Article

pubs.acs.org/IECR

Levulinic Acid Production Using Solid-Acid Catalysis

Ilian Guzmán, Arkaitz Heras, M. B. Güemez, Aitziber Iriondo, Jose F. Cambra, and Jesús Requies*
Faculty of Engineering (UPV/EHU), Alameda Urquijo s/n, 48013 Bilbao, Spain

ABSTRACT: Levulinic acid (LA) is one of the compounds included in

the list of the 12 chemicals, known as “building blocks” obtained from
biomass. One route to synthesize levulinic acid is from furfuryl alcohol
(FA), which is a compound that can be obtained from biomass. For this
route, the hydration and ring opening of FA is necessary. Usually, the
hydration takes place using homogeneous strong acid catalysts, being
the disadvantages of using homogeneous acid catalysts well-known.
Downloaded by UNIV CATOLICA DE TEMUCO at 08:32:08:787 on May 29, 2019

Therefore, this work has studied the production of LA using

heterogeneous catalysts such as ion exchange resins, zeolites, and acidic
clays. The LA yield was increased by the optimal control of FA feed.
The initial catalyst screening study showed results up to 62% in LA
yield. Then, an optimization procedure was developed using the ZSM-5
from https://pubs.acs.org/doi/10.1021/acs.iecr.5b04190.

catalyst, reaching a maximum LA yield of 77%.

1. INTRODUCTION alternate oligomeric products (Scheme 1).8−12 The formation

The route to synthesize levulinic acid (LA) from furfuryl
alcohol (FA) is the hydration and ring opening of FA.1−4 The
synthesis of LA from FA has been studied since the mid-20th
century, and the majority of studies have been patented by
various authors.1−4 However, published scientific literature is
not abundant. Usually, the hydration of FA to LA occurs using
homogeneous strong acid catalysts, as sulfuric or hydrochloric
acids.2,4,5 The disadvantages of using homogeneous acid
catalysts are well-known: risk in handling, high toxicity, the
need of special infrastructures for their use, with the
corresponding associated cost, large amounts of catalyst, and
the difficulty involved in their separation and recovery.
Therefore, promising studies about this reaction has been
included using heterogeneous catalysts with adequate acidity
and textural properties.3,6,7 Catalysts such as ion exchange
resins, zeolites, and acidic clays are gaining importance to
obtain high-purity products. These processes use heteroge-
neous catalysts, with an easier separation step of the catalyst
from the reaction mixture and lower corrosion issues,
minimizing the need for additional workup procedures and
avoiding the generation of large volumes of acid wastes.
The best results obtained in homogeneous catalysis (from
the work of Masatomi et al.2), showed a 93 mol % LA yield
using a semibatch reactor with hydrochloric acid as the catalyst
and methyl ethyl ketone (MEK) as the solvent to dilute the FA
feed. However, in heterogeneous catalysis, the best results were
published in 1956 by Redmond et al.,1 who reported a 55
mol % LA yield, using Amberlite IR-120 as a catalyst in a
semibatch process, via the addition of concentrated FA to
water. In an acidic aqueous medium, FA polymerizes to form
of oligomeric resins in the hydration reaction of FA cause not
only low yields, but also generates some operational problems
in the process. The oligomeration occurs via a condensation
among the hydroxyl group of the methyl group of one furan
ring and the hydrogen atom in the fifth position of another
furan ring, leading to water elimination and the formation of a
methylene linkage.12 An alternative to avoiding or limiting
these undesired reactions is controlling the FA concentration in
the reaction media: concentrations of <2 wt % are recom-
mended.8 To achieve this low concentration of FA and limit the
formation of undesirable byproducts, an organic inert co-
solvent may be added to the reaction media.8
At high concentrations of FA, the polymerization reaction is
the predominant one, as determined by the kinetics of the
different reactions. Kim et al.8 established that polymerization
of the FA is generated by the formation of a primary
carbocation (−CH2+) from the protonation of a FA hydroxyl
group. According to their hypothesis, the presence of a solvent
in the reaction medium can generate a competition with the
carbocation of FA by interactions as solvation proceeds, thus
reducing the formation of resins. Moreover, Otto et al.,13
recently suggested that solvent can affect the reaction rates
Special Issue: International Conference on Chemical and Biochem-
ical Engineering 2015
Received: November 5, 2015
Revised: March 23, 2016
Accepted: March 29, 2016
Published: March 29, 2016

© 2016 American Chemical Society 5139 DOI: 10.1021/acs.iecr.5b04190

Ind. Eng. Chem. Res. 2016, 55, 5139−5144
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Scheme 1. Main Reactions of Furfuryl Alcohol in an Aqueous Acid Medium
through steric effects. Others authors also studied the aqueous
reaction of FA, without reporting LA yields. Hronec et al.6
found that the major compound obtained was 4-hydroxy-2-
cyclopentenone (4-HCP), which is catalyzed by hydrogen ions
formed via the autodissociation of water. Maldonado et al.7
asserted that germinal diol species (4,5,5-trihydroxypentan-2-
one) were formed as main intermediate to LA via the use of
Amberlyst 15 as a catalyst. In addition to this, some other
authors have also studied the effect of using organic solvents to
extract organic molecules from the aqueous acidic reaction
medium and minimize the undesired condensation products,
using alkyl alcohols,14 alkyl phenols,15 cyclopentyl methyl
ether,16 or traditional solvents (such as toluene or tetrahy-
drofuran (THF)).5 Furthermore, if an alcohol is incorporated
in the FA acid reaction medium, then high yields to levulinate
esters are obtained.17
Since the best result was reached by Otsuka et al.,2 using
homogeneous catalysis, this work is focused on the study of the
production of LA from FA via the hydration and ring opening
of FA, using different heterogeneous acids catalysts as a
substitute for hydrochloric acid (HCl). Even more, a water-
soluble aliphatic ketone was added to the reaction media in
order to obtain a higher efficiency in the production of LA.2
2. EXPERIMENTAL SECTION
2.1. Preparation of Catalysts. The screening of catalyst
was carried out by preparing the following catalysts: inorganic
catalysts as HZSM-5 zeolite (H-Z(50)), beta zeolite (H-β),
ultrastable zeolite (H-USY), heteropolyacid-type phospho-
tungstic acid (PTA), zirconia sulfated superacid (ZrO2/
SO42−), and the organic commercial ion exchange resins
Amberlyst 35 Wet (A35) and Amberlyst 47 (A47). These
materials have a substantial amount of Brönsted acid sites,18−22
and different textural properties as surface area and pore size, as
well as thermal stability. The ZSM5 (SiO2/Al2O3:50) and β-
zeolites (SiO2/Al2O3:25) were purchased from Zeolyst Interna-
tional (ammonia form). These were calcined at 823 K to their
protonated forms H-Z(50) and H-β. The H-ZD(50) is the
zeolite H-Z(50), which was subjected to a desilication process,
via the extraction of silica in a solution of NaOH (0.2 M),
according to the following procedure. H-ZD(50) was added to
NaOH (0.2 M) at 353 K and stirred for 2 h. Then, the solids
were separated by centrifugation and washed with doubly
distilled water until neutral pH; afterward, these were dried
overnight at 383 K. The obtained zeolites were also treated
with NH4Cl (0.5 M) to 333 K; the samples were newly
centrifuged and washed until all chlorides were eliminated;
then, the solid was dried to 383 K and subsequently calcined at
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823 K during 4 h, to exchange NH4+ to H+. The ZrO2/SO42−
superacid catalyst was synthesized via a precipitation method,
using an ultrasound system at low temperature, according to
the following procedure. ZrN2O7·H2O was dissolved in distilled
water, and then the pH was adjusted at 9.0 via the addition of
aqueous ammonium (NH4OH, 30%). The solution was
introduced into ultrasonic equipment, and it was dried at 383
K by 6 h. The dried solid was immersed in 50 mL of H2SO4(0.5
M) for 12 h, and then the solid was separated by filtration and
dried at 383 K. Finally, the solid was calcinated at 923 K. The
hydrated PTA (Alfa Aesar) was supported on ultrastable Y-
zeolite and ZSM5 zeolite (referenced hereafter as PTA-USY
and PTA-Z(50), respectively). These materials were prepared
containing 10 wt % PTA (12WO3·H3PO4·xH2O), equivalent to
7.6 wt % tungsten; in both cases, 0.3 g of PTA was dissolved in
doubly distilled water (50 mL), and the content was transferred
to a rotary evaporator with 3 g of previously degasified zeolite.
The temperature and pressure of impregnation were set to 313
K and 5 mbar, respectively. The solids obtained were calcined
in air at 523 K. The Amberlyst 47 (A47) and Amberlyst 35 Wet
(A35) are commercial ion exchange resins that were provided
by Rohm Haas. They were dried overnight to 333 K before use.
2.2. Characterization of Catalysts. Textural parameters
were determined by using N2 adsorption−desorption techni-
ques at 77.35 K. The specific surface areas were obtained by
applying the Brunauer−Emmett−Teller (BET) method, and
the total pore volume was calculated at a relative pressure of P/
P0 = 0.976.
Temperature-programmed desorption of ammonia (NH3-
TPD) was used in order to measure the amount and strength of
acid sites on the catalysts. The TPD profiles were monitored
using a thermal conductivity (TCD) detector and recorded
from 272 K to 823 K at a heating rate of 10 K/min. The catalyst
was pretreated in a helium flow at 773 K for 1 h to remove the
physisorbed water and the intracrystalline water. Then, the
sample was cooled to 373 K and then NH3 was adsorbed using
pulsed injections at 373 K until saturation. The TCD signal was
collected and processed to obtain the results.
2.2.1. Catalytic Tests. For the activity tests, a semibatch-type
reactor with a capacity of 50 mL (Parker-Autoclave Engineers)
was used with a temperature and stirring controller (Iberfluid,
Model IB-50), and a liquid pump (Gilson, Model 307). The
reactor was loaded with 20 mL of a mixture that consisted of
4.2 mL of water (double-distilled) and 15.8 mL of the organic
solvent. The organic solvents used were methyl ethyl ketone
(MEK) (Alfa Aesar, 99%), cyclopentyl methyl ether (CPME)
(Sigma−Aldrich, ≥99.90%), THF (Panreac, 99.5%), and
acetone (Scharlau, 99.5%). The selected quantity of catalyst
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Table 1. Properties of Different Solid-Acid Catalysts Studied and Activity Results Obtaineda
LA yield conversion surface area determined via the BET method, average pore diameter, dp mesoporosity
catalyst (%) (%) SBET (m2/g) (Å) (%) acidity
A47 26.01 99.55 50 240 100 4.7 mequiv H+/g
A35 62.39 99.12 50 300 100 ≥5.2 mequiv H+/g
H-β 20.70 91.56 441 6 0 1.282 mmol NH3/g
PTA-USY 19.79 90.18 494 20 10 0.720 mmol NH3/g
H-Z(50) 58.22 99.45 395 24 50 0.826 mmol NH3/g
H-ZD(50)b 56.38 99.80 407 37 75 0.661 mmol NH3/g
H-ZDR(50) 300 42 70 0.727 mmol NH3/g
PTA-Z(50) 58.10 100.00 342 25 34 0.703 mmol NH3/g
ZrO2/SO42− 0.18 58.93 108 34 95 0.338 mmol NH3/g
a
Reaction conditions: 0.4 g of catalyst, 413 K, 10 bar of H2, MEK as solvent, 26.2 vol % FA in MEK, 1 h of reaction after 3.5 h of flow being fed. bH-
ZD(50) denotes zeolite obtained by using a desilication process.

was introduced in the reactor. Once the reactor was closed, it
was purged with N2 gas and then the pressure was increased up
to 10 bar using a gaseous medium (N2 or H2). Finally, it was
preheated to the desired temperature, and the pumping was
started. A side solution consisting of organic solvent and FA
(Sigma−Aldrich, 98%) was pumped for 3.5 h at a liquid flow
rate of 0.03 mL min−1. After this time, the pump was switched
off and the time set at t = 0. The test continued with heating
and stirring. Once the test was finished, the product inside the
reactor was filtered with 0.45 μm filters and weighed for later
calculations. A sample was taken to be analyzed via gas
chromatography in an Agilent Model 6890N GC with flame
ionization (FID) and TCD detectors.
3. RESULTS AND DISCUSSION
The results obtained in the preliminary screening are shown in
Table 1. The high reactivity of FA can be observed. Only the
superacid catalyst did not reach complete conversion of the FA;
nevertheless, the LA yield was very different. The higher LA
yield corresponds with the lower carbon balance error. The
main problem was the formation of furanic resins (the presence
of these furanic resins was confirmed by the brown-black color
of the reaction media); consequently, their contribution in the
carbon balances was not included. In addition, there were some
small peaks that were not identified in the gas chromatog-
raphy−mass spectroscopy (GC-MS) analysis; therefore, they
also were not included in the carbon balance. In any case, for
the best LA yields. the mass balance error of the carbon balance
was ∼20%.
In the preliminary results, it can be observed (Table 1) that,
under the conditions studied, the A35 ion-exchange resin
exhibited the best performance, attaining LA yields of up to 62
mol %, followed by H-Z(50) zeolite (58 mol %) and PTA-
Z(50) (58 mol %). The catalyst properties are also summarized
in Table 1, showing that the high acidity and mesoporosity of
A35 influenced the increase in LA yield. The incorporation of
PTA on Z(50) zeolite did not present improvements in the LA
yield, with respect to the support. The modified zeolite H-
ZD(50) did not show differences in LA yield, with respect to
the original support. In this case, although the desilication
process caused a slight increase in pore diameter and surface
area, the decrease in LA yield can be related to the acidity loss.
The activity results using H-β zeolite showed a low LA yield;
the surface characterization indicates that H-β has a high
acidity, but a low pore diameter value, and this property could
affect the reaction mechanism related to the access of molecules
to acid sites, causing the low LA yield. Very low activity was
also observed for the sulfated zirconium catalyst which showed
the lowest FA conversion (59 mol %), without a relevant
selectivity to LA; the low acidity value reported in Table 1
explains the inactivity of this catalyst in the reaction studied.
According to the results obtained, the H-Z(50) zeolite, in its
protonated form, was selected to be used for optimization of
operating parameters in the reaction system, because this
catalyst has better thermomechanical stability than the
Amberlyst catalysts.
3.1. Optimization of Operating Parameters Using H-
ZSM5 Zeolite (H-Z(50)). The optimization consisted of the
evaluation of the effect of the main operation conditions in the
LA yield. The variables that were considered for optimization
included the following: the use of hydrogen and nitrogen as
reaction atmospheres, the effect of solvent, the effect of the
amount of catalyst loaded, variation in the concentration of FA
in the feed stream, and the effect of temperature.
3.1.1. Effect of the Reaction Atmosphere. In the
preliminary catalytic screening, the reaction atmosphere was
hydrogen. The first step in the optimization of operating
parameters was the effect of the reaction atmosphere. For this
purpose, the initial operating conditions chosen in the catalytic
screening were 0.4 g of catalyst, 413 K, 10 bar of H2, MEK as
solvent, 26.2 vol % FA in MEK, and 1 h of reaction. The
reaction was studied under inert and hydrogenating atmos-
pheres, excluding the oxidant atmosphere, which is not suitable
for this reaction, because of the negative effect which is caused
by the formation of undesirable byproducts from furfuryl
alcohol oxidation. In Figure 1, it can be observed that the
presence of hydrogen increased the LA yield by almost 20
mol %. This increment of the LA yield is related to the decrease
in the formation of furanic polymers. The liquid obtained in the
Figure 1. Effect of the reaction atmosphere.

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reaction media, in the case of the inert atmosphere, was darker
than that obtained under a hydrogenating atmosphere,
indicating a greater amount of furan resins (polymers) in the
case of the inert atmosphere. The polymers are formed on the
catalytic surface continuously via the partial polymerization of
intermediate compounds formed from FA. Furthermore, the
different adsorption−desorption properties of the reactant and
products on the catalyst in different solvents23 or reaction
media24 might potentially affect the product selectivity.
In order to confirm the positive effect of hydrogen addition,
an additional experiment was developed, increasing the
hydrogen pressure from 20 bar to 50 bar and maintaining the
other operating conditions. Under these set of conditions, high
differences in the conversion and the LA selectivity were not
observed. The selectivity increased 0.5 mol % and the
conversion decreased to 99.3 mol %, within the range of the
experimental error. Therefore, the main conclusions of this part
is that the combination of the solvent and H2 in the reaction
media improved the LA yield. Nevertheless, there is a limit in
the amount of hydrogen producing this beneficial effect.
In addition, no hydrogenation products, such as 2-
methylfuran (MF) or tetrahydrofurfuryl alcohol (THFA),
were detected by GC (TCD-FID and MS) and HPLC,
probably because of the absence of metals such as nickel,
copper, ruthenium, or platinum, which favors hydrogen
adsorption on the catalyst surface and the corresponding
hydrogenation reaction. Thus, more research should be done in
order to explain the exact role of the presence of hydrogen in
this complex reaction system.
3.1.2. Effect of Solvent. The use of solvent has a high
importance in this reaction, because its presence in the reaction
media limits the resin formation, thus increasing the LA yield.4,8
The marked tendency of furan derivatives to form resins has
motivated studies on the incorporation of an organic cosolvent
to prevent their formation to a great extent. This solvent
mainly different alcohols such as ethanol, methanol, and 2-
propanolreacts with FA to form the corresponding levulinate
esther. In the case of the production of 5-hydromethylfurfural
from biomass, acetonitrile, ethyl acetate, THF, and 2-
butylphenol were used as solvents.25 To obtain furfural from
xylosa, solvents such as dioxane, γ-valeroctone, and THF were
also used.26 Compounds with a ketone group are also usually
added as co-solvents. These include MEK and pentanone;2 in
addition, several authors reported the use of water-soluble
aliphatic ketone in the reaction media to obtain LA with high
efficiency.2,5 Since the focus of this work is LA production,
alcohols were not used as solvents. For this work, two cyclic
structures were chosen: CPME and THF. CPME is a green
solvent with good properties for this type of process, whereas
THF is a typical solvent in different biomass processes. Finally,
two linear ketone solvents also were chosen: MEK and acetone,
because of the high efficiency of ketones as a solvent in the
production of LA.2
The results obtained are shown in Figure 2. In most cases,
the FA conversion was ∼100%: only the THF did not reach
complete conversion. CPME is a hydrophobic solvent;
therefore, the presence of water and CPME produces a
biphasic reaction system. The FA is dissolved in both phases,
but FA is mostly located in the organic phase; therefore, in the
aqueous phase, the FA concentration remains quite low.
Because the reaction occurs in the aqueous phase, the FA
gradually crosses to the aqueous phase through the interface to
maintain the equilibrium. Using a biphasic reactor, the LA yield
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Figure 2. Effect of the solvent in reaction media.
was very low (11%) with total conversion. That observation
could be related to the low FA concentration in the water
phase, limiting the kinetics of the transformation of FA to
furanic resins. The other solvents were soluble in water; the
worst solvent was THF. This finding was surprising, because
Dumesic et al.27 reached a high LA yield, using a similar
THF:water ratio and the H-ZSM-5 zeolite. These authors claim
that the hydrophobic nature of H-ZSM-5 alter the internal
solvent microenvironment within the zeolite framework,
allowing for high LA yields, even at low THF solvent
concentrations. Probably the presence of H2SO4 helped to
maintain this internal solvent microenvironment to increase the
LA yield. In the present study, it was observed that the presence
of THF did not prevent the formation of resins; therefore, the
yield was very low. The high yield obtained with MEK and
acetone indicated that linear ketone groups could act as
inhibitors to resin formation, since furan resins were not
evidenced into reactor after reaction. The linear ketone group
with higher molecular weight reached higher efficiency than
acetone; it seems that the presence of this linear ketone avoided
or limited the adsorption of the furanic resins on the catalytic
surface, increasing the LA yields.
3.1.3. Effect of the Amount of Catalyst Loaded and
Variation in the Concentration of FA in the Feed Stream. LA
yield as a function of FA concentration is shown in Figure 3. In
all cases, the conversion of FA was 100%. It can be appreciated
as an increase in LA yield, with a maximum value of 33.8 vol %
FA in MEK. After this value, a substantial decrease in yield is
observed. Thus, low LA yield at high FA concentrations could
be attributed to the tendency of FA to form furan resin,
according to the above-referenced results. Low concentrations
of FA feed also exhibited low LA yields, which, in this case, is
attributed to the formation of 4-hydroxy-2-cyclopentenone (4-
HCP), which is a byproduct of reaction with FA. The formation
of 4-HCP is favored at low FA/H2O ratios. The high range of
variation in LA yield shown in Figure 3, which is shown to be
up to 40 mol %, indicates that it is an important variable to be
controlled in this process. The number of moles of FA fed per
gram of catalyst (mol FA/gcat) was also a parameter that was
selected for the optimization in a semibatch system using H-
Z(50) as a catalyst. The evolution of LA yields with this
parameter is also shown in Figure 3. The representation of
results indicates that the yield increased as the mol FA/gcat ratio
increased; however, the yield was stable between values of 0.04
and 0.06. Therefore, the optimal FA concentration was defined
as 33 vol % (Figure 3) and the quantity of catalysts was chosen
as the average value between the two maximum points obtained
in Figure 3; this value corresponds to 0.5 g of catalyst.
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Figure 3. Effect of the FA concentration and the amount of catalyst.
3.1.4. Effect of Temperature. Figure 4 shows the effect of
temperature on the LA yield. A slight decrease in the LA yield
Figure 4. Effect of the temperature on LA yield.
was observed when the temperature was increased in the range
between 413 K and 463 K, being more remarkable at 463 K.
However, the differences only reached a variation up to 5
mol % in the LA yield. Although the effect of temperature on
LA yield was insignificant in the range studied, the formation of
some byproducts was affected by such changes. This is the case
for 4-HCP as the byproduct, which was formed mainly at low
temperatures. On the other hand, the increase in temperature
could favor the formation reaction of furan resins, as reported
by some authors.6,8
3.1.5. Effect of Reaction Time. The evolution of the LA
yield was followed alongside the reaction time. Figure 5 shows
the integrated signal intensities corresponding to the three
main compounds identified in the reaction system: FA, LA, and
4-HCP. As it can be seen, the LA concentration continues to
increase even when the reactive FA already is not present. This
Figure 5. Effect of reaction time in the product distribution in the GC
(FID signal). (Operation conditions: 0.5 g of H-ZSM5 catalyst, 413 K,
20 bar of H2, MEK as cosolvent, 36.8 vol % FA.)
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confirms the existence of an intermediate compound in the
reaction mixture, which could not be detected in the gas
chromatographic analysis (Figure 5). A maximum LA yield was
observed 23 h after the feeding pump was stopped. This value
corresponds to a LA yield of 77.7 mol % and 100 mol % FA
conversion (Figure 6). The differences in yield obtained
Figure 6. Effect of the reaction time on the LA yield. (Operation
conditions: 0.5 g of H-ZSM5 catalyst, 413 K, 20 bar of H2, MEK as co-
solvent, 36.8 vol % FA.)
between 1 h and 23 h of reaction reached up to 18 mol %. This
small difference in yield, compared to the long reaction time,
may not be economically feasible; therefore, to avoid high
energy consumption, a lower reaction time must be selected,
considering a slight loss in yield.
3.2.6. Recovery of the Catalysts. After optimization of all of
the catalytic parameters, the used catalyst was recovered and
again calcined for its activation; it was named H-ZR(50). These
regenerated catalysts presented different structural character-
istics and acidity than the fresh one (H-Z(50)). Table 1
summarized the textural properties of the fresh and recycled
catalyst. After the second calcination, the SBET decreased and
the mesopore area also slightly decreased. Regarding the
acidity, the recovered catalyst has lower total acidity. These two
factors reduce the mesopority, and lower acidity decreased the
LA yield by 12 mol % (to 65 mol %) with a total conversion of
FA. Nonetheless, the viability of recovery and recycling of the
H-ZD(50) zeolite is positive, because the yield decreased but
not too much, which is a very important factor, relative to
economic feasibility.
4. CONCLUSIONS
After the screening of catalysts with inorganic structure, the H-
ZSM5 zeolite showed higher levulinic acid (LA) yields,
compared to other materials evaluated as heteropolyacids
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(PTA), zirconium sulfated super acid, and other zeolites. An
adequate porosity and acidity is the key to this higher LA yield.
The reaction system was a semicontinuous reactor, which
allowed the increased LA, minimizing the formation of
undesired furan resins, via the incorporation of methyl ethyl
ketone (MEK) as a solvent of furfural alcohol (FA) in the feed.
Also, the use of a gaseous hydrogen (H2) atmosphere
minimized the formation of furanic resins, improving the LA
yield.
Optimization of previous parameters, along with optimiza-
tion of the other conditions of operation, such as the ratio of
FA fed to the amount of catalyst and the temperature of
reaction, increased the LA yield up to 77 mol % within 23 h of
reaction after 3.5 h of FA feeding.
■ AUTHOR INFORMATION
Corresponding Author
*Tel.: +34 96 6017242. E-mail: jesus.requies@ehu.eus.
Notes
The authors declare no competing financial interest.
■ ACKNOWLEDGMENTS
In memorial of Arkaitz Heras: you will always be alive in our
minds. This work was supported by University of the Basque
Country (UPV/EHU), European Union through the European
Regional, Development Fund (FEDER) (Spanish MICIN
Project No. CTQ2012-38204-C03-03), and the Basque
Government (Researcher Training Programmer of the Depart-
ment of Education, Universities and Research).
■
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