Conversion of glucose into 5-hydroxymethylfurfural on granular zeolite catalysts
Biomass-derived 5-hydroxymethylfurfural (5-HMF) is a potential raw material for the production of a wide range of valuable chemicals and biofuels. Industrial production of 5-HMF from hexoses on solid catalysts is promising nowadays. Acid zeolites have great potential in application as catalysts for...
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V.P. Kukhar Institute of Bioorganic Chemistry and Petrochemistry of the National Academy of Sciences of Ukraine
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Catalysis and petrochemistry| _version_ | 1872009041957355520 |
|---|---|
| author | Patrylak, Lyubov K. Konovalov, Serhii V. Yakovenko, Angela V. Pertko, Oleksandra P. Povazhnyi, Volodymyr A. Melnychuk, Oleksandr V. |
| author_facet | Patrylak, Lyubov K. Konovalov, Serhii V. Yakovenko, Angela V. Pertko, Oleksandra P. Povazhnyi, Volodymyr A. Melnychuk, Oleksandr V. |
| author_institution_txt_mv | [
{
"author": "Lyubov K. Patrylak",
"institution": "V.P Kukhar Institute of Bioorganic Chemistry and Petrochemistry of NAS of Ukraine. Kharkivske shosse, 50, Kyiv-02160, Ukraine"
},
{
"author": "Serhii V. Konovalov",
"institution": "V.P Kukhar Institute of Bioorganic Chemistry and Petrochemistry of NAS of Ukraine. Kharkivske shosse, 50, Kyiv-02160, Ukraine"
},
{
"author": "Angela V. Yakovenko",
"institution": "V.P Kukhar Institute of Bioorganic Chemistry and Petrochemistry of NAS of Ukraine. Kharkivske shosse, 50, Kyiv-02160, Ukraine"
},
{
"author": "Oleksandra P. Pertko",
"institution": "V.P Kukhar Institute of Bioorganic Chemistry and Petrochemistry of NAS of Ukraine. Kharkivske shosse, 50, Kyiv-02160, Ukraine"
},
{
"author": "Volodymyr A. Povazhnyi",
"institution": "V.P Kukhar Institute of Bioorganic Chemistry and Petrochemistry of NAS of Ukraine. Kharkivske shosse, 50, Kyiv-02160, Ukraine"
},
{
"author": "Oleksandr V. Melnychuk",
"institution": "V.P Kukhar Institute of Bioorganic Chemistry and Petrochemistry of NAS of Ukraine. Kharkivske shosse, 50, Kyiv-02160, Ukraine"
}
] |
| author_sort | Patrylak, Lyubov K. |
| baseUrl_str | https://kataliz.org.ua/index.php/journal/oai |
| collection | OJS |
| datestamp_date | 2023-01-20T09:54:45Z |
| description | Biomass-derived 5-hydroxymethylfurfural (5-HMF) is a potential raw material for the production of a wide range of valuable chemicals and biofuels. Industrial production of 5-HMF from hexoses on solid catalysts is promising nowadays. Acid zeolites have great potential in application as catalysts for the dehydration of sugars. The purpose of this work was to obtain granular zeolite catalysts with optimal acidity and evaluate their effectiveness depending on the nature of the binder used. A zeolite catalyst without binder and samples with 10 wt % of kaolin/alumina were prepared. Their porous characteristics and acidity were studied by means of nitrogen low temperature adsorption/desorption, ammonia thermo-programmed desorption, and pyridine adsorption with IR control. The activity and selectivity of the catalysts for 5-HMF synthesis from glucose in the dimethyl sulfoxide medium at 160 ◦C were studied. The high efficiency of granular samples in glucose transformation into 5-HMF is confirmed. They are not only not inferior to, but even superior to, powdered samples. The component sources of Brønsted and Lewis acidity of the ammonium form of zeolite, which demonstrates acceptable activity (selectivity for 5-HMF is 34 %) despite the small number of Lewis centers, are considered in detail. The highest efficiency is demonstrated by the sample with aluminum oxide, which not only does not significantly deteriorate the microporous characteristics but also improves the mesoporosity of the catalyst. The selectivity towards 5-HMF on it reaches 44%. However, the developed mesoporosity of the sample with aluminum oxide is not critical to its activity. The main influence on the effectiveness of the catalyst in the synthesis of 5-HMF is played by the presence of acid centers of medium strength. |
| doi_str_mv | 10.15407/kataliz2022.33.038 |
| first_indexed | 2026-03-12T15:50:15Z |
| format | Article |
| fulltext |
38 Каталіз та нафтохімія, 2022, №33
ISSN 2707-5796. Catalysis and Petrochemistry, 2022, 33
UDC 66.093.48; 661.77; 577.114.3
https://doi.org/10.15407/kataliz2022.33.038
Conversion of glucose into 5-hydroxymethylfurfural on granular zeolite
catalysts
Lyubov K. Patrylak1,2, Serhii V. Konovalov1, Angela V. Yakovenko1, Oleksandra P. Pertko1,
Volodymyr A. Povazhnyi1, Oleksandr V. Melnychuk1,2
1V.P Kukhar Institute of Bioorganic Chemistry and Petrochemistry of NAS of Ukraine. Kharkivske shosse, 50,
Kyiv-02160, Ukraine; e-mail: lkpg@ukr.net
2National Technical University of Ukraine “Igor Sikorskyi Kyiv Politechnical Institute”, Peremohy ave., 37,
Kyiv-03056, Ukraine
Biomass-derived 5-hydroxymethylfurfural (5-HMF) is a potential raw material for the production of a wide
range of valuable chemicals and biofuels. Industrial production of 5-HMF from hexoses on solid catalysts is
promising nowadays. Acid zeolites have great potential in application as catalysts for the dehydration of sugars. The
purpose of this work was to obtain granular zeolite catalysts with optimal acidity and evaluate their effectiveness
depending on the nature of the binder used. A zeolite catalyst without binder and samples with 10 wt % of
kaolin/alumina were prepared. Their porous characteristics and acidity were studied by means of nitrogen low
temperature adsorption/desorption, ammonia thermo-programmed desorption, and pyridine adsorption with IR
control. The activity and selectivity of the catalysts for 5-HMF synthesis from glucose in the dimethyl sulfoxide
medium at 160 ◦C were studied. The high efficiency of granular samples in glucose transformation into 5-HMF is
confirmed. They are not only not inferior to, but even superior to, powdered samples. The component sources of
Brønsted and Lewis acidity of the ammonium form of zeolite, which demonstrates acceptable activity (selectivity for 5-
HMF is 34 %) despite the small number of Lewis centers, are considered in detail. The highest efficiency is
demonstrated by the sample with aluminum oxide, which not only does not significantly deteriorate the microporous
characteristics but also improves the mesoporosity of the catalyst. The selectivity towards 5-HMF on it reaches 44%.
However, the developed mesoporosity of the sample with aluminum oxide is not critical to its activity. The main
influence on the effectiveness of the catalyst in the synthesis of 5-HMF is played by the presence of acid centers of
medium strength.
Keywords: zeolite, glucose conversion, 5-hydroxymehtylfurfural, binder.
____________________________________________________________________________________________________
Introduction
Biomass carbohydrates are an important
inexhaustible natural source of energy. Biomass-
derived 5-hydroxymethylfurfural (5-HMF) is a
potential raw material for the production of a wide
range of valuable chemicals and biofuels [1, 2].
Industrial production of the latter was realized in 2014
by AVA Biochem based only on fructose [3]. Glucose
dehydration is not an industrial process now, but a lot
of researchers around the world are paying attention to
development of this two-stage reaction.
Isomerization of glucose into fructose is followed
by dehydration of the latter to 5-HMF. Lewis acid
centers are thought to catalyze the first stage, the
isomerization of glucose to fructose via the mechanism
of 1,2-hydride transfer, while Brønsted acid centers
promote the second stage, the dehydration of fructose
to 5-HMF [4, 5]. HMF can also degrade into levulinic
and formic acids, as well as polymerize into humins.
As a result, the acidity nature and acid strength of
catalysts are critical factors in the conversion of
glucose to 5-HMF. Inorganic acids (H2SO4, HCl,
H3PO4) are the most widely studied catalysts for
fructose dehydration, whereas catalysts for glucose
transformation are typically a mixture of mineral acids
with metal salts as Lewis acids. There is not much
information in the scientific literature about the effect
of acid strength on 5-HMF yield. Only a few papers
remained focused on this question [6, 7]. It was
demonstrated, that using of moderate HCl
concentrations as well as weak maleic acid lead to
better results in comparison with concentrated acid.
The utilization of heterogeneous catalysis in the
transformation of hexoses is regarded as a forward-
thinking and promising direction that will contribute to
the development of technologically feasible processes
for obtaining platform substances from sugars. Some
solid acids have been tested in the conversion of
glucose or fructose. Oxides, phosphates,
heteropolyacids, mesoporous acids, and ion exchange
resins are being investigated as "green" catalysts for
the formation of 5-HMF [1, 6]. Unfortunately, because
solid acids do not dissociate in water, it is difficult to
compare their acidity to that of liquid mineral acids.
Каталіз та нафтохімія, 2022, №33 39
ISSN 2707-5796. Catalysis and Petrochemistry, 2022, 33
Their acidity is obviously described by using the
sorption of basic compounds, especially
thermoprogrammed desorption (TPD) technique of
basics. The acidity of zeolites is thought to be
comparable to that of mineral acids [7], whereas the
zeolite lattice structure with pores and channels
ranging in size from nanometers to micrometers, as
well as the crystalline arrangement of pores in space,
transforms zeolites into nanostructured materials with
unique properties as molecular sieves. In paper [8]
commercial ultrastable zeolite Y (HUSY) modified
with mineral acids (10-30% H3PO4 and H2SO4) shown
the best 5-HMF yields on the H3PO4-treated sample
with medium-strength acidity. These findings are
consistent with the conclusions of above-mentioned
studies [6, 7].
The importance of using a solid acid catalyst with
a certain spectrum of acidity (with a predominance of
acid centers of medium strength) to improve the
efficiency of zeolite catalysts for the synthesis of 5-
HMF was established in our recent work [9]. Weak-
strength acid sites as well as strong-strength acid sites
seems to be responsible for formation of side products.
However, as is well known that powdered zeolite
catalysts have a number of disadvantages when used,
so the purpose of this work was to obtain granular
zeolite catalysts with optimal acidity and evaluate their
effectiveness depending on the nature of the binder
used.
Experiment
Synthesis of catalyst samples
Two bases for catalysts with kaolin (K-37) and
aluminum oxide (K-38) as a binding component in the
amount of 10 wt% were obtained by mechanical
mixing with synthetic powdered zeolite type X
(SiO2/Al2O3=2.3), followed by pressing and grinding
with the selection of a fraction of 1-2 mm.
Kaolin of Prosyana deposit (Dnipropetrovs'k
region, Ukraine) was used as a binder. It is composed
of 97 wt% kaolinite, 3 wt% mica, and traces of quartz.
The following are the chemical compositions: 46%
SiO2, 38% Al2O3, 1.12% Fe2O3, 1.16% TiO2, 0.52%
CaO, 0.28% MgO, 0.6% K2O, 0.31% Na2O, 12.0%
H2O. Gamma alumina (DSTU 8136-85) was produced
by JS Katalizator (Kamjanske, Ukraine).
The acidic properties to the samples were given
by means of consistent ion exchange of native zeolite
sodium on calcium, lanthanum, and ammonium cations
using aqueous solutions of their nitrates (1 mol/dm3) at
150 oC for 3 h [10, 11]. Following each exchange
filtrates were analyzed for cation content. The
inductively coupled plasma optical emission
spectrometry (ICP OES, Plasma Quant® PQ 9000
Elite, Analytik Jena GmbH) was used for analysis of
filtrates. Table 1 shows cation composition of
synthesized catalyst samples. The calcium-lanthanum-
ammonium form of synthetic zeolite type X (K-35)
and the ammonium form of zeolite type Y (K-36,
SiO2/Al2O3=4.7) were used as comparison samples.
Table 1. Composition of the catalysts
Sample Cations, % of total exchange capacity
Ca2+ La3+ NH4
+ Na+
К-35 28 60 12 <0.5
K-36 - - 72 28
К-37 30 55 15 <0.5
К-38 28 52 20 <1
Catalytic test
The transformation of glucose solutions in
dimethyl sulfoxide (DMSO) was carried out in
stainless steel autoclaves (20 cm3) with
polytetrafluoroethylene inserts. Zeolite catalyst
samples (0.25 g) with 5 g of 10 wt% glucose solution
were heated in autoclaves using an oil bath. The
experiments were carried out at 160 °C for 4 hours.
Experimental details as well as conditions of gas
chromatographic analysis are given in our recent paper
[9].
Catalyst characterization
The porous characteristics of the kaolin-based
samples were determined using nitrogen
adsorption/desorption isotherms measured at low
temperatures (-196 °C) with a Nova 1200e
(Quantochrome) high-speed surface area and a pore
size analyzer.
The Lewis and Brønsted acidity of the samples
were investigated by utilizing pyridine sorption with
IR-spectroscopic control in the range of 1400–1700
cm−1 (Shimadzu IR Affinity-1S FTIR spectrometer).
The ammonia thermoprogrammed desorption
(TPD) curves were recorded in a gas chromatograph
setup that contained a microreactor [13].
The conditions for catalyst characterization are
shown in paper [9].
Results and Discussions
The porous properties of granular zeolite catalysts
and powder comparison samples were investigated by
low-temperature nitrogen adsorption/desorption.
40 Каталіз та нафтохімія, 2022, №33
ISSN 2707-5796. Catalysis and Petrochemistry, 2022, 33
Figure 1 shows isotherms for zeolite-containing
catalysts. A number of isotherms (samples K-35, K-37
and K-36) are classical for microporous objects (type I
IUPAC classification) with a small content of larger
pores, while the K-38 isotherm corresponds to type IV
according to the IUPAC and reflects the presence of
different porosities—a combination of microporosity
and mesoporosity [12]. The latter is reflected by the
presence of a slight hysteresis loop caused by capillary
condensation in mesopores of 2–50 nm. Table 2
summarizes the calculated data on the porous
characteristics of the samples.
0,2 0,4 0,6 0,8 1,0
100
150
200
0,2 0,4 0,6 0,8 1,0
100
150
200
0,2 0,4 0,6 0,8 1,0
100
150
200
0,2 0,4 0,6 0,8 1,0
100
150
200
К-35
V
,
c
m
3
/g
p/p
s
K-36
V
,
c
m
3
/g
p/p
s
К-37
V
,
c
m
3
/g
p/p
s
К-38
V
,
c
m
3
/g
p/p
s
Fig. 1. Nitrogen low temperature adsorption/desorption isotherms for catalysts K-35, K-36, K-37, and K-38
Table 2. Adsorption properties of the catalysts
Sample
SBET,
m2/g
St,
m2/g
St
miсro,
m2/g
Vt
micro,
cm3/g
VΣ,
cm3/g
Vmicro/VΣ,
%
RDFT,
nm
RBJH(des),
nm
R,
nm
К-35 572 7.2 565 0.257 0.240 93.4 2.64 0.90 3.06
К-36 528 12.7 515 0.262 0.233 88.9 1.53 0.99 1.65
К-37 423 9.3 414 0.17 0.19 87 2.8 2.0 0.9
К-38 518 35 482 0.19 0.27 70 2.6 2.0 1.1
As can be seen from the calculations, catalysts
based on powdered zeolite without a binder (K-35 and
K-36) have the largest BET specific surfaces and
micropore surfaces—more than 500 m2/g. They are
characterized by the highest proportions of micropores
(89–93%). Samples obtained with the use of a binder
are distinguished by higher values of the outer surface.
The addition of kaolin has less effect on the outer
surface, but significantly reduces the BET surface and
microporosity. At the same time, no significant
occurrence of mesoporosity is observed. Apparently,
small kaolin particles to some extent block access to
zeolite cavities. When aluminum oxide is used, on the
contrary, microporosity does not suffer much, and
mesoporosity becomes noticeable. Its part increases to
30% (K-38) compared to 13% for the K-37 sample.
This is also confirmed by the pore size distribution
curves presented in Fig. 2, 3. The dominant diameters
are 2 and 3 nm in the case of all samples according to
BJH and DFT theories, respectively. However, if for
Каталіз та нафтохімія, 2022, №33 41
ISSN 2707-5796. Catalysis and Petrochemistry, 2022, 33
K-35, K-37 and K-36 the volume of pores larger than
2-3 nm is 0.015 cm3/g, then for K-38 it is 0.05 cm3/g,
i.e. three times more (Fig. 2). Thus, the increase in
pore sizes is more significant for the sample with
aluminum oxide.
0 5 10 15 20
0,00
0,05
d
V
/d
r
V
,
c
m
3
/g
d
V
/d
r
К-35
0 5 10 15 20
0,00
0,05
К-36
r, nm
r, nmr, nm
0 5 10 15 20
0,00
0,05
0 5 10 15 20
0,00
0,05
0 5 10 15 20
0,00
0,05
К-37
r, nm
0 5 10 15 20
0,00
0,05
К-38
d
V
/d
r
d
V
/d
r
d
V
/d
r
d
V
/d
r
d
V
/d
r
V
,
c
m
3
/g
V
,
c
m
3
/g
ads des
0 5 10 15 20
0,00
0,05
0 5 10 15 20
0,00
0,05
V
,
c
m
3
/g
V
,
c
m
3
/g
V
,
c
m
3
/g
V
,
c
m
3
/g
0,00
0,02
0,04
V
,
c
m
3
/g
0,00
0,02
0,04
0,00
0,02
0,04
r, nm
0,00
0,02
0,04
0,00
0,02
0,04
r, nm
0,00
0,02
0,04
r, nm
r, nm
0,00
0,02
0,04
d
V
/d
r
0,00
0,02
0,04
Fig. 2. Integral and differential pore size distributions calculated from BJH theory using the adsorption (left) and
desorption (right) branches of isotherms for catalyst K-35, K-36, K-37, and K-38
42 Каталіз та нафтохімія, 2022, №33
ISSN 2707-5796. Catalysis and Petrochemistry, 2022, 33
0 5 10 15 20
0,1
0,2
0,3
r, nm
d
V
/d
r
V
,
c
m
3
/g
d
V
/d
r
К-35
0 5 10 15 20
0,1
0,2
0,3
К-37
r, nm
0 5 10 15 20
0,1
0,2
0,3
К-38
0 5 10 15 20
0,1
0,2
0,3
К-36
r, nm
V
,
c
m
3
/g
V
,
c
m
3
/g
0,00
0,02
V
,
c
m
3
/g
0,00
0,02
0,00
0,02
d
V
/d
r
0,00
0,02
d
V
/d
r
r, nm
Fig. 3. DFT-calculated integral and differential pore size distributions for samples K-35, K-36, K-37, and K-38
The acidity of the samples was determined by
means of thermoprogrammed desorption of ammonia
(Table 2). The total number of acid centers in the
samples is quite close. Naturally, for the sample with
kaolin, which has deteriorated the porous
characteristics, the acidity is the lowest because the
access to the acid centers in the micropores is
impaired. All four samples have a significant number
of acid centers of medium strength, but most of them
are in the ammonium form (K-36). However, as is
known, the acidity according to TPD of ammonia
reflects the total number of both Brønsted and Lewis
centers.
If in the case of polycationic samples with
lanthanum cations having free electronic orbitals, the
presence of Lewis acidity is not in doubt, it is not so
clear for the ammonium form of zeolite.
Table 2. Number of acid sites in the catalysts
Sample Number of acid sites, mol/g
200-350 оС 350-450 оС 450-550 оС Total
К-35 0.45 0.50 0.56 1.51
К-36 0.29 0.81 0.55 1.65
К-37 0.40 0.52 0.50 1.42
К-38 0.35 0.61 0.78 1.74
Fig. 4 shows the spectrum of adsorbed
pyridine on a sample of the ammonium form zeolite K-
36. The spectrum shows a significant Brønsted acidity
(intense band at 1543 cm-1) with an indistinct Lewis
acidity (weak band at 1454 cm-1). The band reflecting
the combined Brønsted and Lewis acidity (1489 cm-1)
is also intense. However, based on the chemical
composition of the sample containing exclusively
ammonium cations and native sodium, only the latter
cations can act as weak Lewis sites together with
extra-framework aluminum. Its existence is highly
probable in view of the lower BET surface and
micropore surface compared to the polycation sample
K-35. Although, in general, this sample clearly has
mainly Brønsted acidity.
Каталіз та нафтохімія, 2022, №33 43
ISSN 2707-5796. Catalysis and Petrochemistry, 2022, 33
1700 1650 1600 1550 1500 1450 1400
350 ОС
145414891543
n, cm-1
250 ОС
150 ОС
Fig. 4. IR spectra of catalyst K-36 in the region of
adsorbed pyridine
Table 3 shows the results of glucose dehydration
at 160 oC for 4 hours in the presence of synthesized
samples. Analyzing the results, it should be noted that,
firstly, glucose conversion was almost complete in all
experiments. In our work [9], we showed the existence
of a correlation between the activity of samples and the
content of ammonium cations in them—the higher the
content of ammonium cations, the higher the activity.
This tendency is generally confirmed on these samples.
The postulated need for acidity of medium strength
according to ammonia desorption is also confirmed. It
is interesting that this medium acidity is largely
contributed by the acidity caused by the presence of
ammonium cations (desorption maximum of 375-400
oC). However, one should not forget about the features
of the pure ammonium form, which has only a weak
Lewis acidity. As it was shown by the sorption of
pyridine, Brønsted acidity is present in it, but it should
be taken into account that during its determination, the
decomposition of the ammonium cation occurred
during vacuuming of the sample at 400 °C. This
decomposition will not occur in the case of catalysis at
160 °C without prior dehydration of the sample. The
ammonium form, which is traditionally used as an
intermediate in the production of zeolite hydrogen
form with classic hydroxyl bridging Brønsted centers,
also has a certain intermediate Brønsted acidity [14]. It
is possible to expect protonation of carbohydrates on it
by analogy with well-known processes implemented in
the water environment:
NH4
+ + H2O —-> NH3 + (H3О)+
NH4
+ + С6Н12O6 —-> NH3 + (С6Н13O6)+
That is why the synthesized samples, even
without decomposition of the ammonium form to the
hydrogen form, still show the appropriate activity,
which is the lowest in the case of the pure polycationic
sample K-35 with the lowest content of ammonium
and medium acid centers, higher for K-37 and the
highest for K-38. In the last sample, in addition to
acidity, the influence of porous characteristics, in
particular mesoporosity, should not be completely
rejected. Diffusion complications for the K-38 sample
are the least since the improvement of mesopores in it
is 30%. K-37 with kaolin as a binder shows worse
porous characteristics (total pore volume significantly
lower) and, accordingly, the lower selectivity.
Table 3. Results of glucose conversion on synthesized zeolite catalysts
Catalyst Conversion, % Selectivity for 5-HMF, mol%
К-35 98 33.3
К-36 99.1 34.4
К-37 99 40.9
К-38 99.5 43.9
Conclusions
Thus, the conducted studies showed, firstly, that
zeolite catalysts formed by mixing with a binder are
not inferior in activity in the conversion of glucose to
5-HMF in the DMSO environment and may even be
superior to pure powdered zeolites. Secondly, the use
of gamma-aluminum oxide as a binder looks more
promising for obtaining granular zeolites. Its use does
not deteriorate the microporosity of the sample, while
improving its mesoporosity. The optimal strength of
Brønsted acidity for the studied transformation is
provided by the introduction of an ammonium cation
into the composition of zeolite samples, which is
reflected in the formation of acid centers of medium
strength, which ensure the course of the target reaction
of dehydration to 5-HMF.
Acknowledgments
The publication contains the results of studies
conducted by grant from the National Research
Foundation of Ukraine project 2020.01/0042.
44 Каталіз та нафтохімія, 2022, №33
ISSN 2707-5796. Catalysis and Petrochemistry, 2022, 33
References
1. Esteban J., Yustos P., Ladero M. Catalytic
Processes from Biomass-Derived Hexoses and
Pentoses: A Recent Literature Overview.
Catalysts, 2018, 8, 637-678.
2. Chen N., Zhu Z., Ma H., Liao W., Lü H. Catalytic
upgrading of biomass-derived 5-
hydroxymethylfurfural to biofuel 2,5-
dimethylfuran over Beta zeolite supported non-
noble Co catalyst. Mol. Catal., 2020, 486,
110882.
3. Kläusli T. AVA Biochem: commercialising
renewable platform chemical 5-HMF. Green
Process Synth., 2014, 3, 235–236.
4. Choudhary V., Mushrif S.H., Ho C., Anderko
A., Nikolakis V., Marinkovic N.S., Frenkel
A.I., Sandler S.I., Vlachos D.G. Insights into the
interplay of Lewis and Brønsted acid catalysts in
glucose and fructose conversion to 5-
(hydroxymethyl)furfural and levulinic acid in
aqueous media. J. Am. Chem. Soc., 2013, 135
(10), 3997-4006.
5. Li Y., Meng X., Luo R., Zhou H., Lu S., Yu S.,
Bai P., Guo X., Lyu J. Aluminum/Tin-doped UiO-
66 as Lewis acid catalysts for enhanced glucose
isomerization to fructose. Appl. Catal. A: Gen.,
2022, 632, 118501.
https://doi.org/10.1016/j.apcata.2022.118501
6. Kuster B.F.M. 5-Hydroxymethylfurfural (HMF).
A Review Focusing on its Manufacture. Starch –
Stärke, 1990, 42, 314–321.
7. Weitkamp J., Hunger M. Acid and Base Catalysis
on Zeolites. In: Cejka J, Van Bekkum H, Corma
A, Schueth F (eds), Introduction to Zeolite
Molecular Sieves. 2007. Elsevier, 787-836.
8. Pande A., Niphadkar P., Pandare K., Bokade V.
Acid modified H-USY zeolite for efficient
Catalytic Transformation of Fructose to
5-Hydroxymethyl Furfural (Biofuel Precursor) in
Methyl Isobutyl Ketone−Water Biphasic System.
Energy Fuels, 2018, 32, 3783–3791.
9. Patrylak L.K., Konovalov S.V., Yakovenko A.V.,
Pertko O.P., Povazhnyi V.A., Voloshyna Yu.G.,
Melnychuk O.V., Filonenko M.M. Micro–
mesoporous kaolin-based zeolites as catalysts for
glucose transformation into 5-
hydroxymethylfurfural. Appl. Nanosci., 2022.
10. Patrylak L., Konovalov S., Pertko O., Yakovenko
A., Povazhnyi V., Melnychuk O. Obtaining
glucose-based 5-hydroxymethylfurfural on large-
pore zeolites. Eastern-European Journal of
Enterprise Technologies, 2001, 2, N 6 (110), 38–
44.
11. Patrylak L.K., Yakovenko A.V. Alkylation of
isobutane with butenes under microcatalytic
conditions in pulse regime. Voprosy khimii i
khimicheskoi tekhnologii, 2021, 134 (1) 55-61 [in
Ukrainian].
12. Rouqerol F., Rouqerol J., Sing K. Adsorption by
Powders and Porous Solids: Principles,
Methodology and Applications. Academic Press:
San Diego, 1999, 201 .
13. Yakovenko A.V., Patrylak L.K., Manza I.A.,
Patrylak K.I. Study of the acidity of zeolite
alkylation catalysts by temperature programmed
ammonia desorption. Theor. Exp. Chem., 2000,
36, 228–230.
14. Lanzafame P., Barbera K., Papanikolaou G.,
Perathoner S., Centi G., Migliori M., Catizzone
E., Giordano G. Comparison of H+ and NH4
+
forms of zeolites as acid catalysts for HMF
etherification. Catal. Today, 2018, 304, 97-102.
Надійшла до редакції 19.09.2022 р
https://pubmed.ncbi.nlm.nih.gov/?term=Choudhary+V&cauthor_id=23432136
https://pubmed.ncbi.nlm.nih.gov/?term=Mushrif+SH&cauthor_id=23432136
https://pubmed.ncbi.nlm.nih.gov/?term=Ho+C&cauthor_id=23432136
https://pubmed.ncbi.nlm.nih.gov/?term=Anderko+A&cauthor_id=23432136
https://pubmed.ncbi.nlm.nih.gov/?term=Nikolakis+V&cauthor_id=23432136
https://pubmed.ncbi.nlm.nih.gov/?term=Marinkovic+NS&cauthor_id=23432136
https://pubmed.ncbi.nlm.nih.gov/?term=Frenkel+AI&cauthor_id=23432136
https://pubmed.ncbi.nlm.nih.gov/?term=Sandler+SI&cauthor_id=23432136
https://pubmed.ncbi.nlm.nih.gov/?term=Vlachos+DG&cauthor_id=23432136
45 Каталіз та нафтохімія, 2022, №33
ISSN 2707-5796. Catalysis and Petrochemistry, 2022, 33
Перетворення глюкози до 5-гідроксиметилфурфуролу на гранульованих
цеолітних каталізаторах
Любов К. Патриляк1,2, Сергій В. Коновалов1, Анжела В. Яковенко1, Олександра П. Пертко 1,
Володимир А. Поважний 1, Олександр В. Мельничук 1,2
1Інститут біоорганічної хімії та нафтохімії ім. В.П. Кухаря НАН України.
Харківське шосе, 50, Київ 02160, Україна; e-mail: lkpg@ukr.net
2Національний технічний університет України «Київський політехнічний інститут ім. Ігоря Сікорського»,
просп. Перемоги, 37, Київ 03056, Україна
Одержаний з біомаси 5-гідроксиметилфурфурол (5-ГМФ) є потенційною сировиною для виробництва
широкого спектру цінних хімічних речовин і біопалива. Перспективним напрямком є промислове
виробництво 5-ГМФ із гексоз на твердих каталізаторах. Кислотні цеоліти мають великий потенціал у
застосуванні як каталізаторів дегідратації цукрів. Метою даної роботи було отримання гранульованих
цеолітних каталізаторів з оптимальною кислотністю та оцінка їх ефективності в залежності від природи
використовуваного зв’язуючого. Було одержано цеолітний каталізатор без зв’язуючого та зразки з додаванням
10 мас. % каоліну/оксиду алюмінію. Їх пористі характеристики та кислотність вивчали за допомогою
низькотемпературної адсорбції/десорбції азоту, термопрограмованої десорбції аміаку та адсорбції піридину з
ІЧ-контролем. Досліджено активність та селективність каталізаторів для синтезу 5-ГМФ з глюкози в
середовищі диметилсульфоксиду при 160 ◦С. Підтверджено високу ефективність гранульованих зразків у
перетворенні глюкози в 5-ГМФ. Вони не тільки не поступаються, а навіть перевершують порошкоподібні
зразки. Детально розглянуто джерела кислотності Бренстеда і Льюїса амонійної форми цеоліту, яка
демонструє прийнятну активність у перетворенні глюкози (селективність за 5-ГМФ 34%), незважаючи на
незначну кількість центрів Льюїса. Найвищу ефективність демонструє зразок із оксидом алюмінію, який не
тільки не погіршує мікропористі характеристики, але й вдосконалює мезопористість каталізатора.
Селективність за 5-ГМФ на ньому досягає 44 %. Однак розвинена мезопористість зразка із оксидом алюмінію
все ж не є визначальною у його активності. Основний вплив на ефективність каталізатора у одержанні 5-ГМФ
відіграє наявність кислотних центрів середньої сили.
Ключові слова: цеоліти, конверсія глюкози, 5-гідроксиметилфурфурол, зв’язуюче.
|
| id | oai:katalizorgua:article-80 |
| institution | Catalysis and petrochemistry |
| keywords_txt_mv | keywords |
| language | English |
| last_indexed | 2026-03-12T15:50:15Z |
| publishDate | 2022 |
| publisher | V.P. Kukhar Institute of Bioorganic Chemistry and Petrochemistry of the National Academy of Sciences of Ukraine |
| record_format | ojs |
| resource_txt_mv | katalizorgua/06/5a3d86390ed3d052c06df0675bed5c06.pdf |
| spelling | oai:katalizorgua:article-802023-01-20T09:54:45Z Conversion of glucose into 5-hydroxymethylfurfural on granular zeolite catalysts Conversion of glucose into 5-hydroxymethylfurfural on granular zeolite catalysts Patrylak, Lyubov K. Konovalov, Serhii V. Yakovenko, Angela V. Pertko, Oleksandra P. Povazhnyi, Volodymyr A. Melnychuk, Oleksandr V. zeolite, glucose conversion, 5-hydroxymehtylfurfural, binder цеоліти, конверсія глюкози, 5-гідроксиметилфурфурол, зв’язуюче Biomass-derived 5-hydroxymethylfurfural (5-HMF) is a potential raw material for the production of a wide range of valuable chemicals and biofuels. Industrial production of 5-HMF from hexoses on solid catalysts is promising nowadays. Acid zeolites have great potential in application as catalysts for the dehydration of sugars. The purpose of this work was to obtain granular zeolite catalysts with optimal acidity and evaluate their effectiveness depending on the nature of the binder used. A zeolite catalyst without binder and samples with 10 wt % of kaolin/alumina were prepared. Their porous characteristics and acidity were studied by means of nitrogen low temperature adsorption/desorption, ammonia thermo-programmed desorption, and pyridine adsorption with IR control. The activity and selectivity of the catalysts for 5-HMF synthesis from glucose in the dimethyl sulfoxide medium at 160 ◦C were studied. The high efficiency of granular samples in glucose transformation into 5-HMF is confirmed. They are not only not inferior to, but even superior to, powdered samples. The component sources of Brønsted and Lewis acidity of the ammonium form of zeolite, which demonstrates acceptable activity (selectivity for 5-HMF is 34 %) despite the small number of Lewis centers, are considered in detail. The highest efficiency is demonstrated by the sample with aluminum oxide, which not only does not significantly deteriorate the microporous characteristics but also improves the mesoporosity of the catalyst. The selectivity towards 5-HMF on it reaches 44%. However, the developed mesoporosity of the sample with aluminum oxide is not critical to its activity. The main influence on the effectiveness of the catalyst in the synthesis of 5-HMF is played by the presence of acid centers of medium strength. Biomass-derived 5-hydroxymethylfurfural (5-HMF) is a potential raw material for the production of a wide range of valuable chemicals and biofuels. Industrial production of 5-HMF from hexoses on solid catalysts is promising nowadays. Acid zeolites have great potential in application as catalysts for the dehydration of sugars. The purpose of this work was to obtain granular zeolite catalysts with optimal acidity and evaluate their effectiveness depending on the nature of the binder used. A zeolite catalyst without binder and samples with 10 wt % of kaolin/alumina were prepared. Their porous characteristics and acidity were studied by means of nitrogen low temperature adsorption/desorption, ammonia thermo-programmed desorption, and pyridine adsorption with IR control. The activity and selectivity of the catalysts for 5-HMF synthesis from glucose in the dimethyl sulfoxide medium at 160 ◦C were studied. The high efficiency of granular samples in glucose transformation into 5-HMF is confirmed. They are not only not inferior to, but even superior to, powdered samples. The component sources of Brønsted and Lewis acidity of the ammonium form of zeolite, which demonstrates acceptable activity (selectivity for 5-HMF is 34 %) despite the small number of Lewis centers, are considered in detail. The highest efficiency is demonstrated by the sample with aluminum oxide, which not only does not significantly deteriorate the microporous characteristics but also improves the mesoporosity of the catalyst. The selectivity towards 5-HMF on it reaches 44%. However, the developed mesoporosity of the sample with aluminum oxide is not critical to its activity. The main influence on the effectiveness of the catalyst in the synthesis of 5-HMF is played by the presence of acid centers of medium strength. V.P. Kukhar Institute of Bioorganic Chemistry and Petrochemistry of the National Academy of Sciences of Ukraine 2022-10-26 Article Article application/pdf https://kataliz.org.ua/index.php/journal/article/view/80 10.15407/kataliz2022.33.038 Catalysis and petrochemistry; No. 33 (2022): Catalysis and petrochemistry; 38-45 Каталіз та нафтохімія; № 33 (2022): Каталіз та нафтохімія; 38-45 2707-5796 2412-4176 10.15407/kataliz2022.33 en https://kataliz.org.ua/index.php/journal/article/view/80/73 Copyright (c) 2022 Catalysis and petrochemistry |
| spellingShingle | цеоліти конверсія глюкози 5-гідроксиметилфурфурол зв’язуюче Patrylak, Lyubov K. Konovalov, Serhii V. Yakovenko, Angela V. Pertko, Oleksandra P. Povazhnyi, Volodymyr A. Melnychuk, Oleksandr V. Conversion of glucose into 5-hydroxymethylfurfural on granular zeolite catalysts |
| title | Conversion of glucose into 5-hydroxymethylfurfural on granular zeolite catalysts |
| title_alt | Conversion of glucose into 5-hydroxymethylfurfural on granular zeolite catalysts |
| title_full | Conversion of glucose into 5-hydroxymethylfurfural on granular zeolite catalysts |
| title_fullStr | Conversion of glucose into 5-hydroxymethylfurfural on granular zeolite catalysts |
| title_full_unstemmed | Conversion of glucose into 5-hydroxymethylfurfural on granular zeolite catalysts |
| title_short | Conversion of glucose into 5-hydroxymethylfurfural on granular zeolite catalysts |
| title_sort | conversion of glucose into 5-hydroxymethylfurfural on granular zeolite catalysts |
| topic | цеоліти конверсія глюкози 5-гідроксиметилфурфурол зв’язуюче |
| topic_facet | zeolite glucose conversion 5-hydroxymehtylfurfural binder цеоліти конверсія глюкози 5-гідроксиметилфурфурол зв’язуюче |
| url | https://kataliz.org.ua/index.php/journal/article/view/80 |
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