Colloidal and Nanosized Catalysts in Organic Synthesis: XXIV. Study of Hydrogenation of Furan and Its Derivatives in the Presence of MgO-Supported Nickel and Cobalt Nanoparticles

Article abstract of DOI:10.1134/S1070363220060018

Abstract: The processes of hydrogenation of furan and its derivatives (2-methylfuran, furfuryl alcohol, and furfural) in plug-flow type reactor under atmospheric hydrogen pressure at 20–220°С in the presence of supported nickel nanoparticles prepared via chemical reduction have been investigated. It has been found that nickel nanoparticles supported on magnesium oxide surface are the most reactive and stable under the considered conditions. This catalyst allows the corresponding hydrogenation products with 100percent yield and complete conversion of the substrate.

Full text of DOI:10.1134/S1070363220060018

ISSN 1070-3632, Russian Journal of General Chemistry, 2020, Vol. 90, No. 6, pp. 931–935. © Pleiades Publishing, Ltd., 2020.
Russian Text © The Author(s), 2020, published in Zhurnal Obshchei Khimii, 2020, Vol. 90, No. 6, pp. 823–828.
Colloidal and Nanosized Catalysts in Organic Synthesis:
XXIV.1 Study of Hydrogenation of Furan and Its Derivatives
in the Presence of MgO-Supported Nickel
and Cobalt Nanoparticles
Yu. V. Popova,*, V. M. Mokhova, D. N. Nebykova, P. M. Shirkhanyana,
T. A. Gendlera, and V. V. Shemeta
a Volgograd State Technical University, Volgograd, 400006 Russia
*e-mail: tons@vstu.ru
Received December 20, 2019; revised December 20, 2019; accepted December 26, 2019
Abstract—The processes of hydrogenation of furan and its derivatives (2-methylfuran, furfuryl alcohol, and furfural)
in plug-flow type reactor under atmospheric hydrogen pressure at 20–220°С in the presence of supported nickel
nanoparticles prepared via chemical reduction have been investigated. It has been found that nickel nanoparticles
supported on magnesium oxide surface are the most reactive and stable under the considered conditions. This cata-
lyst allows the corresponding hydrogenation products with 100% yield and complete conversion of the substrate.
Keywords: catalysis, nanoparticles, nickel, cobalt, furfural, furan
DOI: 10.1134/S1070363220060018
Development of processes based on renewable sources
has become an extremely important field of chemical
engineering. One of the major products of biomass
conversion is furfural [2] which is in its turn a precursor
of a series of valuable organic compounds such as furfuryl
alcohol, tetrahydrofurfuryl alcohol, 2-methylfuran,
2-methyltetrahydrofuran, furan, and tetrahydrofuran
[3, 4].
1 atm of hydrogen has allowed tetrahydrofurfuryl alcohol
with 14.9% yield [12]. Hydrogenation of furfural in
the presence of Ru/C in liquid 1-butanol (165°С and
25 atm of hydrogen) has afforded furfuryl alcohol,
furfural conversion being 91% and the product yield
being 42.4% [13].
Ruthenium catalysts have been utilized in the
production of tetrahydrofurfuryl alcohol via hydrogenation
if furfuryl alcohol [14–16]. The reaction occurs at
40–120°С and excessive pressure 20–60 atm. Nickel–
palladium catalysts have also exhibited high efficiency in
this reaction. For example, the yield of tetrahydrofurfuryl
alcohol of 96% has been achieved in the presence of
Ni–Pd/SiO2 at 40°С and 40 atm, the reaction duration
being 2 h [17].
Industrial hydrogenation of furfural is performed
in the presence of copper-chromium catalysts at high
pressure (up to 250 atm) and temperature 60–220°С,
the yield with respect to furfuryl alcohol being 60–97%
[5]. Hydrogenation of furfural with hydrogen can be
also performed at pressure up to 20 atm and temperature
up to 260°С when catalyzed with copper nanoparticles
immobilized on various supports, the furfuryl alcohol
being 96% [6–8].
2-Methyltetrahydrofuran has been obtained in 100%
yield via hydrogenation of 2-methylfuran in the presence
of Pd/C at 200°С and H2 : 2-methylfuran molar ratio of
(10–25) : 1 [18].
Copper catalysts have been utilized in hydrogenolysis
of furfural yielding 2-methylfuran (51.1–93.5%) at
hydrogen pressure of 1–90 atm and temperature 150–
280°С [9–11]. Hydrogenation of furfural with molecular
hydrogen in the presence of NiO/SiO2 at 200°С and
Processes of furan hydrogenation in the presence
of rhodium and rhenium catalysts at temperature up to
200°С and pressure 60 atm have been described [19–24];
the reactions have led to the formation of products of
hydrogenolysis and ring opening.
1 For communication XXIII, see [1].
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POPOV et al.
Fig. 2. Composition of the catalysate as a function of
temperature of 2-methylfuran hydrogenation at 1b : H2 molar
ratio 1 : 2.5 [specific substrate feeding rate 0.3 L/(kgcat h), Ni0/
MgO]; (1) 2-methyltetrahydrofuran, (2) 2-methylfuran, and
(3) ring opening products.
Fig. 1. Composition of the catalysate as a function of
temperature of furan hydrogenation at 1a : H2 molar ratio
1 : 2.5 [specific substrate feeding rate 0.3 L/(kgcat h), Ni0/
MgO]; (1) tetrahydrofuran and (2) furan.
We have earlier investigated the processes of hydro-
electrons detector: CBS, elemental analysis method:
EDS). The catalysts showed variable shape and size of
the particles and their agglomerates. The particles with
size starting from 70–100 nm were obtained, depending
on the used support.
genation of a series of unsaturated hydrocarbons in a
plug-flow reactor at atmospheric pressure of hydrogen
in the presence of nickel nanoparticles immobilized on
various supports [25]. The nanostructured nickel catalysts
have exhibited high efficiency in the said processes.
The present study aimed to investigate the processes of
hydrogenation of furan and its derivatives (2-methylfuran,
furfural, and furfuryl alcohol) in a plug-flow reactor at
atmospheric pressure of hydrogen using nickel and cobalt
catalysts applied on various supports: γ-Al2O3, NaX
zeolite, SiO2, and MgO (Scheme 1).
Preliminary assessment of the efficiency of the
obtained catalysts (hydrogenation of furan 1a at 100°С,
other conditions also being identical) revealed that the
yield of the target product 2a was significantly dependent
on the nature of the carrier. The yield of the hydrogenation
product 2a and the substrate 1a conversion did not
exceed 1–1.5% in the presence of Co0/γ-Al2O3 or 13%
in the presence of Ni0/γ-Al2O3. When cobalt and nickel
particles supported on NaX or SiO2 were used in the same
reaction, the yield of the product 2a was below 4%. The
use of MgO as the support significantly enhanced the
yield of the product 2a. For example, 20% yield of the
hydrogenation product 2a and the substrate 1a conversion
were achieved in the presence of Co0/MgO.
The experiments were performed using a plug-
flow reactor (Parr 5400 Tubular Reactor System) at
temperature 20–220°С, atmospheric pressure, 2.5-fold
molar excess of hydrogen, specific feeding rate of the
hydrogenated substrate 0.36 L/(kgcat h), in bulk. The
reaction mixtures were analyzed by means of 1Н NMR
spectroscopy, GLC, and chromato–mass spectrometry.
The catalysts were prepared via impregnation of a
support with an aqueous solution of the corresponding
metal salt during 24 h, followed by filtration, washing with
distilled water, and reduction with sodium borohydride
in water at 20–25°С [26]. The obtained catalysts were
analyzed by means of scanning electron microscopy using
a FEI Versa 3D Dual Beam instrument (working distance
10 mm, secondary electrons detector: ETD, backscattered
Elucidation of the effect of the amount of nickel on
MgO support on the hydrogenation product yield revealed
that the optimal ratio between nickel(II) chloride and
MgO, was 1.2 : 1. Hydrogenation of compound 1a in
the presence of Ni0/MgO afforded product 2a in 68%
yield at temperature as low as 25°С; the products of ring
opening were not detected in the catalysate. The increase
in temperature to 100°С allowed tetrahydrofuran 2a with
100% yield (Fig. 1). Further increase in temperature led
to the formation of the ring opening products (butan-1-ol,
26% at 160°С). It was found that the hydrogenation of
furan 1a in the presence of Ni0/MgO led to the product
2a yield and the substrate 1a conversion were 45–80%
higher than in the presence of Co0/MgO, other conditions
being the same.
Scheme 1.
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933
Fig. 3. Composition of the catalysate as a function of
Fig. 4. Composition of the catalysate as a function of
temperature of furfuryl alcohol hydrogenation at 1c : H2 molar
ratio 1 : 2.5 [specific substrate feeding rate 0.3 L/(kgcat h), Ni0/
MgO]; (1) tetrahydrofurfuryl alcohol, (2) furfuryl alcohol, and
(3) 2-methyltetrahydrofuran.
temperature of furfural hydrogenation at 3 : H2 molar ratio
1 : 2.5 [specific substrate feeding rate 0.3 L/(kgcat h), Ni0/
MgO]; (1) tetrahydrofurfuryl alcohol, (2) furfuryl alcohol,
(3) furfural, and (4) 2-methyltetrahydrofuran.
Similarly, 2-methylfuran 1b was involved in
the hydrogenation in the presence of Ni0/MgO.
2-Methyltetrahydrofuran 2b was obtained with yield up
to 94% and selectivity 100% at the specific feeding rate
of the substrate 1b 0.3 L/(kgcat h), 2.5-fold molar excess
of hydrogen, pressure 1 atm, and temperature (Fig. 2).
Further increase in temperature also led to the formation
of the furan ring opening products (16.6% at 140°С).
at complete conversion of the substrate was achieved at
temperature as high as 200°С. The said effect was due to
the influence of the steric and electron-accepting factors
of the СН2ОН group on the ring stability [27].
Furfural 3 produced via biomass conversion is
an important source for the synthesis of furan and
its derivatives [28]. Hydrogenation of aldehyde 3 in
the presence of Ni0/MgO was studied at temperature
120–200°С, specific feeding rate of the substrate
0.36 L/(kgcat h), and 2.5-foldmolar excess of hydrogen
(Scheme 2, Fig. 4).
It should be noted that furan 1a was more prone
to hydrogenation under the considered conditions in
comparison with 2-methylfuran 1b, likely due to the
steric effect of the substituent. For example, conversion
of compound 1a at 60°С (other conditions being identical)
was found 15% higher in comparison with compound 1b.
Similar results have been earlier obtained in the presence
of the Adams catalysts [27]. The rate constant of furan
1a hydrogenation has been found 12% higher than that
of 2-methylfuran 1b.
Analysis of the experimental data suggested that
the decrease in the reactivity of the furan ring in the
aldehyde 3 towards hydrogenation (the presence of the
type 2 substituent, НС=О) led to a two-stage process: the
hydrogenation of the ring affording product 2c started
only upon the reduction of the carbonyl group of the
substrate 3 into the hydroxyl one (compound 1c). The
highest yield of the alcohol 2c at 200°С was of 53% at
complete conversion of aldehyde 3. Further increase
in temperature led to the increase in the fraction of the
hydrogenolysis of the hydroxyl group of the alcohol 1c
yielding compound 1b, its content in the catalysate being
13% at 240°С.
Hydrogenation of furfuryl alcohol 1c in the presence
of Ni0/MgO was performed at 100–200°С, specific
feeding rate of alcohol 1a 0.36 L/(kgcat h), and 2.5-
fold molar excess of hydrogen. The composition of
catalysate obtained in that reaction as function of the
process temperature is shown in Fig. 3. It should be
noted that hydrogenation of the alcohol 1c occurred at
higher temperature in comparison with compounds 1a
and 1b. 94% yield of tetrahydrofurfuryl alcohol 2c 94%
It should be noted that the attempt to hydrogenate
the furan ring in ethyl 2-furoate under the conditions of
hydrogenation of compound 3 failed, since the electron-
Scheme 2.
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POPOV et al.
accepting ethoxycarbonyl group was not involved in the
hydrogenation.
73.8 (71) [M + 1]+, 70.9 (100) [M – 1], 70.0 (8), 69.0 (3),
55.0 (3), 42.9 (2), 42.0 (2), 41.0 (8), 40.1 (2).
b. Compound 1a [0.3 L/(kgcat h)] and hydrogen
[230 L/(kgcat h)] were fed to 6 g of the Ni0/MgO catalyst
at 100°С. Conversion of furan 1a 98.7%, selectivity with
respect to product 2a 100%, yield 98.7%.
In summary, we found that nickel nanoparticles
stabilized on the MgO surface exhibited high catalytic
activity towards hydrogenation of furan and its derivatives
at pressure of 0.1 MPa and temperature 120–200°С,
affording the hydrogenation products in up to 100%
yield and selectivity in a plug-flow reactor. The obtained
data (upon comprehensive investigation of the kinetic
features and further optimization) can form a basis for the
development of new efficient process for hydrogenation
of furan and its derivatives.
c. Compound 1a [0.3 L/(kgcat h)] and hydrogen
[230 L/(kgcat h)] were fed to 6 g of the Co0/MgO catalyst
at 25°С. Conversion of furan 1a 20%, selectivity with
respect to product 2a 100%, yield 20%.
2-Methyltetrahydrofuran (2b). a. Compound 1b
[0.3 L/(kgcat h)] and hydrogen [190 L/(kgcat h)] were fed
to 6 g of the Ni0/MgO catalyst at 20°С. Conversion of
2-methylfuran 1b 56.5%, yield 56.5%. Mass spectrum
(EI), m/e (Irel, %): 86.7 (3) [M + 1]+, 72.7 (5), 56.8 (87),
55.8 (91), 54.9 (46), 43.0 (30), 41.0 (100), 40.2 (13).
EXPERIMENTAL
Chromato–mass spectroscopy analysis was performed
using a Saturn 2100 T/GC3900 instrument (EI, 70 eV).
Catalysts preparation. The catalysts were prepared
via impregnation of a solid support (MgO, SiO2, γ-Al2O3,
or NaX zeolite) with an aqueous solution of nickel(II) or
cobalt(II) chloride hexahydrate (0.25–1.2 g of the salt per
1 g of the support) during 5–6 h, followed by filtration,
washing with distilled water, and the treatment with an
aqueous solution of sodium borohydride at 20–25°С
during 20–30 min. The nickel particles size at the surface
of the so obtained catalyst was of 70–100 nm [29]. The
moist catalyst was loaded in the reactor and dried in a
hydrogen stream at 120–300°С prior to the process.
b. Compound 1b [0.3 L/(kgcat h)] and hydrogen
[190 L/(kgcat h)] were fed to 6 g of the Ni0/MgO catalyst
at 100°С. Conversion of 2-methylfuran 1b 97.7%,
selectivity with respect to product 2b 96.6%, yield 94.4%.
Tetrahydrofurfuryl alcohol (2c). a. Compound 3
[0.3 L/(kgcat h)] and hydrogen [210 L/(kgcat h)] were fed
to 6 g of the Ni0/MgO catalyst at 200°С. Conversion of
aldehyde 3 98.5%, yield 52.7%. Mass spectrum (EI), m/e
(Irel, %): 102.8 (5) [M + 1]+, 42.8 (14), 71.0 (100), 70.0
(11), 43.0 (52), 42.0 (12), 41.0 (50). Furfuryl alcohol
(1c), yield 37.9%. Mass spectrum (EI), m/e (Irel, %): 98.8
(4) [M + 1]+, 97.8 (51) [M]+, 96.8 (10), 81.9 (9), 81.0 (100),
69.0 (11), 53.0 (10), 41.0 (4). 2-Methyltetrahydrofuran
(2c), yield 3%.
General procedure for hydrogenation. The reactions
were performed in a plug-flow reactor at atmospheric
pressure and temperature 20–200°С. The reactions
could occur either in a gas phase or in the gas–liquid–
solid catalyst system, depending on the boiling point of
the starting compounds. The laboratory-scale reactor
consisted of a 12Kh18N10T steel tube with inner diameter
9 mm and the heating zone height 50 mm put in an electric
oven. The catalyst was loaded in a middle part of the
reactor, surrounded by inert filler (quartz attachment).
Liquid furan or its derivatives were fed at rate of
0.3 L/(kgcat h), hydrogen feeding rate being 190‒
230 L/(kgcat h) (2.5-fold molar excess). The examples
below are given for the catalyst prepared via impregnation
of pressed MgO granules with nickel(II) chloride hexa-
hydrate at the mass ratio 1.2 : 1, followed by reduction.
b. Compound 1c [0.3 L/(kgcat h)] and hydrogen
[210 L/(kgcat h)] were fed to 6 g of the Ni0/MgO catalyst
at 200°С. Conversion of substrate 1c 98.9%, yield 94.5%.
2-Methyltetrahydrofuran (2b), yield 5.3%
FUNDING
This study was financially supported by the Russian
Foundation for Basic Research (project no. 19-33-90117).
CONFLICT OF INTEREST
No conflict of interest was declared by the authors.
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