Colloidal and nanosized catalysts in organic synthesis: XV. Gas-phase hydrogenation of alkenes catalyzed by supported nickel nanoparticles

Article abstract of DOI:10.1134/S1070363216120033

Gas-phase hydrogenation of alkenes and their derivatives, catalyzed by nickel nanoparticles supported on zeolite or silica gel support occurs at 150–250°С and an atmospheric hydrogen pressure and results in a high conversion. The selectivity of the hydrogenation depends on the amount of hydrogen: at a low diene (triene)–hydrogen ratio, selective hydrogenation of one multiple bond in the substrate is possible.

Full text of DOI:10.1134/S1070363216120033

ISSN 1070-3632, Russian Journal of General Chemistry, 2016, Vol. 86, No. 12, pp. 2589–2593. © Pleiades Publishing, Ltd., 2016.
Original Russian Text © Yu.V. Popov, V.M. Mokhov, D.N. Nebykov, S.E. Latyshova, A.O. Panov, A.A. Dontsova, P.M. Shirkhanyan, K.V. Shcherbakova,
2016, published in Zhurnal Obshchei Khimii, 2016, Vol. 86, No. 12, pp. 1951–1955.
Colloidal and Nanosized Catalysts in Organic Synthesis:
XV.1 Gas-Phase Hydrogenation of Alkenes Catalyzed
by Supported Nickel Nanoparticles
Yu. V. Popov*, V. M. Mokhov, D. N. Nebykov, S. E. Latyshova,
A. O. Panov, A. A. Dontsova, P. M. Shirkhanyan, and K. V. Shcherbakova
Volgograd State Technical University, pr. Lenina 28, Volgograd, 400131 Russia
*e-mail: tons@vstu.ru
Received July 6, 2016
Abstract—Gas-phase hydrogenation of alkenes and their derivatives, catalyzed by nickel nanoparticles
supported on zeolite or silica gel support occurs at 150–250°С and an atmospheric hydrogen pressure and
results in a high conversion. The selectivity of the hydrogenation depends on the amount of hydrogen: at a low
diene (triene)–hydrogen ratio, selective hydrogenation of one multiple bond in the substrate is possible.
Keywords: catalysis, nanoparticles, nickel, hydrogenation, alkenes, gas phase, zeolite
DOI: 10.1134/S1070363216120033
The classical method of hydrogenation of carbon–
carbon multiple bonds involves a heterogeneous
nickel, platinum, palladium, rhodium, or ruthenium-
catalyzed gas-phase reaction [2]. Widely used is an
accessible nickel catalyst, but in this case a successful
reaction requires elevated temperature and pressure.
Hydrogenations under milder conditions gave good
results with platinum and palladium catalysts.
Rhodium and ruthenium showed a high selectivity in
the reduction of unsaturated alcohols, halides, and
esters without their hydrogenolysis [3].
catalyze alkene hydrogen at a hydrogenation pressure
of 10–20 atm [8]. Vanyorek et al. studied the
hydrogenation of but-1-ene on a carbon nanotube‒
supported Pt catalyst [9]. The but-1-ene conversion
reached 98%. A series of alkenes were successfully
hydrogenated zeolite-supported rhodium NPs [10]. The
reaction occurred at room temperature and a hydrogen
pressure of 10 atm for 0.25–2 h in an autoclave. It is
interesting that the hydrogenation of crotonaldehyde
with H2 in the presence of gold and silver NPs
supported on a SBA-15 substrate resulted in C=O
reduction, whereas the C=C bond remained intact [11].
In our recent works [4, 5] on the hydrogenation of
carbon–carbon multiple bonds on nickel nanoparticles
(NPs) as colloidal solutions of alkanols or THF we
have demonstrated the promise nanocatalysis offers in
this process. However, the long reaction time (3–10 h),
labor-consuming catalyst regeneration, and batch
nature of the process make it difficult to scale-up.
The goal of the present work was to explore the
possibility of continuous gas-phase flow hydrogena-
tion of alkenes on a supported nickel NP catalyst and
to assess the selectivity of this reaction. As a support
we used zeolite А (fraction 2–2.5 mm). Nickel NPs
were applied on the substrate by a procedure analogous
to that described in [12] and involving ion exchange
between Ni(II) chloride and the calcium form of zeolite
A and reduction of the resulting nickel form with
sodium tetrahydroborate in isopropanol followed by
drying in a flow of hydrogen at 170–220°С (reaction
temperature). According to [13], this procedure gives
rise to nickel NPs about 5 nm in size. Glavee et al. [14]
reported the formation of both nickel and nickel boride
Ni2B nanoparticles, along with NiO, in the reduction of
A number of gas-phase hydrogenations of alkenes
on transition metal NPs have been reported. Deghedi et
al. reported the reduction of styrene and its derivatives
on nickel NPs at temperatures of up to 130°С and a
pressure of about 30 atm [6]. Belykh et al. [7] showed
that hydrogenation of nickel NPs can be accomplished
under milder conditions. Iron NPs were used to
1
For communication XIV, see [1].
2589

2590
POPOV et al.
nickel salts. However, we found that the formation of
nickel NPs as a colloidal solution in isopropanol at
NaBH4–NiCl2 ratios no higher than 2 : 1 is accom-
panied by deposition on the inner walls of the reaction
vessel, when they were overheated, of a nickel metal
mirror. This fact points to either exclusive formation of
nickel NPs or the presence of quite a small fraction of
nickel boride in the given colloidal system. In this
connection, the formation in zeolite A pores of just
nickel particles seems the most likely option. Indirect
evidence for this suggestion is provided by the low
resistance of the resulting catalysts to air and moisture,
leading to its rapid deactivation, which is characteristic
of metal nanoparticles [8].
contact with air. Such properties can be explained by
the fact that the catalyst contains much more boron
atoms in the crystal lattice, and this enhances the
oxidative stability of nickel NPs.
For the substrates for hydrogenation we chose cyclic
and aromatic alkenes, including those containing func-
tional groups. A Parr series 5400 continuous flow
catalytic tubular reactor system was used. The reaction
was performed in the gas phase at temperatures higher
than the boiling points of the alkenes, at 1 atm on
catalysts prepared both in isopropanol and in water.
It was found that zeolite-supported nickel NPs,
irrespective of how they were prepared, exhibit a high
catalytic activity in the hydrogenation of carbon–
carbon multiple bonds. In particular, cinnamyl alcohol
(1), methyl cinnamate (3), and indene (5) were
successfully hydrogenated at 170–220°С, a 2–5-fold
molar excess of hydrogen, and a 1-atm total pressure;
therewith, neither the functional groups nor aromatic
rings were involved in the reaction. The contact time
calculated from the reactor volume, catalyst porosity,
and volume of the gas phase under the reaction
conditions was 2–7 s.
In view of the low hydrolytic stability of the catalyst,
special requirements are imposed for its application,
specifically, water-proof conditions of loading to the
reactor and dehydration of hydrogen and the substrate
to be hydrogenated. We found that a similar hydrogena-
tion catalyst can be prepared under conditions when
nickel ions are reduced with sodium tetrahydroborate
in an aqueous medium. The resulting catalyst is
hydrolytically stable and shows fair stability on short
R
R
H2 (1 atm), 180_240oC
Ni0
1, 3
2, 4
R = CH2OH (1, 2), C(O)OMe (3, 4).
H2 (1 atm), 180oC
Ni0
6
5
Cyclic alkenes are hydrogenated under the same
conditions. Thus, cyclohexene 7 is hydrogenated to
cyclohexane 8 within 2–3 s.
optimized for selective hydrogenation of one of several
carbon–carbon multiple bonds.
H2 (1 atm), 180οC
Ni0
H2 (1 atm), 120οC
Ni0
9
10
7
8
H2 (1 atm), 240οC
Ni0
With a 6–7-fold molar excess of hydrogen, ex-
haustive hydrogenationе of cyclic dienes and trienes 9
and 11 takes place. However, with a 3-fold excess of
hydrogen and the calculated contact time 2.5 s, diene 9
converts to cyclooctene 10 with the selectivity of 80%.
In the same way, we could realize selective (96%)
partial hydrogenation of triene 11 to cyclodeca-1,5-
diene 12. This result suggests that the process can be
11
12
It was found that the contact time (volume feed rate
of alkene) has a weaker effect of the selectivity of
hydrogenation of dienes and trienes than the alkene–
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COLLOIDAL AND NANOSIZED CATALYSTS IN ORGANIC SYNTHESIS: XV.
2591
hydrogen molar ratio. Thus, the hydrogenation of
triene 11 for 2.3 s gave a mixture containing 26% of
the hydrogenation product by one double bond (com-
pound 12) and 68% of cyclododecene. The triene
could be selectively (up to 97%) hydrogenated to the
diene on another substrate (on KSMG silica gel instead
of zeolite). The hydrogenation of cyclooctadiene on
silica gel‒supported nickel NPs gave cyclooctene 10 in
78% yield (diene conversion 81%).
The hydrogenation of limonene 13 on a zeolite-
supported nickel at a 3-fold excess of hydrogen and the
contact time of 3.6 s occurred with a low selectivity.
The following products were identified: the hydrogena-
tion product of the cyclohexene double bond 14 (30%),
hydrogenation product of the isopropenyl group 15
(44%), exhaustive hydrogenation product 17, as well
as limonene aromatization product 1-isopropyl-4-
methylbenzene (16) (ca. 21%).
H2 (1 atm), 180οC
Ni0
+
+
+
13
14
15
16
17
The formation of compound 16 can be explained by
the reversible dehydrogenation of the cyclohexene ring
that takes place at a 3-fold excess of hydrogen, as well
as by the high thermodynamic stability of the benzene
ring in this product. It should be noted that benzene
was not found among the hydrogenation products of
cyclohexene. The reaction with a 5-fold excess of
hydrogen gave less dehydroaromatization product 16
(6%), but the selectivity of hydrogenation of the
multiple bonds in limonene was still low.
example, in 4.4 s at 180°С the yield of compound 19
reaches 91%, whereas in 2.4 s under the same
conditions the highest yield (77%) is characteristic of
the hydrogenation half-product dihydrodicyclopenta-
diene, whereas the yield of alkane 19 is as low as 20%.
Diene 18 was also hydrogenated at a 2 : 1
hydrogen : diene ratio. The reaction within 5.2 s at
200°С gave 8% dihydrodicyclopentadiene and 87%
tetrahydrodicyclopentadiene 19. The reaction at a
higher temperature resulted in a lower conversion of
the starting compounds, probably, on account of a
weaker interaction between the substrate and catalyst.
Even though hydrogenation can be performed not
using an excess of hydrogen, this approach is
undesirable in view of the rapid deac-tivation of the
catalyst because of the higher rate of adsorption of
hydrocarbons on the catalytic centers compared to
hydrogen.
The prepared catalyst proved to be effective in the
hydrogenation of dicyclopentadiene (18). We could
obtain the exhaustive hydrogenation product tetrahyd-
rodicyclopentadiene (19) (180°С, 2.5–4 s, 5–6-fold
molar excess of Н2). Note that to hydrogenate dicyclo-
pentadiene on a commercial nickel catalyst requires a
pressure of 3.5 atm [15].
H2 (1 atm), 180οC
Ni0
Earlier we could not hydrogenate camphene and
pinenes in the liquid phase with a high conversion [4].
In the gas phase at 170°С α-pinene (20) was exhaust-
tively hydrogenated to form pinane 21.
18
19
We also studied the effect of reaction conditions on
the composition and yields of the hydrogenation pro-
ducts of diene 18. Thus, with a 5-fold molar excess of
hydrogen, the diene undergoes exhaustive hydro-
genation within 2–2.5 s in the temperature range 180–
210°С. With a 3 : 1 hydrogen:diene ratio (1.5-fold
molar excess per one double bond), both the hydro-
genation product of the norbornene ring and alkane 19
form, but their ratio depends on conditions. For
H2 (1 atm), 180οC
Ni0
20
21
Thus, zeolite A–supported nickel NPs showed a
high catalytic activity in the hydrogenation of alkenes
of different structures. The use of KSMG silica gel as a
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2592
POPOV et al.
substrate gave worse results in terms of the activity
and durability of the resulting catalyst. Varying the
hydrogen–alkene ratio and contact time allows, in
some cases, selective hydrogenation one of several
double bonds in unsaturated compounds. The catalyst
exhibits a high activity in the absence of contact with
air and moisture and at a high excess of hydrogen. The
present research gave evidence showing that gas-phase
hydrogenation of carbon–carbon multiple bonds with
hydrogen on nanosized catalysts without using high
pressures and temperatures deserves further research
62%. Mass spectrum, m/e (Irel, %): 136 (5) [М]+, 117
(100), 91 (71), 77 (12), 65 (2).
Hydrogenation of methyl cinnamate (3).
Alkene:hydrogen molar ratio 1 : 6, reaction time 2.3 s,
reaction temperature 260° C. Yield of methyl phenyl-
propionate (4) 74%. Mass spectrum, m/e (Irel, %): 164
(5) [М]+, 131 (3), 117 (7), 104 (100), 91 (47), 77 (19),
51 (12).
Hydrogenation of indene (5). Alkene:hydrogen
molar ratio 7 : 1, reaction time 2.8 s, reaction
temperature 190°C. Yield of indane (6) 57%. Mass
spectrum, m/e (Irel, %): 118 (43) [М]+, 117 (100), 91
(15), 63 (10).
EXPERIMENTAL
Gas chromatography–mass spectrometry analysis
was performed on a Saturn 2100 T/GC3900 instrument
(electron impact, 70 eV).
Hydrogenation of cyclohexene (7). Alkene :
hydrogen molar ratio 5 : 1, reaction time 2.44 s,
reaction temperature 120°C. Yield of cyclohexane (8)
71%. Mass spectrum, m/e (Irel, %): 85(7), 84 (100) [M]+.
The catalyst was prepared by impregnating zeolite
А (fraction 2–2.5 mm) with aqueous nickel(II) chloride
hexahydrate for 5–6 h. The resulting material was
filtered off, dried in air, and then treated with a sus-
pension of sodium tetrahydroborate in isopropanol at
40–50°С or in water at 20–25°С for 1–2 h. The wet
catalyst was loaded into the reactor and then dried
from isopropanol or water in a flow of hydrogen
immediately before reaction.
Hydrogenation of cycloocta-1,5-diene (9). а.
Alkene : hydrogen molar ratio 3 : 1, reaction time 2.5 s,
reaction temperature 180°C. Yield of cyclooctene (10)
78%. Mass spectrum, m/e (Irel, %): 110 (21) [М]+, 96
(70), 82 (81), 69 (93), 55 (100), 41 (100).
b. Alkene:hydrogen molar ratio 5 : 1, reaction time
1.8 s, reaction temperature 175°C. Yield of cyclo-
octene (10) 65%. Mass spectrum, m/e (Irel, %): (21)
[М]+, 96 (70), 82 (81), 69 (93), 55 (100), 41 (100).
Yield of cyclooctane 15%. Mass spectrum, m/e (Irel,
%): 112 (1) [М]+, 97 (6), 84 (26), 70 (46), 57 (100), 41
(62).
Catalytic hydrogenation was performed in a Parr
series 5400 continuous flow catalytic tubular reactor
system (reactor volume 20 cm3, tube length 0.5 m,
catalyst weight 6–8 g depending on porosity). The
reactor is designed as a steel tube (inner diameter 7 mm,
heating zone height 300 mm) embedded in an electric
oven. The catalyst bed is placed in the central part of
the reactor, and an inert packing (quartz) are placed
before and after the catalyst bed. The source of
hydrogen is a GV-7 generated with controlled gas feed.
Hydrogenation of cyclododeca-1,5,9-triene (11).
а. Alkene:hydrogen molar ratio 3 : 1, reaction time
3.3 s, reaction temperature 240°C. Yield of cyclodo-
deca-1,5-diene (12) 96%. Mass spectrum, m/e (Irel, %):
164 (3) [М]+, 134 (18), 120 (60), 92 (58), 79 (100), 65
(24), 41 (35).
General hydrogenation procedure.
A
steel
reactor was loaded with 6.5 g of a wet catalyst
(porosity 0.5), a 100-mm layer of a quartz packing
(fraction 2–2.5 mm) was then poured on top, and a
flow of hydrogen was then passed through the system
for 0.5–1 h; as this took place, the temperature was
gradually raised to 180°С. After the catalyst was
ready, a liquid alkene and the required quantity of
hydrogen were dosed to the reactor. Hydrogen was fed
simultaneously with alkene.
b. Alkene:hydrogen molar ratio 5 : 1, reaction time
2.3 s, reaction temperature 240°C. Yield of cyclo-
dodeca-1,5-diene (12) 25%. Mass spectrum, m/e (Irel,
%): 164 (3) [М]+, 134 (18), 120 (60), 92 (58), 79 (100),
65 (24), 41 (35). Yield of cyclododecene 65%. Mass
spectrum, m/e (Irel, %): 166 (3) [М]+, 134 (17), 120
(43), 106 (15), 93 (44), 81 (70), 67 (100), 54 (23), 41
(39).
Hydrogenation of limonene (13). Alkene :
hydrogen molar ratio 1:3, reaction time 3.6 s, reaction
temperature 180°C. Yield of 1-isopropyl-4-methyl-
cyclohexane (14) 30%. Mass spectrum, m/e (Irel, %):
Hydrogenation of cinnamyl alcohol (1). Alkene :
hydrogen molar ratio 1:6, reaction time 2.6 s, reaction
temperature 260° C. Yield of 3-phenylporpan-1-ol (2)
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COLLOIDAL AND NANOSIZED CATALYSTS IN ORGANIC SYNTHESIS: XV.
2593
138 (10) [М]+, 123 (20), 95 (100), 81 (35), 69 (78), 41
(76). Yield of 1-methyl-4-isopropylcyclohex-1-ene
(15) 44%. Mass spectrum, m/e (Irel, %): 138 (4) [М]+,
123 (18), 95 (100), 81 (70), 67 (100), 41 (19). Yield of
1-isopropyl-4-methylbenzene (16) 23%. Mass
spectrum, m/e (Irel, %): 134 (4) [М]+, 133 (32), 119
(100), 117 (15). Yield of 1-isopropyl-4-methylcyclo-
hexane (17) 5%. Mass spectrum, m/e (Irel, %): 140 (2)
[М]+, 96 (77), 68 (29), 55 (100).
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Hydrogenation of dicyclopentadiene (18). Alkene :
hydrogen molar ratio 3 : 1, reaction time 6.88 s,
reaction temperature 180°C. Yield of tetrahydrodi-
cyclopentadiene (19) 98%. 1Н NMR spectrum, δ, ppm:
1.20 t (2H, СН2, J = 8.4 Hz), 1.25–1.58 m (10H, СН2),
2.02 s (2H, СН), 2.27 s (2H, СН).
Hydrogenation of α-pinene (20). Alkene : hydrogen
molar ratio, reaction time 2.6 s, reaction temperature
170°C. Yield of pinane (21) 97%. Mass spectrum, m/e
(Irel, %): 138 (3) [М]+, 95 (91), 81 (93), 67(100), 55
(58), 41 (34).
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