Colloid and nanosized catalysts in organic synthesis: XI. Hydrogenation of alkynes catalyzed by nickel nanoparticles

Article abstract of DOI:10.1134/S1070363216010084

The reaction of alkynes with hydrogen under atmospheric pressure in the presence of nickel nanoparticles as a catalyst led to the exhaustive hydrogenation of the triple bond.

Full text of DOI:10.1134/S1070363216010084

ISSN 1070-3632, Russian Journal of General Chemistry, 2016, Vol. 86, No. 1, pp. 43–45. © Pleiades Publishing, Ltd., 2016.
Original Russian Text © Yu.V. Popov, V.M. Mokhov, D.N. Nebykov, 2016, published in Zhurnal Obshchei Khimii, 2016, Vol. 86, No. 1, pp. 47–50.
Colloid and Nanosized Catalysts in Organic Synthesis:
XI. Hydrogenation of Alkynes Catalyzed by Nickel Nanoparticles
1
Yu. V. Popov, V. M. Mokhov, and D. N. Nebykov
Volgograd State Technical University, pr. Lenina 28, Volgograd, 400131 Russia
e-mail: tons@vstu.ru
Received June 29, 2015
Abstract—The reaction of alkynes with hydrogen under atmospheric pressure in the presence of nickel
nanoparticles as a catalyst led to the exhaustive hydrogenation of the triple bond.
Keywords: nickel nanoparticles, catalysis, hydrogenation, alkynes, alkanes
DOI: 10.1134/S1070363216010084
Selective hydrogenation of acetylene derivatives is
used as one of the purification methods of olefins from
alkynes admixtures: particularly, for hydrogenation of
phenylacetylene formed as admixture at styrene prepa-
ration. Moreover, exhaustive hydrogenation of alkynes
as components of various products of oil processing
allows improvement of a number of characteristics of
the corresponding fractions for their efficient use.
pressure of 3 at and temperature of 25–60°C [6].
Partial hydrogenation of alkynes with hydrogen in the
presence of palladium nanoparticles immobilized on
the polymeric borate complex was done in a
continuous flow under pressure of 1.5 at in methanol at
room temperature [7]; alkynols, alkyndiols, phenylpro-
piolic acid esters, and phenylacetylene were used as
substrates. The corresponding alkenes were obtained in
7
5–95% yield; content of the cis-isomer was 93–95%.
Selective removal of acetylene hydrocarbons
admixtures from olefins and particularly phenyl-
acetylene from industrial styrene is essential condition
for the preparation of high-quality polymers. At
present this task is solved by hydrogenation of
acetylene derivatives in the presence of bimetallic
catalysts based on ultradisperse palladium particles
with additives of other metal, like silver [2].
Palladium nanoparticles obtained by reduction of its
salts with sodium borohydride and immobilized on
aluminum oxide have been also applied as the catalyst
to the hydrogenation of phenylacetylene to styrene [8].
Nickel nanoparticles prepared by reduction of
nickel chloride with metallic lithium were also used as
the catalyst for alkynes hydrogenation [9]. It was
found that partial hydrogenation of alkynes to alkenes
was possible at the use of ethanol or isopropanol as a
source of hydrogen; the reaction was operative both
with internal and terminal alkynes. Similarly prepared
nanoparticles were used for exhaustive hydrogenation
of alkynes with hydrogen in statu nascendi (through
the reaction of lithium with water existing in the
reaction mixture) [10].
Processes of reduction of various acetylenes have
been widely described in the literature; special
attention was paid to selective hydrogenation of
acetylene alcohols [3] and phenylacetylene [4].
Nanosized gold particles (2–10 nm) applied on γ-
Al O displayed high activity and stability at hydro-
2
3
genation of phenylacetylene to styrene in a phenyl-
acetylene–styrene mixture. With reduction of the
average size of gold particles from 8 to 2.5 nm, the
molar ratio styrene–ethylbenzene in the reaction
products increased from 2 : 1 to 30 : 1 [5]. Selective
hydrogenation of phenylacetylene and diphenyl-
acetylene to alkenes was performed on stabilized
nanoparticles of palladium (3–5 nm) under hydrogen
Nanoparticles of nickel phosphide (25 nm) have
been used for the selective liquid-phase hydrogenation
of alkynes with hydrogen under the pressure of 6 at in
anhydrous dioxane at 85°C [11]. Phenylacetylene and
its derivatives with various location of the triple bond
were used as the substrates; the selectivity with respect
to styrene derivatives usually reached 80–100%.
It was interesting that the introduction of nickel into
the composition of palladium catalyst led to the
1
For communication X, see [1].
4
3

4
4
POPOV et al.
increase in the selectivity (up to 95% and more) of
hydrogenation of 1-heptyne to 1-heptene; the catalyst
with 1% content of nickel occurred to be more selec-
tive than Lindlar catalyst [12]. Nickel-carbon nano-
composites have also been used as catalysts for
phenylacetylene hydrogenation [13]: 95% conversion
was achieved at 150°C with selectivity with respect to
styrene 80%. It was also found that liquid-phase
hydrogenation of decyne-1, undecyne-1, and dode-
cyne-1 catalyzed with modified nickel boride, prepared
from Ni(II) salts and sodium borohydride in a ratio
It was assumed that the change of the method of the
nickel particles preparation and an increase in their
average size allowed performance of the selective
hydrogenation of alkynes to alkenes. We tried this
assumption with compound 1c by its hydrogenation
with hydrazine hydrate catalyzed by Ni, Fe, and Co
nanoparticles prepared in situ by their reduction from
the corresponding chlorides with hydrazine hydrate [17].
OH
1
: 5 at 10°C under atmospheric pressure of hydrogen,
led to the formation of the corresponding alkenes with
1c
6
0–100% selectivity [14].
OH
OH
The goal of the present work was to study the
0
0
0
N H , Ni (Co , Fe )
2
4
possibility of acetylenes hydrogenation with gaseous
hydrogen under mild conditions using accessible
catalysts. It was earlier shown that ultradisperse metal
particles catalyzed the selective hydrogenation of
carbon–carbon double bond with hydrogen and the
process proceeded under sufficiently mild conditions [15].
+
i-PrOH
2
c
3c
The yield of compound 3c was about 30% for each
reaction when the conversion of alkynol 1c was 50–
5%; the yield of alkane 2c was 18% regardless of the
5
Phenylacetylene, 2-methyl-3-butyn-2-ol, and 1-ethyl-
cyclohexanol were chosen as the substrates.
metal used as the catalyst. The low conversion of the
starting alkyne under the applied conditions might be
due to the larger size of nanoparticles compared to the
ones prepared by the method in which sodium
borohydride was used as a reducing agent. Better
selectivity by olefin was shown in the investigated
reactions; however, the presence of a significant
amount of the exhaustive hydrogenation product even
at a rather low conversion did not allow application of
the elaborated protocol for the selective hydrogenation
of alkynols to alkenols.
Colloid nickel catalyst was prepared directly before
loading the substrate by reacting nickel chloride with
sodium borohydride [16]. The hydrogenation was
performed by bubbling gaseous hydrogen through the
solution of a substrate in isopropanol at 50–60°C for
7
–8 h in the presence of nickel nanoparticles.
0
H (1 atm), Ni
2
R
C
а−1c
CH
R
C H
2 5
i-PrOH
1
2а−2c
OH
The structure and composition of the synthesized
compounds were confirmed by the mass spectrometry
data; the spectral characteristics of the known com-
pounds matched the ones described in the literature.
R = Ph (а), C(CH ) (OH) (b),
(c).
3
2
The shorter reaction time or decreasing the
temperature to room temperature were found to be the
factors significantly reducing the conversion of the
starting acetylene alcohols; besides that an exhaustive
hydrogenation of the triple bond was observed and the
corresponding olefin alcohols were not detected. In the
case of hydrogenation of phenylacetylene for 1 h some
amount of styrene (15%) was found in the reaction
mixture together with ethylbenzene as the main product;
complete conversion of phenylacetylene to ethylbenzene
was observed at increase in the reaction time. It was
found that 10 mol % of the catalyst load was a
necessary amount for the effective hydrogenation. An-
hydrous solvent and dried hydrogen promoted the reaction.
EXPERIMENTAL
GC-MS analysis was done on a Saturn 2100
T/GC3900 instrument.
Ethylbenzene (2a). Anhydrous NiCl (1 g, 0.008 mol)
2
was gradually added to a suspension of sodium
borohydride (0.6 g, 0.017 mol) in 20 mL of anhydrous
isopropanol at vigorous stirring; black colloid solution
was formed. Then hydrogen was bubbled through the
mixture, and phenylacetylene 1a (15 g, 0.147 mol) was
added to the mixture. The reaction mixture was stirred
at 60°C for 8 h. After the reaction completion the
mixture was cooled, and water (1 mL) was added to
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 86 No. 1 2016

COLLOID AND NANOSIZED CATALYSTS IN ORGANIC SYNTHESIS: XI.
accelerate the catalyst coagulation. The precipitate was
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ACKNOWLEDGEMENTS
This work was performed in the frame of the
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