Effect of the Composition of the Medium on the Selectivity of Deactivation of Skeletal Nickel Catalyst

Article abstract of DOI:10.1134/S1070363218090396

The effect of the composition of the catalytic system (the nature and composition of the solvent, specifically, aqueous solutions of sodium hydroxide and their mixtures with aliphatic alcohols with the alcohol concentration of 0.11 mole fractions) and additions of a catalyst poison (sodium sulfide) on the catalytic activity of skeletal nickel in the liquid-phase hydrogenation of the carbon?carbon double bond in sodium maleate was studied. The assumption was made on the decisive role of the solvent in changing the activity of skeletal nickel in the hydrogenation reaction of sodium maleate, which is primarily associated with the redistribution of individual forms of adsorbed hydrogen. In was found that in the water?sodium hydroxide?monohydric alcohol solvent skeletal nickel undergoes selective deactivation at the NaOH concentration of 0.01 M, antiselective deactivation at the NaOH concentration of 0.10 M, and variable deactivation at the NaOH concentration of 1.0 M. It is shown that in some cases sodium sulfide additions exert a promoting effect on skeletal nickel in the hydrogenation of sodium maleate.

Full text of DOI:10.1134/S1070363218090396

ISSN 1070-3632, Russian Journal of General Chemistry, 2018, Vol. 88, No. 9, pp. 1976–1980. © Pleiades Publishing, Ltd., 2018.
Original Russian Text © A.F. Afineevskii, M.V. Lukin, D.A. Prozorov, 2016, published in Rossiiskii Khimicheskii Zhurnal, 2016, Vol. 60, No. 2, pp. 33–38.
Effect of the Composition of the Medium on the Selectivity
of Deactivation of Skeletal Nickel Catalyst
A. F. Afineevskiia*, M. V. Lukina**, and D. A. Prozorova***
a Research Institute of Chemical Thermodynamics and Kinetics, Ivanovo State University of Chemical Technology,
Sheremetevskii pr. 7, Ivanovo, 153000 Russia
e-mail: *afineevskiy@mail.ru; **lukmv@mail.ru; ***prozorovda@mail.ru
Received March 15, 2016
Abstract—The effect of the composition of the catalytic system (the nature and composition of the solvent,
specifically, aqueous solutions of sodium hydroxide and their mixtures with aliphatic alcohols with the alcohol
concentration of 0.11 mole fractions) and additions of a catalyst poison (sodium sulfide) on the catalytic activity
of skeletal nickel in the liquid-phase hydrogenation of the carbon‒carbon double bond in sodium maleate was
studied. The assumption was made on the decisive role of the solvent in changing the activity of skeletal nickel in
the hydrogenation reaction of sodium maleate, which is primarily associated with the redistribution of
individual forms of adsorbed hydrogen. In was found that in the water‒sodium hydroxide‒monohydric alcohol
solvent skeletal nickel undergoes selective deactivation at the NaOH concentration of 0.01 M, antiselective
deactivation at the NaOH concentration of 0.10 M, and variable deactivation at the NaOH concentration of 1.0 M.
It is shown that in some cases sodium sulfide additions exert a promoting effect on skeletal nickel in the
hydrogenation of sodium maleate.
Keywords: liquid-phase hydrogenation, adsorption complex, catalytic activity, catalytic poison
DOI: 10.1134/S1070363218090396
INTRODUCTION
the required activity of the nickel catalyst and
selectivity of the catalytic systems on its basis in liquid-
phase hydrogenation reactions seems quite urgent [8].
According to [1, 2], hydrogenation of organic
compounds on heterogeneous catalysts can take dif-
ferent pathways, depending first of all on the adsorp-
tion states of the reagents on the catalyst surface. This
is the reason that changes in the adsorption equilibrium
between different individual forms of adsorbed
hydrogen is commonly considered to be primarily
responsible of changes in the kinetic characteristics of
liquid-phase hydrogenation reactions [3]. It was shown
[4‒6] that the highest activity in the hydrogenation of
double bonds is characteristic of adsorbed hydrogen
with a low bond energy. Introduction of a deactivating
agent into the catalytic system will most likely affect
the adsorption equilibrium. First of all this is explained
by the preferential adsorption of poison particleson
some active sites of the surface, and such situation also
takes place in the case of the heterogeneous skeletal
nickel catalyst [7]. Therefore, research into the
selectivity of the deactivation of skeletal nickel and the
possibility of target-oriented shifting the hydrogen–
metal adsorption equilibrium with the aim to ensure
The aim of the present work was to assess the effect
of the composition of an aliphatic alcohol–water–sodium
hydroxide solvent on the catalytic activity of skeletal
nickel the hydrogenation of a model compound in this
solvent, as well as the selectivity of the deactivation of
the catalyst with sodium sulfide.
As the model compound we chose sodium maleate,
taking into account that, according to [1], this
compound reacts with hydrogen in one stage without
formation of by-products and intermediate products.
As the deactivating agent we chose sodium sulfide,
because sulfur compounds, including sulfide ion, are
the most studied catalytic poisons, which block active
canters on the surface of catalysts and thus strongly
decrease their activity in hydrogenation reactions
[4, 9–12]. In this case, the degree of deactivation is
convenient to characterize in terms of either the initial
amount of sodium sulfide per gram of catalyst [4] or a
multiple of a certain amount of poison [13].
1976

EFFECT OF THE COMPOSITION OF THE MEDIUM ON THE SELECTIVITY
1977
Table 1. Order of the hydrogenation of sodium maleate with gaseous hydrogen in the water‒aliphatic alcohol‒sodium
hydroxide solvent with the alcohol fraction of 0.11 ppm
Amount of sodium sulfide n×10–5, mol/g (Ni)
Concentration of sodium
Alcohol
hydroxide, M
0
2.5
0.9
0.9
1.0
0.9
1.1
1.1
0.8
1.2
1.2
7.5
0.9
1.0
1.0
0.9
0.9
0.9
0.9
1.1
1.2
12.5
0.9
1.0
1.0
1.1
1.0
1.0
0.9
1.3
1.3
17.5
0.7
1.0
0.9
0.8
1.0
1.1
0.8
1.0
1.3
Methanol
Ethanol
0.9
1.0
1.1
1.0
1.1
1.2
1.0
1.0
1.2
0.01
Propan-2-ol
Methanol
Ethanol
0.10
1.00
Propan-2-ol
Methanol
Ethanol
Propan-2-ol
Obviously, the catalyst–poison interaction will be
controlled both by the number of active sites and by
the preferential adsorption of the deactivating agent on
certain atomic ensembles on the surface. Bartholomew
[7] proposed to assess the selectivity of poisoning by a
method based on an analysis of the kinetic parameters
of the catalytic process. Therewith, under the term
“selective” poisoning the author meant preferential
adsorption of the poison at its low concentrations on
the most active sites of the surface. In cases where
sites with lower activity were blocked first, the
poisoning was defined as “antiselective,” and this
sometimes could even enhance of the catalytic activity
of the heterogeneous catalyst. When the degree of
deactivation was linearly related to the concentration
of adsorbed poison, the poisoning was defined as
“nonselective.” In [7], the author illustrated such
selectivity analysis by the plots of normalized catalyst
(А) against normalized poison concentration (С),
calculated by Eqs. (1) and (2):
with an intert component: aluminum, magnesium,
silicon, etc.
α = Vτ/V∞,
(3)
(4)
–1
rH = m dα/dτ,
cat
where Vτ is the volume of hydrogen reacted by moment
τ; V∞, total volume of reacted hydrogen, and mcat,
catalyst weight.
The reaction rate was calculated as follows. In the
kinetic experiment we measured the time dependence
of adsorbed hydrogen. The obtained dependence was
processed by OriginPro software to find the first its
derivative which, after normalization per gram of
catalyst and used as a measure of rate r, cm3(H) s–1 g–1
(Ni).
As seen from the resulting data listed in Table 1,
the kinetics of all reactions, except for the reaction in a
1 М NaOH–H2O–C3H7OH (0.11 mole fractions), follows
a first-order law, and, therefore, the apparent reaction
rate constants were calculated by a first-order equation
with account for Eq. (5):
A = r0,C/r0,C=0
,
(1)
(2)
C = ni/nmax
,
kH = rH·ρ·760·α–1·P(H2)–1,
(5)
where r0,C and r0,C=O are the initial rates of
hydrogenation in a given solvent (activities) of the
deactivated and nondeactivated catalysts, respectively;
where ρ is the apparent density of the catalyst (here
4.5 g/cm3); r, apparent rate constant, cm3(H) s–1 g–1
(Ni); α, Bunsen coefficient for hydrogen at 303 K,
cm3(Н) cm–3 (liquid phase); and P, pressure of H2.
ni, amount of poison per gram of catalyst; and nmax
,
amount of poison per gram of catalyst, which
completely deactivates the catalyst.
The data in Table 2 provide evidence for the
suggestion that the organic substrate prefers to react
with molecular weakly bound forms of hydrogen in a
1 : 1 ratio. The largest deviation is observed for
solutions containing propan-2-ol, probably because of
EXPERIMENTAL
Hydrogenation catalyst. Skeletal nickel catalysts
were prepared by treatment of dispersed nickel alloys
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1978
AFINEEVSKII et al.
Table 2. Apparent rates and rate constants of the hydrogenation of sodium maleate on a partially deactivated skeletal nickel
catalyst in a water‒methanol‒sodium hydroxide solution
r0H, cm3(H2) s–1 g–1(Ni)/kH, s–1
n(Na2S),
mmol/g (Ni)
0.01 M NaOH
2.39/2160
1.24/1170
1.01/720
0.1 M NaOH
2.39/6750
2.39/5700
2.02/4200
1.9/4350
1 M NaOH
1.96/16200
1.77/13050
1.46/10350
1.32/8100
0.000
0.025
0.075
0.125
0.175
0.71/540
0.29/270
0.93/1800
1.08/5850
Table 3. Apparent rates and rate constants of the hydrogenation of sodium maleate on a partially deactivated skeletal nickel
catalyst in a water‒ethanol‒sodium hydroxide solution
r0H, cm3(H2) s–1 g–1(Ni)/kH, s–1
n(Na2S),
mmol/g (Ni)
0.01 M NaOH
2.61/6750
1.80/3600
1.28/1950
0.86/1200
0.85/900
0.1 M NaOH
2.88/24750
3.13/ 26550
2.48/20250
1.77/12150
1.43/9000
1 M NaOH
1.63/ 29700
1.84/27900
1.56/25200
1.50/27000
1.28/21600
0.000
0.025
0.075
0.125
0.175
Table 4. Apparent rates and rate constants of the hydrogenation of sodium maleate on a partially deactivated skeletal nickel
catalyst in a water‒propan-2-ol‒sodium hydroxide solution
r0H, cm3(H2) s–1 g–1(Ni)/kH, s–1
n(Na2S),
mmol/g (Ni)
0.01 M NaOH
2.69/17100
1.36/6750
0.1 M NaOH
2.30/51300
2.48/54900
2.28/37800
2.08/30600
1.45/18900
1 M NaOH
1.64/63000
1.68/68400
1.61/63000
1.48/59400
1.32/50400
0.000
0.025
0.075
0.125
0.175
1.01/4050
0.69/2700
0.43/2250
the profound dehydrogenation of this alcohol 18] on
skeletal nickel and increase of the fraction of atomic,
strongly bound forms of adsorbed hydrogen with their
tendency for step reaction.
initial apparent reaction rate and the apparent rate
constant.
At the same time, such catalytic poison as sodium
sulfide can not only decrease the catalytic activity, but
also slightly promote the reaction. This experimental
fact cannot be simply explained by the traditional
blocking of the active sites on the catalyst surface and
calls for a more detailed study.
Table 2‒4 list the experimental reaction rates and
calculated reaction rate constants.
As seen from the data in Tables 2‒4, the r0H and kH
values vary almost in parallel with the composition of
the solvent and the degree of deactivation of skeletal
nickel. Therefore, as the principal characteristics of the
activity of the catalyst in the liquid-phase hydro-
genation of sodium maleate we could use both the
Figure 1 shows an example dependence of the
normalized rate of hydrogenation of sodium maleate
(R) on its conversion (α) on the catalyst at different
degrees of deactivation for the medium containing a
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 88 No. 9 2018

EFFECT OF THE COMPOSITION OF THE MEDIUM ON THE SELECTIVITY
0.01 М of NaOH in water and 0.11 mole fractions of
1979
1
2
3
4
5
1.0
0.8
0.6
0.4
0.2
0.0
propan-2-ol. The normalized rates R and conversions α
were calculated by Eqs. (3) and (6):
R = rH/r0H,
(6)
where rH is the current reaction rate and r0H, initial
reaction rate for the nondeactivated catalyst.
The obtained kinetic data on the activity of the
partially deactivated skeletal nickel allowed us, using
the above-described [see Eqs. (1) and (2)], to assess
the nature of the deactivation of the heterogeneous
catalyst with sodium sulfide. Figure 2а shows the
dependences of the normalized activity on the norma-
lized amount of the deactivating agent for the system
containing skeletal nickel catalyst and solutions of
NaOH in water (0.01 М; 0.1 М; 1 М), and Figs. 2b–2d
0.0
0.2
0.4
0.6
0.8
1.0
α
Fig. 1. Dependence of normalized reaction rate on
conversion for 0.01 M solutions of NaOH in water,
containing 0.11 mole fractions of propan-2-ol and different
quantities of sodium sulfide, mmol (Na2S)/g(Ni): (1) 0;
(2) 0.025; (3) 0.075; (4) 0.125; and (5) 0.175.
(a)
(b)
1.0
1.0
1
1
2
3
0.8
0.8
0.6
0.4
0.2
0.0
2
3
0.6
0.4
0.2
0.0
0.0
0.2
0.4
(c)
0.6
0.8
1.0
0.0
0.2
0.4
0.6
0.8
1.0
C
C
(d)
1.0
1
2
3
1
1.0
2
3
0.8
0.6
0.4
0.2
0.0
0.8
0.6
0.4
0.2
0.0
0.0
0.2
0.4
0.6
0.8
1.0
0.0
0.2
0.4
0.6
0.8
1.0
C
C
Fig. 2. Dependences of normalized activity A on normalized amount of sodium sulfide C for the media containing water,
(1) 0.01 M, ( ) 0.1 M, and ( ) 1 M NaOH and (a) no aliphatic alcohol and 0.11 mole fractions of (b) methanol, (c) ethanol,
and (d) propan-2-ol.
2
3
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 88 No. 9 2018

1980
AFINEEVSKII et al.
show similar dependences for the same solutions but
containing 0.11 mole fraction of a monohydric alcohol.
CONFLICT OF INTERESTS
No conflict of interests was declared by the authors.
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deactivation in the systems containing ethanol and
propan-2-ol still remained antiselective, while the
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