mole-
cule to enter the cage through the pore, but small enough to trap the 0.82
nm diameter cyclic HMF molecule within the cage.
The objective of this investigation was to determine the feasibility of
catalytically dehydrating D-fructose to levulinic acid over LZY zeolite.
Experimentally, D-fructose crystals and LZY zeolite powder were mixed
and then heated to a given temperature for a given reaction time in a
sealed batch reactor. The water-soluble reaction products were then
analyzed by High Performance Liquid Chromatography (HPLC). On the
basis of the reaction product distribution data, we demonstrated that
LZY zeolite catalytically dehydrated D-fructose to levulinic acid with
high yield and selectivity. The details and significance of this key finding
follow.

EXPERIMENTAL

Materials

D-Fructose was obtained in crystalline form from Sigma Chemical


(Cambridge, MA). The molecular weight of D-fructose is 180.16, the
melting point is 103C to 105C, and the mean molecular diameter is 0"9
nm. LZY zeolite, obtained from Linde (Union Carbide Corporation),
served as the solid-acid catalyst. LZY zeolite is a Y-type Faujasite, pos-
sessing cubic symmetry and a pore diameter of 0.75 nm. The chemical
formula of the LZY zeolite is Na~6 (A102)5~ (8iO2)136. The temperature
of stability is 973C.

Procedure

D-Fructose crystals (1.00 g) and 1.00 g of LZY zeolite powder were


added to a 50 ml test tube and physically mixed. The test tube (batch
reactor) was sealed with a rubber stopper and nitrogen was purged
188 J. Jow, G. L. Rorrer, M. C. Hawley, D. T. A. Lamport

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

The water-soluble reaction products were analyzed by High Perform-


ance Liquid Chromatography (HPLC). Unreacted D-fructose was
analyzed separately from H M F and levulinic acid. D-Fructose and other
monosaccharides were separated on a B I O - R A D Aminex HPX-87P
column at 85C. The mobile phase was degassed HPLC-grade water at
0"6 ml min -j. Column effluent sugars were detected by differential
refractive index. Retention time was 12.7 min for D-glucose, and 17.0
min for D-fructose. Levulinic acid and H M F were separated on a Zorbax
ODS column at room temperature. The solvent program was 100 %
heptafluorobutyric acid (HFBA) solution (0.13 wt % H F B A in water) for
15 rain at 0.5 ml min-~, 70 % H F B A solution, 30 % (v/v) acetonitrile for
5 min at 0"5 ml min-1, and finally, 100 % H F B A solution for 5 min at
0-5 ml min- 1. The column effluent was monitored via UV absorbance at
220 nm. Retention time was 8"5 min for levulinic acid and 12.5 min for
HME

RESULTS

Control experiment for catalytic activity

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

1 h, the reaction mixture turned yellow-brown. HPLC analysis of the


water-soluble reaction products revealed that 35-4 % of the original
weight of the o-fructose was converted to levulinic acid. No HMF was
detected. However, a brown insoluble residue was formed.

Reaction kinetics at 140C

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

Reaction o-Fructose HMF Levulinic" o-Glucose Selectivity b


time (wt %) (wt %) acid (wt %)
(h) (wt %)

0-0 100.0 0'0 0'0 0"0


0.5 52.7 0"0 16.8 2.3 oo
1.0 44.7 0-0 25.1 11.3 oo
2.0 29.7 1.2 33"5 7.0 30.3
15.0 4-0 4.4 43.2 5'9 10.7

"Maximum theoretical yield of levulinic acid is 64.5% of the original weight of D-


fructose.
/,Selectivity tool% yield levulinic acid
mol% yield H M F
190 J. Jow, G. L. Rorrer, M. C. Hawley, D. T. A. Lamport

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'-.-
.............. . . . . . . . . _ . ,

0.0 5.0 10.0 15.0


Reaction T i m e (h)

Fig. 1. Product distribution of D-fructose dehydration over LZY-zeolite catalyst at


140C as a function of time. Initial fructose to catalyst ratio was 1:1 by weight.

D-fructose. This corresponds to a 67 % conversion on a levulinic acid


basis. The H M F intermediate was not detected until the reaction had
proceeded for nearly 2 h and even then only appeared in small amounts
relative to levulinic acid. Small levels of o-glucose were also detected.

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

D-Fructose HMF Levulinic Acid

.
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

Fig. 2. Overall reaction scheme for hydronium-ion catalyzed dehydration of


D-fructose.

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

formation can be minimized and levulinic acid production maximized by


optimization of reaction conditions, which was not attempted in this
study.
D-Glucose, another by-product of D-fructose dehydration identified in
this study, was probably formed by the acid-catalyzed isomerization of
D-fructose. Kuster & Van Der Baan 7 also noted D-glucose formation
during the hydronium-ion catalyzed dehydration of D-fructose. As
shown in Table 1 and Fig. 1, the level of glucose production remained
low because the isomerization process sought glucose-fructose equili-
brium, with the rate of D-fructose isomerization much lower than the rate
of D-fructose dehydration. Further, it is not unreasonable to assume that
the D-glucose was also catalytically dehydrated to levulinic acid within
the LZY zeolite, although at a much slower rate relative to D-fructose
dehydration.
According to Kuster's model, formic acid is formed by the acid-
catalyzed dehydration of HMF to levulinic acid. The analytical pro-
cedures used in this study were not designed to detect for formic acid in
the water-soluble product distribution. However, it is believed formic
acid was formed in a 1:1 mole ratio with levulinic acid, consistent with
Kuster's model.
Since the dehydration of D-fructose over the LZY zeolite catalyst is a
heterogeneous reaction, the product phase is readily separated from the
catalyst phase by solvent extraction. The acid would not have to be
reclaimed from the product phase, as would be the case with hydronium-
ion catalyzed D-fructose dehydration. Instead, the LZY-zeolite catalyst
pellets would be regenerated (particularly if 'humin' formation is a
problem) and then recycled back to a fresh batch of D-fructose.
In conclusion, the dehydration of D-fructose over LZY-zeolite catalyst
is feasible and offers: 1 ) a high yield and selectivity of levulinic acid and
2) simple recovery of levulinic acid from the catalyst.
The study of catalytic dehydration of D-fructose to levulinic acid over
LZY zeolite powder presented here was only exploratory in scope.
Much work still remains to be done. First, a laboratory-scale reaction
vessel must be designed to provide uniform heating and mixing of the
reaction mixture. Second, analytical techniques must be refined,
especially for quantifying formic acid and water-insoluble residue, so
that a more complete material balance can be obtained. Third, the
reaction conditions (reaction time, temperature, initial fructose:catalyst
ratio) for maximum levulinic acid production must be optimized. Fourth,
the zeolite catalyst must be optimized by exploring the effect of acidity
(alumina/silica ratio), solvent medium, pore size, and overall particle size
Catalytic dehydration of o-fructose 193

on levulinic acid production. Fifth, the regeneration and recycle of the


zeolite catalyst pellets (after solvent-extraction of water-soluble reaction
products) must be demonstrated. Finally, a quantitative kinetic model for
o-fructose dehydration over zeolite catalysts must be developed.
Although o-fructose was the only sugar studied here, it is possible
other six-carbon sugars can be catalytically dehydrated to levulinic acid
by LZY zeolites. The first six-carbon sugar to consider for catalytic
dehydration over LZY zeolites is o-glucose, o-Glucose is the primary
product of lignocellulose hydrolysis. Traditionally, the D-glucose is fer-
mented to ethanol or other chemicals. Unfortunately, fermentation pro-
cesses require long reaction times in a dilute, aqueous, batch reaction
media and ultimately result in low carbon conversion, because one mole
of carbon dioxide is produced per mole of ethanol. However, by using
LZY-zeolite catalysts for the dehydration of sugar, it may be possible to
circumvent fermentation and convert lignocellulose hydrolysis sugars
directly to levulinic and formic acid and then to useful chemicals and
fuels.

CONCLUSIONS

LZY-zeolite solid-acid catalyst powder dehydrated molten o-fructose to


levulinic acid with high yield and selectivity relative to H M E The model
for D-fructose dehydration over LZY-zeolite catalyst was proposed to be
consistent with the model for hydronium-ion catalyzed o-fructose
dehydration in aqueous solution.

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