Colloid and Nanosized Catalysts in Organic Synthesis: XXII. Hydrogenation of Cycloolefins Catalyzed by Immobilized Transition Metals Nanoparticles in a Three-Phase System

Article abstract of DOI:10.1134/S1070363219100013

The processes of unsaturated cyclic hydrocarbons hydrogenation in a three-phase gas-liquid-solid catalyst system in the presence of nanostructured nickel, cobalt, or iron catalysts in a flow reactor at 130°C and atmospheric pressure have studied. RX3Extra activated carbon, γ-Al₂O₃, NaX zeolite, and Purolite CT-175 cation-exchange resin have been used as supports; NaBH₄ and NH₂NH₂·H₂O were used as reducing agents. The catalytic activity of supported nanoparticles and their selectivity with respect to the product of exhaustive hydrogenation have been investigated.

Full text of DOI:10.1134/S1070363219100013

ISSN 1070-3632, Russian Journal of General Chemistry, 2019, Vol. 89, No. 10, pp. 1985–1989. © Pleiades Publishing, Ltd., 2019.
Russian Text © The Author(s), 2019, published in Zhurnal Obshchei Khimii, 2019, Vol. 89, No. 10, pp. 1479–1485.
Colloid and Nanosized Catalysts in Organic Synthesis:
XXII.1 Hydrogenation of Cycloolefins Catalyzed by Immobilized
Transition Metals Nanoparticles in a Three-Phase System
D. N. Nebykova*, Yu. V. Popova, V. M. Mokhova, S. E. Latyshovaa, K. V. Shcherbakovaa,
N. V. Nemtsevaa, and E. V. Shishkina
a Volgograd State Technical University, pr. Lenina 28, Volgograd, 400131 Russia
*e-mail: nervwho@gmail.com
Received March 12, 2019; revised March 12, 2019; accepted March 14, 2019
Abstract—The processes of unsaturated cyclic hydrocarbons hydrogenation in a three-phase gas–liquid–solid
catalyst system in the presence of nanostructured nickel, cobalt, or iron catalysts in a flow reactor at 130°C and
atmospheric pressure have studied. RX3Extra activated carbon, γ-Al2O3, NaX zeolite, and Purolite CT-175 cation-
exchange resin have been used as supports; NaBH4 and NH2NH2·H2O were used as reducing agents. The catalytic
activity of supported nanoparticles and their selectivity with respect to the product of exhaustive hydrogenation
have been investigated.
Keywords: nanoparticles, nickel, cobalt, iron, hydrogenation, zeolite
DOI: 10.1134/S1070363219100013
Cyclic hydrocarbons are widely applied in different
branches of chemical industry: fuel and energetics, oil
processing, perfumery, pharmaceutics, and polymer
production. For example, tetrahydrodicyclopentadiene
is a component of high-energy propellant and an inter-
mediate in the production of adamantane-based drugs;
cyclooctane is the most efficient precursor of suberic acid
which is used in the production of synthetic fibers, plas-
tics, and drugs; pinane is used in the synthesis of pinane
hydroperoxide which can serve as initiator of butadiene
copolymerization with styrene.
hydrogenation industry development. Metal nanoparticles
can be applied as stabilized colloid solutions in liquid-
phase processes [4] or as supported nanoparticles in
gas-phase processes [5–10]. For example, a mixture of
cyclooctene 5 and cyclooctane 6 has been obtained with
selectivity 24 and 76%, respectively, at complete conver-
sion of starting compound 4 using PEGylated palladium
nanoparticles in an autoclave (liquid phase) at 90°С and
30 atm during 50 min [11]. Palladium nanoparticles have
been used for hydrogenation of dicyclopentadiene 1 at
50°С and 10 atm during 2 h, the yield of exhaustive hy-
drogenation product 3 being 76% at conversion of starting
dicyclopentadiene 1 86% [12].
The mentioned compounds can be obtained via
catalytic hydrogenation of the corresponding unsatu-
rated cyclic hydrocarbons (Scheme 1). In industry, these
processes are mainly performed in a batch reactor, under
relatively harsh conditions in a liquid phase. For example,
dicyclopentadiene 1 can be hydrogenated at temperature
120–130°С and pressure 15 atm [2]. Hydrogenation of
1,5-cyclooctadiene 4 occurs at 70°С and 10 atm on sus-
pended Pd/Al2O3 catalyst [3].
We have earlier studied gas-phase hydrogenation of
unsaturated cyclic hydrocarbons at 140–240°С in the
presence of nickel nanoparticles on different supports
[13]. However, scaling of the process under these condi-
tions can lead to enhancement of side reactions related to
cycle rupture and rearrangement which in its turn results
in the catalyst deactivation with the increase in the inter-
regeneration period. Therefore, in this study we inves-
tigated hydrogenation of the corresponding cycloolefins
in a three-phase system (under conditions of hydrogen
diffusion through a liquid fild of hydrogenated olefin to
active sites of the catalyst).
The use of nanocatalysts which allow significant ac-
celeration of these processes is among modern trends in
1 For communication XХI, see [1]
1985

1986
NEBYKOV et al.
Scheme 1.
H2, cat
H2, cat
p
p
1
2
3
H2, cat
H2, cat
p
p
4
5
6
H2, cat
p
7
8
The experiments were performed in a Parr 5400
TubularReactorSystem flow reactor in the presence of
transition metal nanoparticles (nickel, cobalt, or iron)
immobilized at different supports: RX3Extra activated
carbon, γ-Al2O3, NaX zeolite, or Purolite CT-175 cation-
exchange resin. The efficiency of the probed catalysts
was compared under identical conditions: temperature
130°С, atmospheric pressure, 2-fold molar excess of
hydrogen with respect to a carbon–carbon double bond,
catalyst loading 2 g, and liquid reagent supply 0.0036 L/h
without any solvent. The reaction mixture composition
was analyzed by means of 1Н NNR spectroscopy, GLC,
and chromato–mass spectrometry.
3 (Table 1, Exp. 5–12). The highest conversion of diene
1 was observed in the presence of nickel nanoparticles
on γ-Al2O3 (Table 1, Exp. 7) (99.6%), the selectivity with
respect to product 3 being 99.2%. It should be noted that
direct reduction of cobalt at the support surface with
hydrazine monohydrate was impossible, and the catalyst
preparation demanded additional heating at 400°С during
4 h; yet the obtained catalyst exhibited low activity under
the probed conditions.
Comparison of the nickel catalysts immobilized on
γ-Al2O3, NaX zeolite, or the cation-exchange resin re-
vealed no significant difference in activity and selectivity,
in contrast to the catalysts prepared using the RX3 Extra
activated carbon (Table 1, Exp. 4 and 8).
The catalysts were prepared via impregnation of the
support with an aqueous solution of the corresponding
metal salt during 24 h, followed by the reduction with
sodium borohydride in water at 20–25°С (method a) [14]
or with hydrazine monohydrate in the presence of NaOH
at 80–100°С (method b) [15]. Surface morphology of the
obtained catalysts was different in terms of shape and size
of the particles and their aggregates. Depending on the
support and the reduction method, 40 to 140 nm metal
particles and their aggregates with size up to 250 nm were
formed at the surface.
Iron nanoparticles did not exhibit significant catalytic
activity. The highest conversion of dicyclopentadiene 1
was 15.2% in the presence of iron nanoparticles reduced
with hydrazine monohydrate on γ-Al2O3.
It is interesting to notice that hydrogenation of
1,5-cyclooctadiene 4 at 4-fold excess of hydro-
gen and conditional residence time of the substrate
0.068 h kgcat/mol yielded the product of partial hydro-
genation 5 with selectivity up to 100% when using any
of the studied catalysts (Table 2); that fact could be
explained by low rate of compound 4 hydrogenation
due to transannular interactions [16]. The nickel- and
cobalt-containing catalysts were found the most efficient,
yet in no case did we observe complete conversion of the
substrate (Table 2).
Hydrogenation of dicyclopentadiene 1 was studied at
4-fold excess of hydrogen and conditional residence time
of the substrate 0.074 h kgcat/mol. The highest efficiency
was revealed in the cases of cobalt (method a) and nickel
(methods a and b) nanoparticles. Hydrogenation of dicy-
clopentadiene 1 occurred with sufficiently high selectivity
with respect to the product of exhaustive hydrogenation
Hydrogenation of α-pinene 7 was studied at 2-fold
excess of hydrogen and conditional residence time of
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COLLOID AND NANOSIZED CATALYSTS IN ORGANIC SYNTHESIS: XXII.
1987
Table 1. Conversion of dicyclopentadiene 1 and yield of the hydrogenation products
Yield, %
Exp.
no.
Catalyst
Support
Reducer
NaBH4
Conversion, %
2
3
1
2
Ni
Ni
Ni
Ni
Ni
Ni
Ni
Ni
Co
Co
Co
Co
Fe
Purolite CT-175
Zeolite NaX
γ-Al2O3
98.9
98.7
98.9
97.8
98.6
98.3
99.6
11.7
98.5
97.7
97.5
5.3
1.9
97.0
97.7
97.8
96.7
97.6
97.3
98.8
0.6
NaBH4
1.0
1.1
3
NaBH4
4
RX3Extra
NaBH4
1.1
5
Purolite CT-175
Zeolite NaX
γ-Al2O3
NH2NH2·H2O
NH2NH2·H2O
NH2NH2·H2O
NH2NH2·H2O
NaBH4
1.0
6
1.0
7
0.8
8
RX3Extra
11.1
3.7
9
Purolite CT-175
Zeolite NaX
γ-Al2O3
94.8
94.35
96.2
0.7
10
11
12
15
NaBH4
3.35
1.3
NaBH4
RX3Extra
NaBH4
4.6
γ-Al2O3
NH2NH2·H2O
15.2
12.2
3.0
the substrate 0.087 h kgcat/mol. α-Pinene hydrogenation
could be accompanied by side isomerization reactions,
depending on the support acidity. Those processes were
less pronounced in the cased of the nickel and cobalt
catalysts, the selectivity with respect to product 8 reaching
99.7% (Table 3), except for cobalt nanoparticles on NaX
zeolite (Table 3, Exp. 9), the content of the isomeriza-
tion products being up to 38.7% in the latter case. In the
case of iron nanoparticles, the isomerization processes
were more prominent, and the content of pinane 8 in the
products did not exceed 18.6%.
We further investigated the stability of the most active
catalysts. It was shown that the nickel catalysts immo-
bilized on the cation-exchange resin and γ-Al2O3 were
Table 2. Conversion of cyclooctadiene 4 and yield of the hydrogenation products
Yield, %
Exp.
no.
Catalyst
Support
Reducer
NaBH4
Conversion, %
5
6
0
0
0
0
0
0
0
0
0
0
0
1
2
Ni
Ni
Ni
Ni
Ni
Ni
Ni
Ni
Co
Co
Co
Purolite CT-175
Zeolite NaX
γ-Al2O3
96.5
97.2
96.8
82.1
94.7
96.6
96.1
31.3
92.5
93.6
96.2
96.5
97.2
96.8
82.1
94.7
96.6
96.1
31.3
92.5
93.6
96.2
NaBH4
3
NaBH4
4
RX3Extra
NaBH4
5
Purolite CT-175
Zeolite NaX
γ-Al2O3
NH2NH2·H2O
NH2NH2·H2O
NH2NH2·H2O
NH2NH2·H2O
NaBH4
6
7
8
RX3Extra
9
Purolite CT-175
Zeolite NaX
γ-Al2O3
10
11
NaBH4
NaBH4
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 89 No. 10 2019

1988
NEBYKOV et al.
Table 3. Conversion of α-pinene 7 and yield of the hydrogenation products
Yield, %
otherа
Exp
no.
Catalyst
Support
Reducer
NaBH4
Conversion, %
8
1
2
Ni
Ni
Ni
Ni
Ni
Ni
Ni
Co
Co
Co
Fe
Fe
Fe
Purolite CT-175
Zeolite NaX
γ-Al2O3
99.7
81.5
99.9
99.7
99.9
99.5
99.7
97.7
98.5
97.8
95.3
85.2
96.5
98.6
75.0
99.6
99.5
99.2
96.6
98,6
71.9
59.8
96.4
16.7
0.1
1.1
6.5
NaBH4
3
NaBH4
0.3
4
RX3Extra
NaBH4
0.2
5
Purolite CT-175
Zeolite NaX
γ-Al2O3
NH2NH2·H2O
NH2NH2·H2O
NH2NH2·H2O
NaBH4
0.7
6
2.9
7
1.1
8
Purolite CT-175
Zeolite NaX
γ-Al2O3
25.8
38.7
1.4
9
NaBH4
10
11
12
13
NaBH4
Purolite CT-175
Zeolite NaX
Zeolite NaX
NaBH4
78.6
85.1
77.9
NaBH4
NH2NH2·H2O
18.6
a Products of isomerization and subsequent hydrogenation
the most stable: the substrate conversion and the target
products yield were not reduced over 10 h. Other nickel
and cobalt catalysts exhibited the 10–15% decrease in the
products yield during 10 h, but the catalytic activity was
restored upon 1 h purging with hydrogen.
of scanning electron microscopy using a FEI Versa 3D
DualBeam instrument.
Catalysts preparation. The catalysts were prepared
via impregnation of 2 g of the support (fraction 1–1.5 mm)
with aqueous solution of nickel(II) chloride hexahydrate,
cobalt(II) chloride hexahydrate, or iron(II) sulfate hep-
tahydrate (2 g in 5 mL of water) during 24 h. After the
impregnation, filtering off, and washing with distilled
water, the catalyst was reduced with sodium borohydride
(0.1 g in 10 mL of water) at 20–25°С during 20–30 min
(method a) or with hydrazine monohydrate (10 mL in
10 mL of water) in the presence of 0.5 g of NaOH at
80–100°С during 50–60 min (method b).
In summary, nickel nanoparticles (prepared via reduc-
tion with sodium borohydride or hydrazine monohydrate)
revealed the highest catalytic activity and stability in the
three-phase hydrogenation of unsaturated cyclic hydro-
carbons. The studied nanoparticles could be arranged in
the following series of decreasing catalytic activity: Ni >
Co > Fe. The Purolite CT-175 cation-exchange resin and
γ-Al2O3 were found the optimal supports for the nickel
nanoparticles.
Hydrogenation (general procedure). The reaction
was performed in a Parr 5400 Tubular Reactor System
laboratory device: reactor – steel tube (volume 20 cm3,
length 0.5 m, inner diameter 7 mm) in an electric oven
(heating zone height 300 mm). GV-7 hydrogen genera-
tor with adjustable gas feed served as hydrogen supply.
EXPERIMENTAL
The catalyzates were analyzed by means of chromato–
mass spectrometry using a Saturn 2100 T/GC3900 instru-
1
ment (EI, 70 eV). The Н NMR spectra were obtained
using a Varian Mercury-300 spectrometer operating at
300 MHz. Quantitative GLC analysis of the reaction mass
was performed using a Kristallyuks-4000M instrument
(tstart = 100–210°С, tevap = 250°С, polar column HP-5,
lcol = 50 m, dcol = 0.52 μm, carrier gas: nitrogen, flame
ionization detector, tdet = 250°C, solvent: n-hexane).
Morphology of the catalysts was analyzed by means
Humid catalyst was loaded in the reactor, 100 mm
layer of inert carrier (quartz, same fraction) was applied
from above, and the catalyst was dried in a hydrogen
stream at 130°С prior to the reaction during 1–1.5 h.After
that, the required amounts of the substrate and hydrogen
were fed in the reactor at the desired temperature from
above. The obtained data are collected in Tables 1–3
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 89 No. 10 2019

COLLOID AND NANOSIZED CATALYSTS IN ORGANIC SYNTHESIS: XXII.
1989
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trum, m/e (Irel, %): 136.9 (3.4) [М + 1]+, 136 (30.9), 120.9
(45.9), 95.0 (66.6), 67.0 (99.9).
Dihydrodicyclopentadiene (2). 1Н NMR spectrum,
δ, ppm: 1.11–1.23 m (4H, СН2), 1.35 q (2H, СН2, J =
22.3 Hz), 2.03–2.18 m (4H, СН2 + 2СН), 2.42 m (1H,
СН). 2.89 m (1H, СН), 5.41 m (1H, СН=), 5.51 m (1H,
СН=).
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using 2 g of a catalyst at 130°С, hydrogen to alkene
molar ratio 4 : 1; reagents feed 0.029 mol/h (alkene) and
0.116 mol/h (hydrogen); conditional reaction duration:
0.068 h kgcat/mol.
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67.0 (86.4), 54.0 (46.4), 41.0 (19.4).
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molar ratio 2 : 1; reagents feed 0.023 mol/h (alkene) and
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FUNDING
This study was financially supported by the Russian Foun-
dation for Basic Research (project 18-33-00183).
https://doi.org/10.1134/S1070363218010048
14. Popov, Y.V., Mokhov, V.M., Neby-kov, D.N., Latyshova,
S.E., Panov, A.O., Dontsova, A.A., Shirkhanyan, P.M.,
and Shcherbakova, K.V., Russ. J. Gen. Chem., 2016, vol. 86,
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CONFLICT OF INTEREST
No conflict of interest was declared by the authors.
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