catalysts

Article
Hydroxymethylation of Furfural to HMF with
Aqueous Formaldehyde over Zeolite Beta Catalyst
Shun Nishimura * and Atsuki Shibata
Graduate School of Advanced Science and Technology, Japan Advanced Institute of Science and Technology,
1-1 Asahidai, Nomi, Ishikawa 923-1292, Japan; s1610227@jaist.ac.jp
* Correspondence: s_nishim@jaist.ac.jp; Tel.: +81-761-51-1610




Received: 24 February 2019; Accepted: 28 March 2019; Published: 31 March 2019


Abstract: Hydroxymethylation of 2-furaldehyde (furfural) toward 5-hydroxymethyl-2-furaldehyde

(HMF) was examined in this work among various zeolites with an aqueous formaldehyde as a reagent
in a batch and a flow reactor system. It was found that the zeolite beta gave high activity and good
reusability with calcination treatment before each run for the target reaction in the batch system.
The unique stability of the HMF yield in the liquid-flow system was also observed only in the case
of zeolite beta. The effect of the SiO2 /Al2 O3 ratio in the zeolite beta suggested that hydrophobicity
would be an important factor in faster hydroxymethylation with an aqueous formaldehyde reagent.
The highest turnover frequency (TOF) for HMF production was found to be 2.4 h−1 in the case of
zeolite beta with SiO2 /Al2 O3 = 440 in the batch reactor system. An approximately 30% yield for HMF
was achieved under optimum conditions for zeolite beta catalysts.

Keywords: 2-furaldehyde; 5-hydroxymethyl-2-furaldehyde; formaldehyde; hydroxymethylation;

zeolite beta

1. Introduction
Catalytic biomass transformations towards highly value-added chemicals and materials have
been an attractive research area in recent decades in relation to constructing a green and sustainable
future society [1–6]. Furaldehydes are known as key platform compounds for biomass transformations
in lignocellulosic biomass resources. In particular, 5-hydroxymethyl-2-furaldehyde (HMF) is the most
important furaldehyde: it possesses two functionalities of formyl and hydroxyl groups on a furan
ring at the second and fifth positions and this character enables various successive transformations to
afford 2,5-furandicarboxylic acid [7,8], 2,5-diformylfuran [9,10], 2,5-bis(hydroxymethyl)furan
(BHMF) [11,12], 2,5-dimethylfuran [13–15], 5-hydroxymethylfurfurylamine (HMFA) [16],
1,6-hexanediol [17], levulinic acid [18,19], aldol-adducts [20], and so on [21–23]. On the other hand,
2-furaldehyde (furfural), an abundant furaldehyde which is producible at the plant scale with a large
quantity, has also permitted many conversions towards furoic acid [24,25], furfuryl alcohol [26,27],
2-methylfuran [28,29], furfuriyamine [30,31], 1,5-pentandiol [32,33], succinic acid [34], condensation
products [35–37], cyclopentenones [38–40] and so on [41], as well as HMF reaction protocols. However,
the number of possible derivatives of furfural and those impacts has been much less than those of
HMF [1,6]. Apparently, the structural character of furfural, a formyl group linked on a furan ring at
the second position, decreases its potential as a starting material in comparison with HMF.
To resolve this weakness of furfural, we have recently examined the direct hydroxymethylation of
furfural and its derivatives (C5) with an aqueous formaldehyde reagent to produce the corresponding
HMF-like derivatives (C6), a furan ring composed of two functional groups, by using a sulfuric
functionalized resin catalyst in a batch and a liquid-flow reactor system [42]. The study carried
out a survey of reactivity for the hydroxymethylation reaction among four types of Amberlyst

Catalysts 2019, 9, 314; doi:10.3390/catal9040314 www.mdpi.com/journal/catalysts

Catalysts 2019, 9, 314 2 of 12
Ca ta lysts 2019, 9, x FOR PEER REVIEW 2 of 12

resins
resins constructed
constructed with differentacidity
with a different acidityand/or
and/or surface
surface nature.
nature. TheThe Amberlyst-15
Amberlyst -15 waswas found found
to be
to be the best resin catalyst with a 43.1% yield and 57.5% selectivity for HMF
the best resin catalyst with a 43.1% yield and 57.5% selectivity for HMF production in a batch reaction production in a batch
reaction
system. system.
It possessedIt possessed
significantsignificant
reusability reusability and applicability
and applicability in the generation
in the generation of furfural
of furfural derivatives
derivatives
such as BHMF, such as BHMF,and
HMFA, HMFA, and 5-hydroxymethyl-2-furancarboxylic
5-hydroxymethyl-2-furancarboxylic acid (HMFCA).
acid (HMFCA). However, However,
there
there seems to be a great challenge in fabricating a resin-catalyzed system
seems to be a great challenge in fabricating a resin-catalyzed system for the hydroxymethylation of for the hydroxymethylation
of furfural
furfural cost-effectively.
cost-effectively.
According
Accordingto toprevious
previousworks,
works,Moreau
Moreauand andco-workers
co-workers have
havecontributed
contributed important
important discussion
discussion on
the direct
on the hydroxymethylation
direct hydroxymethylation of furaldehydes
of furaldehydes withwith37%37%aqueous
aqueous formaldehyde
formaldehyde in the presence
in the presence of
dealuminated
of dealuminated mordenite
mordenite as aas
catalyst [43–46].
a catalyst It is noteworthy
[43–46]. It is noteworthythat they
thatrevealed the importance
they revealed the importanceof the
hydrophobicity
of the hydrophobicityof highly of dealuminated
highly dealuminated mordenite to the activity
mordenite to the of hydroxymethylation
activity of hydroxymethylationof furfuryl of
alcohol
furfuryltowards
alcohol BHMF
towards byBHMF
aqueous by formaldehyde
aqueous formaldehyde [46]. Because[4 6]. aBecause
lot of effort
a lot has beenhas
of effort putbeen
into the
put
synthesis of zeoliteof
into the synthesis catalysts at the plant
zeolite catalysts at scale, it is scale,
the plant likelyitthat the development
is likely of zeolite-catalyzed
that the development of zeolite-
hydroxymethylation of C5 to C6 furaldehydes has a fair chance of adding
catalyzed hydroxymethylation of C5 to C6 furaldehydes has a fair chance of adding to sustainable to sustainable technology in
an economical
technology manner.
in an economical manner.
In
In this work, westudied
this work, we studiedthethehydroxymethylation
hydroxymethylation of of
furfural
furfuralto HMF
to HMF in aqueous
in aqueous formaldehyde
formaldehyde as
aasdual solvent
a dual solventandandreagent (Scheme
reagent (Scheme 1) with four
1) with different
four differenttypes
typesof zeolite catalysts.
of zeolite catalysts.TheThe
importance
importance of
the hydrophobic
of the hydrophobic nature of the
nature highly
of the active
highly zeolite
active beta
zeolite catalyst
beta catalystcomposed
composed of different
of differentSiOSiO2 /Al 2O
2/Al 2O33
ratios was also investigated. This study is expected to be interesting and gives
ratios was also investigated. This study is expected to be interesting and gives new insight into how new insight into how to
further
to furtherthethedesign of cheaper
design of cheaperand/or
and/ormore
moreadvanced
advanced systems
systems forfor
thetheupgrading
upgrading of furaldehydes.
of furaldehydes.

Scheme 1. Hydroxymethylation of furfural to 5-hydroxymethyl-2-furaldehyde (HMF) with a

Scheme 1. Hydroxyme thylation of furfural to 5-hydroxyme thyl-2-furalde hyde (HMF) with a
formaldehyde reagent.
formalde hyde re agent.
2. Results and Discussions
2. Results and Discussions
2.1. Catalyst Structure and Physicochemical Properties
2.1. Catalyst Structure and Physicochemical Properties
During our initial survey of the effects of zeolite reactivity on HMF production through the
During our initial
hydroxymethylation survey offour
of furfural, the conventional
effects of zeolite reactivity
types of zeolites on were
HMF investigated.
production through The Japanthe
hydroxymethylation
Reference Catalyst (JRC) of Committee
furfural, four conventional
of the Catalysis Society types of ofzeolites were investigated.
Japan (Tokyo, Japan) kindlyThe Japan
supplied
Reference
four types Catalyst
of zeolites, (JRC)and Committee
these wereofcalcinedthe Catalysis at 823Society
K for 5ofhJapan
before(Tokyo,
use. The Japan)
resultskindly supplied
of the X-ray
four types (XRD)
diffraction of zeolites, and of
analysis these weresupplied
the JRC calcinedzeolites at 823 K forshown
are 5 h before use. The
in Figure 1a. In results of the X-ray
comparison with
diffraction
the (XRD) centre
international analysis forofdiffraction
the JRC supplied data (ICDD) zeolites are shown
database in Figure
obtained 1a. Inacomparison
through PDXL software with
the international
(Rigaku Corp., Tokyo,centre for diffraction
Japan; ver.1.8.0.3)data search (ICDD) database
and fitting obtained
function, through a PDXL
JRC-Z-HB150(1) (SiO2software
/Al2 O3
=(Rigaku Corp., Tokyo, (SiO
150), JRC-Z5-90H(1) Japan; ver.1.8.0.3)
2 /Al 2 O3 = 90),search and fitting(SiO
JRC-Z-HM20(5) function,
2 /Al2 O JRC-Z-HB150(1) (SiO2/Al2O3 =
3 = 18.3), and JRC-Z-HY5.5
150),2 /Al
(SiO JRC-Z5-90H(1)
O
2 3 = 5.6) (SiO
fitted /Al
well
2 2 Oin
3 = 90),
accordance JRC-Z-HM20(5)
with the (SiO
typical 2 /Al O
patterns
2 3 = 18.3),
of zeoliteand JRC-Z-HY5.5
beta (card no.
(SiO2/Al2O3 = 5.6)
00-056-0467), ZSM-5fitted(card
well no.in accordance
00-045-0120), with mordenite
the typical pat (card terns
no.of 00-043-0171),
zeolite beta (card andno. 00-056-
zeolite Y
0467),no.
(card ZSM-5 (card no. 00-045-0120),
00-040-0336), respectively. mordenite
JRC-SAH-1 (card no.(SiO00-043-0171),
2 /Al2 O3 = 2.1) anddisplayed
zeolite Y (card no. 00-040-
a broad peak
0336),
at aroundrespectively.
25 degrees JRC-SAH-1 (SiO2/Al2O3that
(at 2θ), indicating = 2.1) it displayed
was amorphous a broadSiO peak 2 -Alat O
2 3around
. The 25 degrees
zeolite (at
beta
2θ), indicating that it was amorphous SiO -Al O . The zeolite
samples composed of different SiO2 /Al2 O3 ratios were supplied by the JRC and Tosoh Corporation
2 2 3 beta samples composed of different
SiO2/Al2Japan):
(Tokyo, O3 ratios were supplied
JRC-Z-HB25(1) (SiOby2 /Al
the2JRCO3 =and 25),Tosoh Corporation
HSZ-941HOA (SiO2(Tokyo,
/Al2 O3 Japan):
= 42.2), JRC-Z-HB25(1)
HSZ-960HOA
(SiO22/Al
(SiO /Al2OO3
2 3 = 25),
= HSZ-941HOA
104), HSZ-980HOA (SiO /Al
(SiO
2 22O/Al
3 = 42.2),
O
2 3 = HSZ-960HOA
440), and (SiO
HSZ-990HOA 2 /Al 2 O 3 =
(SiO 104),
2 /AlHSZ-980HOA
2 O3 = 1700).
(SiO2/Al
These 2Opossessed
also 3 = 440), and HSZ-990HOA
clear beta structural (SiOforms
2/Al 2Oin 3 =all1700). These
cases, also possessed
as determined by XRD clear beta structural
(Figure 1b).
forms in all cases, as determined by XRD (Figure 1b).
Pore size distribution and specific surface area were determined by Ar (>99.999 pur ity)
adsorption isotherms at 87 K using BELSORP-max (BEL JAPAN, INC., Osaka, Japan). The samples
(100 mg) were pretreated at 623 K for 6 h under vacuum before measurement. A micropore size
distribution was estimated with the Saito-Foley (SF) method [47] using BELMaster7 software
(MicrotracBEL Corp., Osaka, Japan; ver.7.0.18.8). The adsorption sectional area of Ar at 87 K was
Catalysts 2019, 9,
Catalysts x FOR
2019, PEER REVIEW
9, 314 3 of 123 of 12

a b 1.0 kcps SiO2/Al2O3

1.0 kcps 1700
Beta

440

ZSM-5
Intensity (a.u.)

Intensity (a.u.)
150

Mordenite 104

42.2
Y

SiO2-Al2O3 25

10 20 30 40 50 60 70 80 90 10 20 30 40 50 60 70 80 9
2 theta (degree) 2 theta (degree)

Figure 1. X-ray diffraction (XRD) patterns of (a) four types of reference zeolites and normal SiO2 -Al2 O3
Figureand
1. X-ray diffraction
(b) zeolite (XRD) patterns
beta samples of (a)
composed four
with types of
various reference
SiO zeolites and normal SiO2-Al2O3
2 /Al2 O3 ratios.
and (b) zeolite beta samples composed with various SiO2/Al2O3 ratios.
Pore size distribution and specific surface area were determined by Ar (>99.999 purity) adsorption
isotherms at 87 K using BELSORP-max (BEL JAPAN, INC., Osaka, Japan). The samples (100 mg) were
SiO2/Al2O3
0.1 μmol
pretreated at 623 K for 6 h under vacuum before measurement. A micropore size distribution was
1700
0.2 μmol
estimated with the Saito-Foley (SF) method [47] using BELMaster7 software (MicrotracBEL Corp.,
Osaka, Japan; ver.7.0.18.8). The adsorptionBeta sectional area of Ar at 87 K was 0.1420 nm2 . These results
440
are listed in Table 1 (see also Figures S1 and S2 in the Supplementary Materials).

Table 1. Physicochemical properties of catalysts used.

ZSM-5 150
NH3 desorption (μmol g )
-1

-1
NH3 desorption / μmol g

SBET b Average Pore Size b Acid Amount c

Entry Catalyst a
(m2 g−1 ) (nm) (mmol g−1 )
104
1 Beta (25) 494
Mordenite
0.69 0.37
2 Beta (42.2) 639 0.68 0.42
3 Beta (104) 613 0.71 0.24
4 Beta (150) 607 0.73 0.20 42.2
5 Beta (440) 571 0.71 0.076
Y
6 Beta (1700) 565 0.69 0.038
7 ZSM-5 (90) 421 0.60 0.28
a Mordenite b
8 479 0.57 >0.65 25
(18.3) SiO2-Al2O3
9 Y (5.6) 651 0.72 0.38
SiO700 2 -Al2 O3800
400 500 10 600 const.
900
305 400 500N/A 600 700 800
0.42 const.
900
Temperature(2.1)
/K Temperature (K)
a Calcined at 823 K for 5 h; the numbers in parentheses are the SiO /Al O ratios. b Determined by Ar adsorption.
2 2 3
FigureS 2. :NH 3-temperature programed desorption (NH3-TPD) of (a) four types c of reference zeolites
BET a specific surface area determined by the Brunauer-Emmett-Teller theory. Estimated by NH3 -temperature
and normal SiO2-Al
programmed 2O3 and (NH
desorption (b) zeolite
3 -TPD) betas composed
analysis. with various SiO 2/Al 2 O 3 ratios.

To ascertain the acidity

To ascertain of these
the acidity samples,
of these NH3-TPD
samples, was performed
NH3 -TPD was performed usingusing
BelcatBelcat
II (MicrotracBEL
II (MicrotracBEL
Corp., Osaka, Japan). The sample (100 mg) was pretreated at 823 K for 1 h under
Corp., Osaka, Japan). The sample (100 mg) was pretreated at 823 K for 1 h under an He flow an He flow beforebefore
undergoing NH adsorption at 373 K. Thereafter, the vapor treatments were
undergoing NH3 adsorption at 373 K. Thereafter, the vapor treatments were performed three
3 performed three times
times at
at 373
373KKunder
under an He flow.
an He flow.TheThe NHNH 3 desorption was monitored using mass (m/e = 16) for the
3 desorption was monitored using mass (m/e = 16) for the temperature
temperature range 373–873 K at a ramping
range 373–873 K at a ramping rate at 10 K rate
minat-110 K 873
and minK-1 and 873 K for 20 min (const.). The
for 20 min (const.). The obtained profiles
obtained profiles are
are described indescribed
Figure 2. in Figurebeta
Zeolite 2. Zeolite beta2 O
(SiO2 /Al (SiO
3 =2/Al
150)2O 3 = 150)
had had apeak
a single single
atpeak
aroundat around
630 K (acid
630 Kamount:
(acid amount:
0.20 mmol0.20 gmmol g−1) whereas
−1 ) whereas ZSM-5ZSM-5
showed showed
a peaka atpeak at around
around 680 K 680
(acidKamount:
(acid amount:
0.28 mmol
0.28 mmol
− 1 g −1); in other words, the latter possessed a greater abundance and stronger acid sites.
g ); in other words, the latter possessed a greater abundance and stronger acid sites. Mordenite
Mordenite exhibited humped peaks at 519 K and 800 K (acid amount: >0.65 mmol g−1 in total). Note
Catalysts 2019, 9, x FOR PEER REVIEW 3 of 12

a b 1.0 kcps SiO2/Al2O3

1.0 kcps 1700
Catalysts 2019, 9, 314 Beta 4 of 12

440
exhibited humped peaks at 519 K and 800 K (acid amount: >0.65 mmol g−1 in total). Note that a
ZSM-5

Intensity (a.u.)
further higher temperature in NH3 -TPD seemed to be required to ascertain the full acidic nature in

Intensity (a.u.)
150
mordenite. However, application of such experimental conditions was limited because the calcination
temperature was 823 K in this study. Zeolite Y and normal SiO2 -Al2 O3 gave a single peak at 582
K (acid amount: 0.38 mmol g−1 ) and a broad peak Mordenite
with the top of the peak at 557 K (acid amount: 104

− 1
0.42 mmol g ), respectively. The NH3 -TPD profiles for various zeolite beta samples with different
SiO2 /Al2 O3 ratios are also shown in Figure 2b. The fundamental understanding is that a decrease 42.2 in
the SiO2 /Al2 O3 ratio would lead to an increase in the Y acid amounts of the zeolite [48,49]. However,

the peak area for SiO2 /Al2 O3 = 25 (corresponding acid amount: 0.37 mmol g−1 ) was a little smaller
SiO2-Al2O3 25
than that for SiO2 /Al2 O3 = 42.2 (ibid.: 0.42 mmol g−1 ). From the viewpoint of the XRD patterns
10 20
(Figure 1b) and pore size30distribution
40 50 60
(Figure70
S2), 80
it was90found10that20the crystallinity
30 40 50
and 60 70
pore 80
volume 9
2 theta (degree) 2 theta (degree)
of zeolite beta for SiO2 /Al2 O3 = 25 seemed to be slightly poorer than those of the other zeolite beta
samples. Accordingly, we suppose that the BEA crystal imperfection in the case of SiO2 /Al2 O3 = 25
Figure 1. X-ray diffraction (XRD) patterns of (a) four types of reference zeolites and normal SiO2-Al2O3
can lead to such disordering in the peak area in NH3 -TPD, i.e., the acid amount, between SiO2 /Al2 O3
and (b) zeolite beta samples composed with various SiO2/Al2O3 ratios.
= 25 and 42.2. Estimated acid amounts for all samples are listed in Table 1.

SiO2/Al2O3
0.1 μmol
1700
0.2 μmol

Beta
440

ZSM-5 150
NH3 desorption (μmol g )
-1

-1
NH3 desorption / μmol g

104
Mordenite

42.2

a b
25
SiO2-Al2O3

400 500 600 700 800 const.

900 400 500 600 700 800 const.
900
Temperature /K Temperature (K)

2. NH
Figure 2. NH33-temperature programed desorption (NH33-TPD)
-TPD) of
of (a) four types of reference zeolites
zeolites
and normal SiO22-Al22O
O33and
and(b)
(b)zeolite
zeolitebetas
betascomposed
composedwith
withvarious
variousSiO
SiO22/Al
/Al2O O
3
2 3 ratios.
ratios.

2.2. Reactivity
To ascertainamong the Different
acidity ofZeolite
these Structures
samples, NH3-TPD was performed using Belcat II (MicrotracBEL
Corp., Osaka,
Figure Japan).the
3 shows Thetime-based
sample (100 mg) was
reaction pretreated
progress at 823
of the K for 1 h under anofHe
hydroxymethylation flow before
furfural with
undergoing NH adsorption at 373 K. Thereafter, the vapor treatments
aqueous formaldehyde towards HMF production with zeolite beta, ZSM-5, mordenite, zeolite Y,
3 were performed three times
at 373
and K under
normal SiO2 -Al an 2He
O3 . flow.
ZeoliteThe
Y andNHnormal
3 desorption was
SiO2 -Al monitored using mass (m/e = 16) for the
2 O3 were inactive for HMF production. Linear
temperature
increases in HMFrangeyield373–873
wereKobserved
at a ramping rate at
for ZSM-5 10 mordenite.
and K min-1 andNotably,
873 K for 20zeolite
only min (const.).
beta hadThea
obtained profiles are described in Figure 2. Zeolite beta (SiO /Al O = 150) had a
significant impact on HMF production with a high conversion value (see Figure S3). The best catalyst
2 2 3 single peak at around
630 K (acid
studied amount:
for the reaction 0.20 mmol gwith
of furfural −1) whereas ZSM-5 showed a peak at around 680 K (acid amount:
a formaldehyde aqueous solution was zeolite beta (SiO2 /Al2 O3
0.28 mmol g −1 ); in other words,
= 150), which afforded the highest HMF yieldthe latter possessed
of 29% awith
greater
82%abundance
conversion and stronger
of furfural at acid
6 h insites.
the
Mordenite exhibited
batch reactor system. humped peaks at 519 K and 800 K (acid amount: >0.65 mmol g −1 in total). Note
Ca ta lysts 2019, 9, x FOR PEER REVIEW 5 of 12
Catalysts 2019, 9, 314 5 of 12
Ca ta lysts 2019, 9, x FOR PEER REVIEW 5 of 12

50
50 Beta
Beta
ZSM-5
40 ZSM-5
Mordenite
40 Y Mordenite

HMF yield (%)

Y2-Al2O3
SiO

HMF yield (%)

30 SiO2-Al2O3
30

20
20

10
10

0
0
0 2 4 6 8 10 12
0 2 4
Reaction 6 (h) 8
time 10 12
Reaction time (h)
Time-based
Figure3.3.Time
Figure -base d reaction
re actionprogression
progre ssion of the hydroxymethylation
of the hydroxyme thylationof furfural towards
of furfural HMF among
to wards HMF
Figure
four 3. Time
zeolites and -base
normal d re
SiO
among four ze olite s and normal action
2 -Al Oprogre
2SiO in a ssion
batch of the
reactor. hydroxyme
Reaction thylation
conditions: of furfural
furfural (1 to
mmol),wards HMF
formalin
3 2 -Al2 O 3 in a batch re actor. Re action conditions: furfural(1mmol),
(5among
mL), four ze
catalyst olite
(200 s and
mg), normal
temperature SiO -Al
(363
2 2 O
K),
3 in a batch
stirring re
(500 actor.
rpm).
formalin (5 mL), catalyst (200 mg), te mpe rature (363 K), stirring (500 rpm). Re action conditions: furfural (1 mmol),
formalin (5 mL), catalyst (200 mg), te mpe rature (363 K), stirring (500 rpm).
Becausethese
Because thesefourfourtypes
typesofofzeolite
zeolitewere werecomposed
composedofofdifferent
differentSiO SiO 2 /Al
2/Al
O3 ratios
2O32 ratios
in this
in this study,
study, a
a simple discussion
Because these of
four structural
types of impacts
zeolite on
were the hydroxymethylation
simple discussion of structural impacts on the hydroxymet hylation of furfural towards HMF in a
composed of different SiO of furfural
2/Al 2O3 ratiostowards
in thisHMF
study,in
aqueous
aqueous formaldehyde
simple formaldehyde
discussion wasdifficult
of structural
was difficult toachieve.
impacts
to achieve. However,
on theHowever,
hydroxymet interesting phenomena
hylationphenomena
interesting of furfural for forzeolite
zeolite
towards betain
HMF
beta
were also
aqueous
were observed
formaldehyde
also observed in the
in thewas flow reactor
flowdifficult
reactor to system.
achieve.
system. Figure 4
However,
Figure shows
4 shows the results
interesting
the results for
phenomena the application
for zeoliteof
for the application of aa
beta
continuous
were alsoflow
continuous flowreactor
observed reactor system
insystem
the flow over
overreactor
thethe four
system.
four types
types of zeolite
Figure 4 shows
of zeolite catalysts
catalysts thefor for
thethe
results hydroxymethylation
for the application of
hydroxymethylation of a
of furfural towards HMF. As shown in Figure 4a, gradual decreases
furfural towards HMF. As shown in Figure 4a, gradual decreases in furfural conversion value wereof
continuous flow reactor system over the four types of zeolite catalysts in
for furfural
the conversion
hydroxymethylation value
were
detected detected
furfural for all for
towards all
HMF.
zeolite zeolite samples
As shown
samples during in during
Figure the gradual
4a,
the progress progress of thereaction.
of thedecreases
flow flow reaction.
in furfural From
From conversion
the the viewpoint
viewpointvalue were
of the
of the
detectedcatalytic
for all behavior
zeolite affording
samples HMF
during (yield)
the shown
progress of in
the
catalytic behavior affording HMF (yield) shown in Figure 4b, however, zeolite beta showed Figure
flow 4b, however,
reaction. From zeolite
the beta
viewpointshowed
of the
significantly
catalytic different
behavior behavior.
affording In
HMF the case
(yield) of zeolite
shown beta
in only,
Figure a gradual
4b,
significantly different behavior. In the case of zeolite beta only, a gradual increase and constant yield increase
however, and
zeolite constant
beta yield
showed
were
were monitored
significantly
monitored withinbehavior.
different
within 3.5 hhin
3.5 inthe
the flow
In flow
the reaction,
case though
of zeolite
reaction, beta the
though theother
only, other threeincrease
a gradual
three zeolitesgave
zeolites gaveconstant
and aninactive
an inactive
yield
and/or
were decreasing
monitored yield
within for
3.5 HMF.
h in theSuchflow unique
reaction,behavior
though of
and/or decreasing yield for HMF. Such unique behavior of zeolite beta also appeared for various zeolite
the other beta
threealso appeared
zeolites gave for
an various
inactive
SiO
SiO 2 /Al
and/or
2/Al
O3 cases
decreasing
2O23 cases
(vide
(vide yieldinfra).
infra). Note
forNote
HMF. thatthat
Suchthethe initial
unique
initial inductionperiod
behavior
induction ofperiod
zeolitedetected
beta also
detected inina aflow
flowreactor
appeared reactor system
forsystem
various
owes
SiO itself
2/Al 2O3to the
cases pelletizing
(vide infra). treatment
Note that of the
the powder
initial sample.
induction Accordingly,
period
owes itself to the pelletizing treatment of the powder sample. Accordingly, the textural specialty detected the
in atextural
flow specialty
reactor of
system
of
zeolite beta is an attractive subject of attention, even though the different
zeolite beta is an attractive subject of attention, even though the different SiO22/Al22O33ratios were used of
owes itself to the pelletizing treatment of the powder sample. Accordingly,SiO /Althe O ratios
textural were used
specialty
for
for discussion
zeolite beta isof
discussion of
an reactivity
attractive
reactivity among
subject
among four typesof
of attention,
four types ofzeolite
zeolite samples.
even though
samples. the different SiO2/Al2O3 ratios were used
for discussion of reactivity among four types of zeolite samples.
35
100 Beta ZSM-5 Beta ZSM-5 Mordenite Y
30 35
Furfural conversion (%)

100 Mordenite
Beta YZSM-5 Beta ZSM-5 Mordenite Y
80
25 30
Furfural conversion (%)

Mordenite Y
HMF yield (%)

80 a b
HMF yield (%)

60 a 20 25 b
60 15 20
40
40 10 15
20
5 10
20
0 0 5
00 1 2 3 4 00 1 2 3 4
0 1Flow reaction2time (h) 3 4 0 1Flow reaction2time (h) 3 4
Flow reaction time (h) Flow reaction time (h)
Figure 4. Time-based reaction for HMF production in a flow reactor using four different types of
Figure 4. Time
zeolites. -baseconditions:
Reaction d re action furfural
for HMF(10 production in a flow(50
mmol), formalin re actor using four
mL), catalyst (500diffe
mg), retemperature
nt type s of
Figure 4. Time -base d re action
1 ).for HMF production in a flow re actor using four diffe
te re nt type s of
ze olite
(363 s. flow
K), Re action
rate (0.2 mL min−
conditions: furfural (10 mmol), formalin (50 mL), catalyst (500 mg), mpe rature
ze olite
(363 s. Rerate
K), flow action
(0.2conditions:
mL min−1 ). furfural (10 mmol), formalin (50 mL), catalyst (500 mg), te mpe rature
It(363
wasK), flowthat
noted ratezeolite
(0.2 mLbeta,
min−1mordenite,
). and zeolite Y had large-pore structures of ~5.6 Å × 7.6 Å,
~6.5 ItÅwas noted
× 7.0 Å, andthat zeolite
~7.4 Å × beta,
7.4 Å,mordenite, and
respectively, zeolite Y
whereas had large-pore
ZSM-5 possessed structures of ~5.6
a medium-pore Å × 7.6
structure
It was noted that zeolite beta, mordenite, and zeolite Y had large-pore structures of ~5.6
Å , ~6.5 Å × 7.0 Å , and ~7.4 Å × 7.4 Å , respectively, whereas ZSM-5 possessed a medium-pore structure Å × 7.6
Å , ~6.5 Å × 7.0 Å , and ~7.4 Å × 7.4 Å , respectively, whereas ZSM-5 possessed a medium-pore structure
Catalysts 2019, 9, 314 6 of 12
Ca ta lysts 2019, 9, x FOR PEER REVIEW 6 of 12

of
of~5.1
~5.1ÅÅ××5.65.6Å Å[50,51].
[50,51].OnOnthe
thebasis
basisofofthe
thepresent
presentAr Aradsorption
adsorptionanalytical
analytical approach,
approach, mordenite
exhibited
exhibited aa middle
middlepore pore diameter
diameter of Å
of 5.7 5.7(Figure
Å (Figure
S1b), S1b),
whichwhich was a value
was a smaller smallerthanvalue than that
that mentioned
mentioned
above. Because mordenite is constructed with two types of ring, these being an 8-memberedanring
above. Because mordenite is constructed with two types of ring, these being 8-
membered
(~3.4 Å × 4.8ring
Å) (~3.4
and aÅ12-membered
× 4.8 Å ) andring
a 12-membered
(~6.5 Å × 7.0 Å),ring (~6.5
such Å × 7.0 Åwere
differences ), such differences
expected. ZSM-5were
is a
expected.
10-memberedZSM-5ringiszeolite,
a 10-membered ring zeolite,
whereas zeolite whereas
beta and zeolitezeolite beta and zeolite
Y are 12-membered ringYzeolites.
are 12-membered
According
ring zeolites.
to these According
properties, to these
the size properties,
sensitivity and/or thetopology
size sensitivity
derivedand/or topology
from each zeolitederived from have
type would each
zeolite
scarcelytype would have
contributed scarcely
to the contributed
differences to the
in reactivity fordifferences in reactivity
the target reaction. for theittarget
However, reaction.
was interesting
However,
to observeitthat
wastheinteresting
conversionto observe
values ofthat the conversion
furfural dramatically values of furfural
changed acrossdramatically
the differentchanged
zeolites
across the different
(vide supra). There haszeolites
been (vide
some supra).
discussionThere hasimportance
on the been some of discussion onthe
acidity, i.e. theBrønsted/Lewis
importance of
acidity,
amount,i.e.
tothe
try Brønsted/Lewis amount,
to explain the different to try to explain
reactivities obtained thefor
different
variousreactivities obtained
types of zeolites forpresence
in the various
types of zeolites
of water [52,53]. in the presence of water [52,53].

2.3. Reusability
2.3. Reusability of
of Zeolite
Zeolite Beta
Beta
Thereusability
The reusability of zeolite beta (SiO2/Al /Al2O
2O 3=
3 = 150)was
150) wasinvestigated
investigatedinina abatch
batchreactor.
reactor. After
After the
the
present reaction,
present reaction, the reaction media was centrifuged, and then the the spent
spent powder
powder catalyst
catalyst was
was washed
with 0.5 L water and dried at 383 K overnight. Thereafter, the next recycling
with 0.5 L water and dried at 383 K overnight. Thereafter, the next recycling run was performed run was performed
after
after re-calcination
re-calcination treatment
treatment at 823
at 823 K forK for
5 h.5 Because
h. Because weight
weight losloss
s ofof catalystpowder
catalyst powdercould
couldnot
not be
be
prohibited during the catalyst correction and reactivation
prohibited reactivation procedures,
procedures, different scales were applied
for the
for the recycling
recycling tests
tests (see
(see Table
Table S1).
S1). AsAsshown
shownin in Figure
Figure5,5,high
highreusability
reusability for
for the
the above
above three
three
recycling runs
recycling runs was
was achieved
achieved with
with zeolite beta.
beta. ItItshould
shouldbe benoted
notedthatthatre-calcination
re-calcination treatment
treatment was
was
necessary because
necessary because aa significant
significant color
color change
change from
from white
white toto dark
dark gray
gray after
after reaction
reaction occurred
occurred,, i.e.,
i.e.,
strong
strong carbon depositions onto the catalyst surface were expected
catalyst surface were expected during the reaction (see
the reaction (see Figures S4
and S5). In the
and thehigh
highperformance
performanceliquid
liquidchromatography
chromatography (HPLC)
(HPLC) chart, somesome
chart, unidentified peakspeaks
unidentified were
detected (Figure S6). However, the gas chromatography-time of flight
were detected (Figure S6). However, the gas chromatography-time of flight mass (GC-TOFMS)mass (GC-TOFMS) spectrometry
(JEOL Ltd., Tokyo,
spectrometry (JEOLJapan; AccuTOFGCx)
Ltd., Tokyo, of the reaction
Japan; AccuTOFGCx) mixture
of the could
reaction not identify
mixture anyidentify
could not appropriate
any
side reactions,
appropriate such
side as the self-resinification
reactions, of furfural [45,54]
such as the self-resinification and the
of furfural dimerization
[45,54] of as-produced
and the dimerization of
HMF [55,56], for the present situation; some of these products might be trapped
as-produced HMF [55,56], for the present situation; some of these products might be trapped on/in on/in the zeolite,
leading
the to color
zeolite, leadingchanges during
to color the reaction.
changes during the reaction.

100
Conversion Yield Selectivity
80

60
(%)

40

20

0
Fresh Reuse 1 Reuse 2 Reuse 3
Figure 5. Recycling tests on the hydroxymethylation of furfural towards HMF over zeolite beta in a
Figure 5. Re cycling te sts on the hydroxyme thylation of furfural towards HMF ove r ze olite be ta in a
batch reactor. Reaction conditions: furfural (1–3 mmol), formalin (5–15 mL), catalyst (600–200 mg),
batch re actor. Re action conditions: furfural (1–3 mmol), formalin (5–15 mL), catalyst (600–200 mg),
temperature (363 K), time (6 h), stirring (500 rpm). The catalyst was re-calcined at 823 K before
te mpe rature (363 K), time (6 h), stirring (500 rpm). The catalyst was re -calcine d at 823 K be fore e ach
each reuse.
re use .
2.4. Effect of SiO2 /Al2 O3 Ratio on Zeolite Beta
2.4. Effect of SiO2/Al 2O3 Ratio on Zeolite Beta
The effect of the SiO2 /Al2 O3 ratio on the target reaction was evaluated using fine zeolite beta
The fabricated
samples effect of the SiOdifferent
with 2/Al2O3 ratio on the
SiO2 /Al 2 O3 target
ratios. reaction was evaluated
Figure 6 shows using reaction
the time-based fine zeolite beta
progress
samples fabricated with different SiO /Al O ratios. Figure 6 shows the time-based
of the hydroxymethylation of furfural towards HMF among zeolite beta samples composed of different
2 2 3 reaction progress
of
SiOthe hydroxymethylation
2 /Al of furfural
2 O3 ratios in a batch reactor. towards HMF
Corresponding amongof zeolite
alterations betaand
conversion sam plesare
yield composed of
also shown
different SiO /Al O ratios in a batch reactor. Corresponding alterations of conversion and
in Figure S7. Interestingly, SiO2 /Al2 O3 strongly influenced the reaction progress for the target reaction
2 2 3 yield are
also shown in Figure S7. Interestingly, SiO 2/Al2O3 strongly influenced the reaction progress for the
target reaction (Figure 6a). An increase in the SiO2/Al2O3 ratio from 25 to 42.2 led to a great increase
Catalysts 2019, 9, 314 7 of 12

Ca ta lysts 2019, 9, x FOR PEER REVIEW 7 of 12

(Figure 6a). An increase in the SiO2 /Al2 O3 ratio from 25 to 42.2 led to a great increase in HMF yield,
in HMFsimilar
while progress
yield, while of the
similar reactionofwas
progress obtainedwas
the reaction for the range for
obtained 42.4–150. Thereafter,
the range 42.4–150.itThereafter,
seemed to
gradually
it diminish
seemed to in the
gradually cases from
diminish in the440 to 1700.
cases Theto
from 440 highest yield
1700. The of 31.6%
highest with
yield of 3a1.6%
67.9% conversion
with a 67.9%
rate was detected
conversion at detected
rate was 12 h during theh reaction
at 12 forreaction
during the SiO2 /Alfor
O
2 3 =
SiO 104.
2 /Al 2 O3 = 104.

70 3.0
25
42.4
a b c
60 104 2.5
150
HMF concentration (mM)

50 440
1700 2.0
40

TOF (h )
-1
1.5
30
1.0
20

10 0.5

0 0.0
0 2 4 6 8 10 12 0 500 1000 1500
Reaction time (h) SiO2 / Al2O3 ratio (mol/mol)

Figure 6. Time-based reaction progression of the hydroxymethylation of furfural to HMF among

Figure
zeolite 6. Time
beta -base composed
samples d re actionof progre ssion
different SiOof2 /Al
the Ohydroxyme thylation of furfural to HMF among
2 3 ratios in a batch reactor: (a) HMF concentration
ze olite be ta sample s compose d of diffe re nt SiO 2 /Al2 O 3 ratios in a batch re actor: (a)HMF concentration
and (b) initial rate for HMF production per acid amount. (c) Plot of turnover frequency (TOF) values
and
as a (b) initial rate
function for /Al
of SiO HMFOproduction pe r acid amount. (c) Plot of turnove r fre que ncy (TOF) value s
2 2 3 ratio on the basis of the dashed lines in (b) which represent the linear
as a function of results.
approximation SiO 2 /Al2Reaction
O 3 ratio on the basis furfural
conditions: of the dashe d line sformalin
(1 mmol), in (b) which re pre
(5 mL), se nt the
catalyst line
(200 ar
mg),
approximation re sults. Re action
temperature (363 K), stirring (500 rpm).conditions: furfural (1 mmol), formalin (5 mL), catalyst (200 mg),
te mpe rature (363 K), stirring (500 rpm).
To further discuss the details of the differences in reactivity derived from the SiO2 /Al2 O3 ratios,
To further
the initial ratesdiscuss the details
of the reaction of acid
per the differences
amount and in reactivity
the TOF values derivedwere fromplotted
the SiOin2/Al 2O3 ratios,
Figure 6b,c,
the initial rates
respectively. of the
It can bereaction per acid amount
clearly observed that the and
SiO2the
/AlTOF 2 O3 values
ratio waswere plotted
greatly in Figurewith
associated 6b and
the
Figure 6c, respectively.
reactivity of the target Itreaction.
can be clearly observedhad
The reactivity thatbeen
the SiO 2/Al 2O3 ratio
heightened by was greatlythe
increasing associated
SiO2 /Alwith
2 O3
the reactivity
ratio from 25 to of440.
the target reaction.
The highest TOFThe reactivity
value leachedhad been
at 2.4 − 1
h heightened
, which wasbyfour increasing the SiO
times higher 2/Al
than 2O3
that
ratio fromusing
obtained 25 toSiO
440.2 /Al
The2 O highest
3 = 25.TOF value leached
In addition, at 2.4 h −1large
a significantly , whichSiOwas2 /Alfour
2 O3 times
value higher than that
(1700) produced
obtained using SiOin
a drastic decrease 2/Al
the2OTOF
3 = 25. In addition,
value, giving aavalue of 0.5 h−large
significantly 1. SiO2/Al2O3 value (1700) produced a
drastic
In decrease
previousin the TOF
studies value, giving
on zeolite a value
catalysis, manyofresearchers
0.5 h . −1 have insisted on the importance of the
hydrophobic/hydrophilic nature of zeolites within the catalysis [57,58]. To anticipate the association
20
Monolayer adsorption capacity density (cm (STP) / m ) *100

of surface affinity with water, the main reaction media, the H2 O (18.2 kΩ·cm) adsorption isotherm at
298 K was attempted using BELSORP-max. (BEL JAPAN, INC., Osaka, Japan). The samples (100 mg)
2

were pretreated at 573 K for 6 h under vacuum before being measured. The adsorption sectional area
of H2 O at 298 K was 0.1250 15 nm2 . Figure 7 shows the plot of the monolayer adsorption capacity density,
3

which is the monolayer water adsorption capacity value (vm ) (cm3 (STP) g−1 ) divided by a specific
surface area against Ar (m2 g−1 ) as a function of the SiO2 /Al2 O3 ratio in zeolite beta. According
to previous papers [46,59], 10
it was well-known that delamination treatment usually enhances the
hydrophobic nature of zeolites. In fact, the SiO2 /Al2 O3 ratio for zeolite beta involved the monolayer
water adsorption capacity, and the SiO2 /Al2 O3 = 440 ratio which exhibited the highest TOF value (vide
superior) possessed the strongest hydrophobic nature among the zeolite beta samples used in this study.
Note that the difference5 in tendencies observed in the cases of lower/higher SiO2 /Al2 O3 (= 25 and
1700) detected in Figure 7 would be owing to the poor crystallinity of the zeolite and/or the presence
of extra SiO2 or Al2 O3 species. A similar tendency between adsorption capacity and SiO2 /Al2 O3 ratio
has been observed in the 0 case of mordenite in a previous paper [60]. Accordingly, hydrophobicity was
considered to be the one of0 key factors in500 accelerating the target reaction.1500
1000 It is notable that Moreau et al.
also insisted that the hydrophobic character SiO in 2mordenite was a predominant factor in the activity of
/Al2O3 ratio (mol/mol)
hydroxymethylation of furfuryl alcohol by aqueous formaldehyde because the adsorption of organic
substrates
Figure onto the catalyst
7. Monolaye in water
r adsorption as solvent
capacity determined
de nsity as a function theofreaction constant
SiO 2 /Al2 O forzethe
3 ratio with reaction
olite be ta. [46].
STP: standard ambient temperature and pre ssure.
 Figure 6. Time -base d re action progre ssion of the hydroxyme thylation of furfural to HMF among
ze olite be ta sample s compose d of diffe re nt SiO 2 /Al2 O 3 ratios in a batch re actor: (a)HMFconcentration
and (b) initial rate for HMF production pe r acid amount. (c) Plot of turnove r fre que ncy (TOF) value s
as a function of SiO 2 /Al2 O 3 ratio on the basis of the dashe d line s in (b) which re pre se nt the line ar
approximation
Catalysts 2019, 9, 314 re sults. Re action conditions: furfural (1 mmol), formalin (5 mL), catalyst (200 mg),8 of 12
te mpe rature (363 K), stirring (500 rpm).

However, there discuss

To further still remains an open
the details question
of the about in
differences whether
reactivity the relationship
derived frombetween
the SiOthe
2/AlTOF value
2O3 ratios,
and the monolayer adsorption capacity density did not make a linear contribution.
the initial rates of the reaction per acid amount and the TOF values were plotted in Figure 6b and It is supposed that
determination
Figure of the actual
6c, respectively. It can acid sites working
be clearly observedin water
that solvent,
the SiO 2/Al 2Oe.g., thewas
3 ratio impact of water
greatly tolerance
associated with
on Brønsted/Lewis acidity, would be helpful for further understanding the mechanism
the reactivity of the target reaction. The reactivity had been heightened by increasing the SiO2/Al2O3 of zeolite
beta-catalyzed
ratio from 25 tohydroxymethylation
440. The highest TOF ofvalue
furfural to HMF
leached with
at 2.4 h −1aqueous
, which was formaldehyde
four times as a dual
higher solvent
than that
and reagent.
obtained Notably,
using SiO2/Al applications
2O3 = 25. In of various azeolite
addition, betas forlarge
significantly the flow
SiO2reactor system(1700)
/Al2O3 value were also capable
produced a
and showed good stability of HMF yield (see Figure
drastic decrease in the TOF value, giving a value of 0.5 h . S8). −1

20
Monolayer adsorption capacity density (cm (STP) / m ) *100
2

15
3

10

0
0 500 1000 1500
SiO2/Al2O3 ratio (mol/mol)

Figure 7. Monolayer adsorption capacity density as a function of SiO2 /Al2 O3 ratio with zeolite beta.
Figure 7. Monolaye
STP: standard r adsorption
ambient capacity
temperature de nsity as a function of SiO 2 /Al2 O 3 ratio with ze olite be ta.
and pressure.
STP: standard ambient temperature and pre ssure.
3. Materials and Methods

3.1. Batch Reactor System

The reaction was performed in a Schlenk glass flask attached to a condensation cooler. As a general
procedure, first, 37% aqueous formaldehyde solution (stabilized with 5–10% methanol, Wako Pure
Chemical Ind. Ltd., Osaka, Japan) (5 mL) and solid catalyst (200 mg) were mixed well under vigorous
stirring (500 rpm) at 363 K. Thereafter, the substrate of furfural (1 mmol) without purification treatment
(Acros Organic, Geel, Belgium; 99% purity) was injected into the above mixture to initiate the target
reaction. Then, after 12 h of reaction, the catalyst was filtered off with a Milex syringe filter (0.20 µm)
(Merck, Darmstadt, Germany) and the obtained filtrate was analyzed using an HPLC equipped
with a refractive index (RI) detector (Waters 2414). The column was an Aminex HPX-87H (Bio-Rad
Laboratories Inc., Hercules, CA, USA) under 10 mM H2 SO4 aq. flow (0.5 mL min−1 ). The retention
times for HMF and furfural were 39.1 min and 60.0 min, respectively. Conversion and yield values
were estimated with the standard lines adjusted by each reference compound.

3.2. Flow Reactor System

The liquid flow reaction was examined with a simple flow reactor system (MCR-1000; EYELA,
Tokyo, Japan). A powdered zeolite sample was pressed (40 kPa for 30 min) into thin wafers, and then
crushed and screened within a mesh size range of 26–42, before being installed into the reaction bed
tube (ϕ5). The flow rate of the reaction mixture of furfural (10 mmol) and formalin (50 mL) was 0.2 mL
min−1 and the reaction was performed at 363 K. The reactant was analyzed by HPLC using the same
procedure mentioned above.
Catalysts 2019, 9, 314 9 of 12

4. Conclusions
In summary, four types of typical zeolites and normal SiO2 -Al2 O3 were tentatively compared
with regard to their reactivity for the hydroxymethylation of furfural towards HMF in a batch reactor
system and a flow reactor system. Interestingly, the beta-type zeolite was found to be a highly-active,
reusable, and uniquely stable catalyst. The effect of the SiO2 /Al2 O3 ratio for the various zeolite beta
samples was examined using reactivity (TOF), NH3 -TPD, and water adsorption capacity. The zeolite
beta composed of SiO2 /Al2 O3 = 440 gave the highest TOF value of 2.4 h−1 in the batch reactor system
and it possessed a strong hydrophobic nature. According to these results, it may be suggested that
hydrophobicity plays a crucial role in the hydroxymethylation of furfural towards HMF using an
aqueous formaldehyde reagent. In comparison to our previous report, which focused on a sulfuric
functionalized resin catalyst [42], we have observed that there are a variety of ways of constructing
morphology/affinity-controlled zeolite fabrications. Therefore, novel catalysis derived from zeolite
beta in this report is expected to open up new possibilities for future research on the designs of
zeolite-catalyzed hydroxymethylations, and in particular, the upgrading of C5 to C6 furaldehydes
in biorefinery.

Supplementary Materials: The following are available online at http://www.mdpi.com/2073-4344/9/4/314/

s1, Figure S1: Pore size distributions of ZSM-5, mordenite, zeolite Y, and normal SiO2 -Al2 O3 determined by
Ar adsorption, Figure S2: Pore size distributions of zeolite beta with various SiO2 /Al2 O3 determined by Ar
adsorption, Figure S3: Time-based reaction progression of furfural conversion for hydroxymethylation among
four zeolites and normal SiO2 -Al2 O3 in a batch reactor, Table S1: Recycling experiments for the zeolite beta
(SiO2 /Al2 O3 = 150) in a batch reactor, Figure S4: T Photographs of (a) fresh and (b) spent zeolite beta catalyst
(SiO2 /Al2 O3 = 150), Figure S5: TG-DTA curves of spent zeolite beta (SiO2 /Al2 O3 = 150) in a batch reaction, Figure
S6: Example of HPLC chromatograph for the hydroxymethylation of furfural to HMF in aqueous formaldehyde
over zeolite beta, Figure S7: Time-based reaction progression of the hydroxymethylation of furfural to HMF
among zeolite beta samples composed of different SiO2 /Al2 O3 ratios in a batch reactor: (a) furfural conversion
and (b) HMF yield, Figure S8: Time-based reaction for HMF production in a flow reactor using f zeolite beta
samples composed of various SiO2 /Al2 O3 ratios: (a) furfural conversion and (b) HMF yield.
Author Contributions: Conceptualization, S.N.; methodology, S.N. and A.S.; formal analysis, S.N. and A.S.;
investigation, S.N. and A.S.; resources, S.N. and A.S.; data curation, S.N. and A.S.; writing—original draft
preparation, S.N.; writing—review and editing, S.N.; visualization, S.N.; supervision, S.N.; project administration,
S.N.; funding acquisition, S.N.
Funding: This work was supported by JSPS KAKENHI for Young Scientists (A) (grant no. 17H04966), Japan.
Acknowledgments: The authors would like to thank Prof. K. Ebitani (JAIST) for his encouragement of this
research and Dr. D. Mott (Tohoku Univ.) for his careful reading of the manuscript.
Conflicts of Interest: The authors declare that they have no competing financial interest.

References
1. Van Putten, R.J.; van der Waal, J.C.; de Jong, E.; Rasrendra, C.B.; Heeres, H.J.; de Vries, J.G.
Hydroxymethylfurfural, A Versatile Platform Chemical Made from Renewable Resources. Chem. Rev.
2013, 113, 1499–1597. [CrossRef] [PubMed]
2. Isikgor, F.H.; Becer, C.R. Lignocellulosic biomass: A sustainable platform for the production of bio-based
chemicals and polymers. Polym. Chem. 2015, 6, 4497–4559. [CrossRef]
3. Delidovich, I.; Hausoul, P.J.C.; Deng, L.; Pfutzenreuter, R.; Rose, M.; Palkovits, R. Alternative Monomers
Based on Lignocellulose and Their Use for Polymer production. Chem. Rev. 2016, 116, 1540–1599. [CrossRef]
[PubMed]
4. Kobayashi, H.; Fukuoka, A. Synthesis and utilization of sugar compounds derived from lignocellulosic
biomass. Green Chem. 2013, 15, 1740–1763. [CrossRef]
5. Nishimura, S.; Ebitani, K. Selective Oxidation of Biomass-derived Alcohols with Supported Metal Catalysts.
J. Jpn. Petroleum Inst. 2017, 60, 72–84. [CrossRef]
6. Lange, J.P.; van der Heide, E.; van Buijtenen, J.; Price, R. Furfural—A Promising Platform for Lignocellulosic
biofuels. ChemSusChem 2012, 5, 150–166. [CrossRef] [PubMed]
Catalysts 2019, 9, 314 10 of 12

7. Xu, S.; Zhou, P.; Zhang, Z.; Yang, C.; Zhang, B.; Deng, K.; Bottle, S.; Zhu, H. Selective Oxidation of
5-Hydroxymethylfurfural to 2,5-Furandicarboxylic Acid using O2 and a Photocatalyst of Cothioporphyrazine
Bonded to g-C3 N4 . J. Am. Chem. Soc. 2017, 139, 14775–14782. [CrossRef]
8. Gupta, N.K.; Nishimura, S.; Takagaki, A.; Ebitani, K. Hydrotalcite supported gold-nanoparticle-catalyzed
highly efficient base-free aqueous oxidation of 5-hydroxymethylfurfural into 2,5-fudandicarboxylic acid
under atmospheric oxygen pressure. Green Chem. 2011, 13, 824–827. [CrossRef]
9. Yuan, Z.; Liu, B.; Zhou, P.; Zhang, Z.; Chi, Q. Aerobic oxidation of biomass-derived 5-hydrxymtehylfurfural
to 2,5-diformylfuran with cesium-doped manganese dioxide. Catal. Sci. Techonol. 2018, 8, 4430–4439.
[CrossRef]
10. Takagaki, A.; Takahashi, M.; Nishimura, S.; Ebitani, K. One-pot synthesis of 2,5-diformylfuran from
carbohydrate derivatives by sulfonated resin and hydrotalcite-supported ruthenium catalysts. ACS Catal.
2011, 1, 1562–1565. [CrossRef]
11. Perret, N.; Grigoropoulos, A.; Zanella, M.; Manning, T.D.; Claridge, J.B.; Rosseinsky, M.J. Catalytic Response
and Stability of Nickel/Alumina for the Hydrogenation of 5-Hydroxymethylfurfural in water. ChemSusChem
2016, 8, 521–531. [CrossRef] [PubMed]
12. Ohyama, J.; Hayashi, Y.; Ueda, K.; Yamamoto, Y.; Arai, S.; Satsuma, A. Effect of FeOx modification of Al2 O3
on its supported Au catalyst for hydrogenation of 5-hydroxymethylfurfural. J. Phys. Chem. C 2016, 120,
15129–15136. [CrossRef]
13. Roman-Leshkov, Y.; Barrett, C.J.; Liu, Z.Y.; Dumesic, J.A. Production of dimethylfuran for liquid fuels from
biomass-derived carbonhydrates. Nature 2007, 447, 982–985. [CrossRef]
14. Thananatthanachon, T.; Rauchfuss, T.B. Efficient Production of the liquid fuel 2,5-Dimethylfuran from
fructose using formic Acid as a reagent. Angew. Chem. Int. Ed. 2010, 49, 6616–6618. [CrossRef]
15. Nishimura, S.; Ikeda, N.; Ebitani, K. Selective hydrogenation of biomass-derived 5-hydroxymethylfurfural
(HMF) to 2,5-dimethylfuran (DMF) under atomospheric hydrogen pressure over carbon supported PdAu
bimetallic catalyst. Catal. Today 2014, 232, 89–98. [CrossRef]
16. Chandra, D.; Inoue, Y.; Sasase, M.; Kitano, M.; Bhaumik, A.; Kamata, K.; Hosono, H.; Hara, M. A high
performance catalyst of shape-specific ruthenium nanoparticles for production pf primary amines by
reductive amination of carbonyl compounds. Chem. Sci. 2018, 9, 5949–5956. [CrossRef]
17. Tuteja, J.; Choudhary, H.; Nishimura, S.; Ebitani, K. Direct synthesis of 1,6-hexanediol from HMF over
a heterogeneous Pd/ZrP catalyst using formic acid as hydrogen source. ChemSusChem 2014, 7, 96–100.
[CrossRef]
18. Weingarten, R.; Conner, W.C., Jr.; Huber, G.W. Production of levulinic acid from cellulose by hydrothermal
decomposition combined with aqueous phase dehydration with a solid acid catalyst. Energy Environ. Sci.
2012, 5, 7559–7574. [CrossRef]
19. Son, P.A.; Nishimura, S.; Ebitani, K. Synthesis of levulinic acid from fructose using Amberlyst-15 as a solid
acid catalyst. React. Kinet. Mech. Catal. 2012, 106, 185–192. [CrossRef]
20. Pupovac, K.; Palkovits, R. Cu/MgAl2 O4 as Bifunctional Catalyst for Aldol Condensation of
5-Hydroxymethylfurfural and selective Transfer Hydrogenation. ChemSusChem 2013, 6, 2103–2110.
[CrossRef] [PubMed]
21. Buntara, T.; Noel, S.; Phua, P.H.; Melian-Cabrera, I.; de Vries, J.G. Caprolactam from Renewable Resources:
Catalytic Conversion of 5-Hydroxymethylfurfural into Caprolactone. Angew. Chem. Int. Ed. 2011, 50,
7083–7087. [CrossRef]
22. Wozniak, B.; Spannenberg, A.; Li, Y.; Hinze, S.; de Vries, J.G. Cyclopentanone Derivatives from
5-Hydroxymethylfurfural via 1-Hydroxyhexane-2,5-dione as Intermediate. ChemSusChem 2018, 11, 356–359.
[CrossRef]
23. Gomes, R.F.A.; Coelho, J.A.S.; Afonso, C.A.M. Direct Conversion of Activated 5-Hydroxymethylfurfural into
d-Lactone-fused Cyclopentenones. ChemSusChem 2019, 12, 420–425. [CrossRef]
24. Gupta, N.K.; Fukuoka, A.; Nakajima, K. Metal-Free and Selective Oxidation of furfural to Furoic Acid with
an N-heterocyclic Carbone Catalyst. ACS Sustain. Chem. Eng. 2018, 6, 3434–3442. [CrossRef]
25. Douthwaite, M.; Huang, X.; Iqbal, S.; Miedziak, P.J.; Brett, G.L.; Kondrat, S.A.; Edwards, J.K.; Sankar, M.;
Knight, D.W.; Bethell, D.; et al. The controlled catalytic oxidation of furfural to furoic acid using
AuPd/Mg(OH)2 . Catal. Sci. Technol. 2017, 7, 5284–5293. [CrossRef]
Catalysts 2019, 9, 314 11 of 12

26. Lopez-Asensio, R.; Cecilia, J.A.; Jimenez-Gomez, C.P.; Garcia-Sancho, C.; Moreno-Rost, R.; Maireles-Torres, P.
Selective production of furfuryl alcohol from furfural by catalytic transfer hydrogenation over commercial
aluminas. Appl. Catal. A Gen. 2018, 556, 1–9. [CrossRef]
27. Nishimura, S.; Shimura, T.; Ebitani, K. Transfer hydrogenation of furaldehydes with sodium phosphinate
as a hydrogen source using Pd-supported alumina catalyst. J. Taiwan Inst. Chem. Eng. 2017, 79, 97–102.
[CrossRef]
28. Gandarias, I.; Garcia-Fernandez, S.; Obregon, I.; Agirrezabal-Telleria, I.; Arias, P.L. Production of
2-methylfuran from biomass through an integrated biorefinery approach. Fuel Proc. Technol. 2018, 178,
336–343. [CrossRef]
29. Sitthisa, S.; An, W.; Resasco, D.E. Selective conversion of furfural to methylfuran over silica-supported Ni-Fe
bimetallic catalysts. J. Catal. 2011, 284, 90–101. [CrossRef]
30. Komanoya, T.; Kinemura, T.; Kita, K.; Kamata, K.; Hara, M. Electronic effect of ruthenium nanoparticles on
efficient reductive amination of carbonyl compounds. J. Am. Chem. Soc. 2017, 139, 11493–11499. [CrossRef]
31. Nishimura, S.; Mizuhori, K.; Ebitani, K. Reductive amination of furfural toward furfurylamine with aqueous
ammonia under hydrogen over Ru-supported catalyst. Res. Chem. Intermed. 2016, 42, 19–30. [CrossRef]
32. Liu, S.; Amada, Y.; Tamura, M.; Nakagawa, Y.; Tomishige, K. Performance and characterization
of rhenium-modified Rh-Ir alloy catalyst for one-pot conversion of furfural into 1,5-oentandiol.
Catal. Sci. Technol. 2014, 4, 2535–3549. [CrossRef]
33. Lee, J.; Burt, S.P.; Carrero, C.A.; Alba-Rubio, A.C.; Ro, I.; O’Neil, B.J.; Kim, H.J.; Jackson, D.H.K.; Kuech, T.F.;
Hermans, I.; et al. Stabilizating cobalt catalyst for aqueous-phase reactions by strong metal-support
interaction. J. Catal. 2015, 330, 19–27. [CrossRef]
34. Choudhary, H.; Nishimura, S.; Ebitani, K. Highly efficient aqueous oxidation of furfural to succinic acid
using reusable heterogeneous acid catalyst with hydrogen peroxide. Chem. Lett. 2012, 41, 409–411. [CrossRef]
35. Yang, J.; Li, N.; Li, G.; Wang, W.; Wang, A.; Wang, X.; Cong, Y.; Zhang, T. Solvent-Free Synthesis of C10
and C11 Branched Alkanes from Furfural and Methyl Isobutyl Ketone. ChemSusChem 2013, 6, 1149–1152.
[CrossRef] [PubMed]
36. Xu, W.; Xia, Q.; Zhang, Y.; Guo, Y.; Wang, Y.; Lu, G. Effective Production of Octane from Biomass Derivatives
under Mild Conditions. ChemSusChem 2011, 4, 1758–1761. [CrossRef]
37. Shirotori, M.; Nishimura, S.; Ebitani, K. One-Pot Synthesis of Furfural Derivatives from Pentoses using Solid
Acid and Base Catalysts. Catal. Sci. Technol. 2014, 4, 971–978. [CrossRef]
38. Nunes, J.P.M.; Afonso, C.A.M.; Caddick, S. Synthesis of 2,4-bifunctionalized cyclopentenones from
2-furaldehyde. RSC Adv. 2013, 3, 14975–14978. [CrossRef]
39. Nardi, M.; Costanzo, P.; Nino, A.D.; Gioia, M.L.D.; Olivito, F.; Sindona, G.; Procopio, A. Water excellent
solvent for the synthesis of bifunctionalized cyclopentenones from furfuram. Green Chem. 2017, 19, 5403–5411.
[CrossRef]
40. Gioia, M.L.D.; Nardi, M.; Costanzo, P.; Nino, A.D.; Maiuolo, L.; Oliverio, M.; Procopio, A. Biorenewable
Deep Eutectic Solvent for Selective and Scalable Conversion of Furfural into Cyclopenenone Derivatives.
Molecules 2018, 23, 1891. [CrossRef]
41. Koh, P.F.; Wang, P.; Huang, J.M.; Loh, T.P. Biomass derived furfural-based facile synthesis of protected
(2S)-phenyl-3-piperidone, a common intermediate for many drugs. Chem. Commun. 2014, 50, 8324–8327.
[CrossRef]
42. Nishimura, S.; Shibata, A.; Ebitani, K. Direct Hydroxymethylation of Furaldehydes with Aqueous
Formaldehyde over a Reusable Sulfuric Functionalized Resin Catalyst. ACS Omega 2018, 3, 5988–5993.
[CrossRef]
43. Lecomte, J.; Finiels, A.; Geneste, P.; Moreau, C. Kinetics of furfuryl alcohol hydroxymethylation with aqueous
formaldehyde over a highly dealuminated H-mordenite. J. Mol. Catal. A Chem. 1998, 133, 283–288. [CrossRef]
44. Lecomte, J.; Finiels, A.; Geneste, P.; Moreau, C. Selective hydroxymethylation of furfuryl alcohol with
aqueous formaldehyde in the presence of dealuminated mordenites. Appl. Catal. A Gen. 1998, 168, 235–241.
[CrossRef]
45. Lecomte, J.; Finiels, A.; Moreau, C. A new selective route to 5-hydroxymethylfurfural from furfural and
furfural derivatives over microporous solid acidic catalysts. Ind. Crops Prod. 1999, 19, 235–241. [CrossRef]
Catalysts 2019, 9, 314 12 of 12

46. Lecomte, J.; Finiels, A.; Geneste, P.; Moreau, C. Attempt to quantify the hydrophobic character of highly
dealuminated H-mordenites in hydroxymethylation of furfuryl alcohol with aqueous formaldehyde. J. Mol.
Catal. A Chem. 1999, 140, 157–163. [CrossRef]
47. Everett, D.H.; Powl, J.C. Adsorption in slit-like and cylindrical micropores in the henry’s law region. A model
for the microporosity of carbons. J. Chem. Soc. Faraday Trans. 1976, 72, 619–636. [CrossRef]
48. Ono, Y.; Hattori, H. Solid Base Catalysis. In Springer Series in Chemical Physics 101; Springer:
Berlin/Heidelberg, Germany; Tokyo Institute of Technolgy Press: Tokyo, Japan, 2011.
49. Imelik, B.; Naccache, C.; Taarit, Y.B.; Vedrine, J.C.; Coudurier, G.; Praliaud, H. Catalysis by Zeolites. In Studies
in Surface Science and Catalysus 5; Elsevier: Amsterdam, The Netherlands, 1980.
50. He, Y.; Hoff, T.C.; Emaadi, L.; Wu, Y.; Bouraima, J.; Liu, D. Catalytic consequences of micropore topology,
mesoporosity, and acidity on the hydrolysis of sucrose over zeolite catalysts. Catal. Sci. Technol. 2014, 4,
3064–3073. [CrossRef]
51. Li, H.; Yang, S.; Riisager, A.; Pandey, A.; Sangwan, R.S.; Saravanamurugan, S.; Luque, R. Zeolite and
zeotype-catalysed transformations of biofuranic compounds. Green Chem. 2016, 18, 5701–5735. [CrossRef]
52. Otomo, R.; Yokoi, T.; Kondo, J.N.; Tatsumi, T. Dealuminated Beta zeolite as effective bifunctional catalyst
for direct transformation of glucose to 5-hydroxymethylfurfural. Appl. Catal. A Gen. 2014, 470, 318–326.
[CrossRef]
53. Otomo, R.; Tatusmi, T.; Yokoi, T. Beta zeolite: A universally applicable catalyst for the conversion of various
type of sacchrides into furfural. Catal. Sci. Technol. 2015, 5, 4001–4007. [CrossRef]
54. Gebresillase, M.N.; Shavi, R.; Seo, J.G. A comprehensive investigation of the condensation of furanic platform
molecules to C14 –C15 fuel precursors over sulfonic acid functionalized silica supports. Green Chem. 2018, 20,
5133–5146. [CrossRef]
55. Arias, K.S.; Al-Resayes, S.I.; Climent, M.J.; Corma, A.; Iborra, S. From Biomass to Chemicals: Synthesis
of precusors of Biodegradable Surfactants from 5-Hydroxymethylfurfural. ChemSusChem 2013, 6, 123–131.
[CrossRef]
56. Galkin, K.I.; Krivodaeva, E.A.; Romashov, L.V.; Zalesskiy, S.S.; Kachala, V.V.; Burykina, J.V.; Ananikov, V.P.
Critical Infulence of 5-Hydroxymethylfurfural Aging and Decomposition on the Utility of Biomass
Conversion in Organic Synthesis. Angew. Chem. Int. Ed. 2016, 55, 8338–8342. [CrossRef]
57. da Silva, C.X.A.; Goncalves, V.L.C.; Mota, C.J.A. Water-tolerant zeolite catalyst for the acetalisation of glycerol.
Green Chem. 2009, 11, 38–41. [CrossRef]
58. Zapata, P.A.; Faria, J.; Ruiz, M.P.; Jentoft, R.E.; Resasco, D.E. Hydrophobic Zeolites for Biofuel Upgrading
Reactions at the Liquid-Liquid Interface in Water/Oil Emulsions. J. Am. Chem. Soc. 2012, 134, 8570–8578.
[CrossRef] [PubMed]
59. Kuwahara, Y.; Aoyama, J.; Miyakubo, K.; Eguchi, T.; Kamegawa, T.; Mori, K.; Yamashita, H.
TiO2 photocatalyst for degradation of organic compounds in water and air supported on highly hydrophobic
FAU zeolite: Structural, sorptive, and photocatalytic studies. J. Catal. 2012, 285, 223–234. [CrossRef]
60. Chen, N.Y. Hydrophobic Properties of Zeolite. J. Phys. Chem. 1976, 80, 60–64. [CrossRef]

© 2019 by the authors. Licensee MDPI, Basel, Switzerland. This article is an open access
article distributed under the terms and conditions of the Creative Commons Attribution
(CC BY) license (http://creativecommons.org/licenses/by/4.0/).