Deactivation of Supported Nickel-Based Hydrogenation Catalysts with Sulfide Ions

Article abstract of DOI:10.1134/S0036024419110220

Abstract: Kinetics of the liquid-phase hydrogenation of a multiple carbon bond is studied in an aqueous medium on supported nickel catalysts at different hydrogen pressures in the system under conditions of partly controlled deactivation of the active surface sites with sulfide ions. The pattern of deactivation of the active surface sites of Ni/SiO₂ catalysts containing different amounts of the active metal on the surface with sulfide ions in water is determined. The resistance of the studied catalysts to deactivation during the reduction of diethyl maleate (DM) and propen-2-ol-1 is determined experimentally. It is shown that the catalyst is more resistant to deactivation during the hydrogenation of propen-2-ol-1; this finding is attributed to the steric factor. It is found that the hydrogen pressure in the system does not affect the deactivation pattern. Excessive pressure slightly alters the deactivation resistance of the catalyst during the hydrogenation of propen-2-ol-1. It is shown experimentally that the catalytic properties of nickel in liquid-phase hydrogenation reactions can be controlled by introducing small amounts of a catalytic poison into the system at high hydrogen pressures.

Full text of DOI:10.1134/S0036024419110220

ISSN 0036-0244, Russian Journal of Physical Chemistry A, 2019, Vol. 93, No. 11, pp. 2158–2162. © Pleiades Publishing, Ltd., 2019.
Russian Text © The Author(s), 2019, published in Zhurnal Fizicheskoi Khimii, 2019, Vol. 93, No. 11, pp. 1681–1686.
CHEMICAL KINETICS
AND CATALYSIS
Deactivation of Supported Nickel-Based
Hydrogenation Catalysts with Sulfide Ions
D. A. Prozorova,*, A. V. Afineevskiia,**, A. V. Knyazevb, Ya. P. Sukhacheva, and M. D. Sukhachevaa
aIvanovo State University of Chemistry and Technology, Ivanovo, 153000 Russia
bLobachevsky State University, Nizhny Novgorod, 603022 Russia
* e-mail: prozorovda@mail.ru
** e-mail: afineevskiy@mail.ru
Received April 9, 2019; revised April 9, 2019; accepted May 14, 2019
Abstract—Kinetics of the liquid-phase hydrogenation of a multiple carbon bond is studied in an aqueous
medium on supported nickel catalysts at different hydrogen pressures in the system under conditions of partly
controlled deactivation of the active surface sites with sulfide ions. The pattern of deactivation of the active
surface sites of Ni/SiO2 catalysts containing different amounts of the active metal on the surface with sulfide
ions in water is determined. The resistance of the studied catalysts to deactivation during the reduction of
diethyl maleate (DM) and propen-2-ol-1 is determined experimentally. It is shown that the catalyst is more
resistant to deactivation during the hydrogenation of propen-2-ol-1; this finding is attributed to the steric fac-
tor. It is found that the hydrogen pressure in the system does not affect the deactivation pattern. Excessive
pressure slightly alters the deactivation resistance of the catalyst during the hydrogenation of propen-2-ol-1.
It is shown experimentally that the catalytic properties of nickel in liquid-phase hydrogenation reactions can
be controlled by introducing small amounts of a catalytic poison into the system at high hydrogen pressures.
Keywords: liquid-phase hydrogenation, adsorption complex, catalyst activity, catalytic poison
DOI: 10.1134/S0036024419110220
INTRODUCTION
bonding to the catalyst surface [3–5]. The adsorption
states of hydrogen are in turn directly related to the
energy of intermediate interactions. We may therefore
assume it is the nature and energy characteristics of
adsorbed hydrogen that determine the rate and selec-
tivity of hydrogenation reactions. Concepts of differ-
ent reactivities of individual adsorbed hydrogen forms
are frequently used to interpret the kinetic laws of
hydrogenation of different classes of compounds [6,
7]. However, the published approaches to estimating
the reactivity of adsorbed hydrogen are extremely lim-
ited. The authors of [2, 8] proposed an approach to
experimentally determining the reactivity parameters
and thermodynamic characteristics of adsorbed
hydrogen that was based on the partly controlled deac-
tivation of active surface sites of metals due to intro-
ducing small amounts of catalytic poisons into a cata-
lyst system without changing the composition and
structure of the reaction system in general. The cited
authors showed that this approach allows us to esti-
mate the reactivity of individual adsorbed hydrogen
forms in liquid-phase hydrogenation reactions
according to the regional rate [8]; in addition, we can
select optimal catalyst systems with predetermined
In the last 30 years, catalytic processes of the
hydrogenation of organic compounds of different
classes with gaseous hydrogen have almost supplanted
all other industrial reduction techniques. The most
commonly used catalysts are systems that contain
nickel, palladium, platinum (less frequently), and
other transition metals as the main active metal that
can be promoted with different compounds. Accord-
ing to well-known theoretical principles [1, 2], the
laws governing the adsorption of reactants determine
the activity and selectivity of heterogeneous catalysts.
An understanding of these laws is necessary for the
development of scientifically grounded methods for
the selection of optimum catalyst systems and the pre-
diction of the catalytic effect. It is not by chance that
the expansion of the areas of application of the theory
of adsorption in studies of the kinetics and mecha-
nisms of heterogeneous catalytic processes is consid-
ered to be a priority direction of the development of
the theory of catalysis formulated by the European
Federation of Catalytic Societies (EFCATS).
It has been shown experimentally that during
adsorption on the surfaces of metals and catalysts
based on them, hydrogen is adsorbed in different
adsorption states that differ in type and the energy of activity and selectivity.
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DEACTIVATION OF SUPPORTED NICKEL-BASED HYDROGENATION CATALYSTS
2159
Table 1. Main physicochemical properties of the studied nickel catalysts
Ssp, m2/g
No.
[NiO], wt %
С, %
R, μm
d, nm
l, nm
1
2
3
4
5
6
23.2
16.4
15.8
8
6.9
4.7
264 0.7
296.3 0.9
317.6 0.5
338.4 0.5
362 0.9
11
9
7
5
4
5
5
5
5
5
5
0.297
0.287
0.293
0.288
0.275
0.255
17.7
15.5
10.0
9.8
9.5
9.1
364 0.8
0.6
[NiO] is the amount of supported NiO, C is the active metal content, r is the particle radius, d is the interplanar spacing, and l is the
crystallite size.
The aim of this work was to study the pattern of introduced per gram of catalyst, at which the catalyst
deactivation of silica gel-supported nickel catalysts for completely loses activity.
the liquid-phase hydrogenation of multiple carbon
bonds by introducing measured amounts of sulfide
ions into the system at atmospheric and high hydrogen
pressures in the system.
In this case, selective etching is understood as the
preferential adsorption of the poison at low poison
concentrations on the most active surface sites. The
preferred blocking of regions with lower activity leads
to antiselective deactivation. If the drop in activity is
linearly dependent on the concentration of the
adsorbed poison, the poisoning is nonselective.
EXPERIMENTAL
A number of silica-supported nickel catalysts
(Ni/SiO2) with different concentrations of the active
metal were used in this work. The catalysts were syn-
thesized as described in [9]. Silica gel L 5/40 was used
for the synthesis. The average particle radius was 5 μm,
and the specific surface area was 390 5 m2/g. The
structural and mechanical properties of the catalysts
are presented in Table 1.
Our kinetic studies of the liquid-phase hydrogena-
tion reaction were conducted by static means under
unsteady conditions in a pressurized liquid reactor
with vigorous stirring at a hydrogen pressure in the sys-
tem of 0.1–0.9 MPa. Catalyst activity was estimated
from the rates of hydrogenation of a model compound
at conversion of less than 0.1.
The deactivation selectivity was estimated accord-
ing to Bartholomew [10], based on an analysis of the
kinetic parameters of the studied process and specially
modified for liquid-phase hydrogenation reactions.
This required determination of the preferential
adsorption of the deactivating agent particles on cer-
tain atomic ensembles of the surface.
This approach is based on analyzing a plot con-
structed in the A = f(C) coordinates, where catalyst
activity A and specific amount of the catalytic poison
in the system C are normalized to the equations
Diethyl maleate (DM) and propen-2-ol-1 were
selected as model hydrogenated compounds contain-
ing multiple carbon bonds. These compounds interact
with hydrogen in a 1 : 1 stoichiometry to form negligi-
ble amounts of byproducts and intermediates. The
controlled deactivation of the active catalyst sites was
achieved as described in [2] by adding strictly defined
amounts of a 0.05 M sodium sulfide solution with a
pH value corresponding to the pH of the reaction
medium to the bulk phase. The catalyst was etched in
the titration mode in a hydrogen atmosphere with vig-
orous stirring of the liquid phase. According to prelim-
inary studies, the maximum drop in catalyst activity at
a certain amount of the etching agent is achieved
within 15 min; a further increase in the deactivation
time at a test temperature of 303 K does not result in
an appreciable drop in the activity of the nickel cata-
lyst; most commonly, it is within the experimental
error. Water was used as the solvent.
Direct potentiometry was used to determine the
S2– ion concentrations. Measurements of the residual
sulfide ion concentrations after catalyst deactivation
suggest the amount of sulfide remaining in the solu-
tion was below the detection limit.
The effect hydrogenation has on the structural and
mechanical properties was determined on a TESCAN
VEGA 3 SBHSEM scanning electron microscope
combined with an energy dispersive spectrometer with
an Oxford Instruments NanoAnalysis x-ACT detec-
tor. Elemental mapping of the catalyst surface was
(1)
A = r0,C /r0,C =0
,
(2)
C = n /nmax
,
i
where r0,C and r0,C=0 are the initial hydrogenation reac- conducted before the kinetic testing and immediately
tion rates in a given solvent (activity) for deactivated after the testing. An example of elemental mapping of
and nondeactivated catalysts, respectively; ni is the catalyst 2 (see Table 1) after DM hydrogenation at a
amount of the catalytic poison introduced per gram of hydrogen pressure of 0.9 MPa and a temperature of
catalyst; and nmax is the amount of the catalytic poison 30°С is shown in Fig. 1.
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PROZOROV et al.
Si Kα1
O Kα1
Ni Kα1
S Kα1
25 μm
25 μm
25 μm
25 μm
(а)
(b)
(c)
(d)
Fig. 1. Scanning microscope-synchronized electronic map of elemental distribution over the surface for catalyst 2 (see Table 1)
after DM hydrogenation in water at a hydrogen pressure of 0.9 MPa, a temperature of 30°C, and an amount of sodium sulfide
introduced per gram of catalyst of 0.840 mmol(Na S)/g(Ni).
2
apparent density of the catalyst (4.5 g/cm3 for the
RESULTS AND DISCUSSION
selected catalyst), and
is the hydrogen pressure in
PH
To determine the effect deactivation processes have
on the activity of supported nickel in the studied liq-
uid-phase hydrogenation reactions, apparent rates rapp
and rate constants kapp of the processes were first cal-
culated with the equations
2
the test.
The kinetic laws of the reduction of the model
compounds in the presence of the supported nickel
catalyst at a hydrogen pressure in the system of 0.1 and
0.9 MPa and different amounts of the catalytic poison
introduced into the system are shown in Figs. 2–5.
According to the data shown in Figs. 2–5, deacti-
vation of the catalyst’s surface does not alter the
kinetic laws; it only reduces the catalyst’s activity; the
reaction rate constant calculated with formula (4)
remains virtually unchanged at different hydrogen
pressures in the system. The results from the mathe-
matical processing of the kinetic laws according to
ΔV
Δt
rappρ × 760
(3)
(4)
rapp
=
,
kapp
=
,
αPH × 60
2
where
is the amount of hydrogen (mL) that reacts
ΔV
within time
(s), α is the Bunsen coefficient for
Δt
hydrogen at 303 K (cm3(H2)/cm3(l. ph.)), ρ is the
r, сm3(H2)(s g(Ni))−1
r, сm3(H2)(s g(Ni))−1
1
2
3
4
5
4
3
2
1
1
2
3
4
5
5
4
5
3
2
1
0
0.2
0.4
0.6
0.8
1.0
0
0.2
0.4
0.6
0.8
1.0
α
α
Fig. 2. Rate of hydrogen absorption during DM hydroge-
nation in water at different amounts of introduced sodium
sulfide: (1) 0, (2) 0.050, (3) 0.100, and (4)
Fig. 3. Rate of hydrogen absorption during propen-2-ol-1
hydrogenation in water at different amounts of introduced
sodium sulfide: (1) 0, (2) 0.050, (3) 0.100, and (4)
0.500 mmol(Na S)/g(Ni). Conditions of hydrogenation:
0.500 mmol(Na S)/g(Ni). Conditions of hydrogenation:
2
2
Т = 30°С; m = 2.5 g; amount of reduced metal (Ni),
Т = 30°С; m = 2.5 g; amount of reduced metal (Ni),
cat
cat
11%; pressure, 0.1 MPa.
11%; pressure, 0.1 MPa.
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DEACTIVATION OF SUPPORTED NICKEL-BASED HYDROGENATION CATALYSTS
2161
r, сm3(H2)(s g(Ni))−1
r, сm3(H2)(s g(Ni))−1
20
15
10
5
1
1
2
3
4
5
2
3
4
5
20
10
0
0.2
0.4
0.6
0.8
1.0
0
0.2
0.4
0.6
0.8
1.0
α
α
Fig. 5. Rate of hydrogen absorption during propen-2-ol-1
hydrogenation in water at different amounts of introduced
sodium sulfide: (1) 0, (2) 0.210, (3) 0.420, (4) 0.630, and
Fig. 4. Rate of hydrogen absorption during DM hydroge-
nation in water at different amounts of introduced sodium
sulfide: (1) 0, (2) 0.210, (3) 0.420, (4) 0.630, and
(5) 0.840 mmol(Na S)/g(Ni). Conditions of hydrogena-
2
(5) 0.840 mmol(Na S)/g(Ni). Conditions of hydrogena-
2
tion: Т = 30°С; m = 2.176 g; amount of reduced metal
cat
tion: Т = 30°С; m = 2.177 g; amount of reduced metal
cat
(Ni), 11%; pressure, 0.9 MPa.
(Ni), 11%; pressure, 0.9 MPa.
Bartholomew [10] suggest the catalyst’s surface under- induced deformations of the active metal surface and
goes deactivation selectively; the deactivation becomes thus a smaller loss of activity. The data can also be
nonselective only at substantial sulfide ion concentra- attributed to the steric factor: a propen-2-ol-1 mole-
tions in the system. In addition, catalyst deactivation cule is smaller than a DM molecule, so it has more
with respect to the reduction of DM and propen-2-ol- opportunities to approach the surface of a catalyst that
1 proceeds at different rates, as is shown in Table 2.
The data in Table 2 suggest that in the case of DM
is partly blocked by sulfide ions.
According to [5, 11], the distribution of hydrogen
reduction, introducing a catalytic poison into the sys- over the surfaces of bulk and supported nickel-based
tem leads to a more rapid loss of catalyst activity than catalysts with respect to individual forms remains
with propen-2-ol-1 hydrogenation. The catalyst was approximately constant in different solvents; the
more resistant to deactivation at atmospheric hydrogen greatest contribution to the shift of the adsorption
pressure; upon an increase in pressure to 0.9 MPa, the equilibrium of hydrogen comes from the catalyst deac-
dependence of the degree of deactivation on the cata- tivation [12, 13]. However, though the kinetic laws of
lytic poison concentration becomes more complex. We the hydrogenation of compounds containing carbon–
believe this finding can be attributed to the heat of carbon double bonds are of the same type at hydrogen
hydrogenation of propen-2-ol-1 (–(127–130) kJ/mol) pressures in the system of 1–9 atm, they differ in activ-
being lower than that of DM (−(141–158) kJ/mol). ity at low conversions of the hydrogenated compound
This ensures smaller adsorption- and catalysis- and in the susceptibility to deactivation caused by the
Table 2. Deactivation coefficients calculated by the Bartholomew method for the supported nickel catalyst at different
hydrogen pressures in the system
1
2
3
4
5
6
Kd,aver
Compound
Kd, g(Ni)(mmol(Na2S))−1
0.1 MPa
DM
Propen-2-ol-1
4.4
1.3
4.7
1.6
6.3
2.0
6.5
1.5
5.8
1.6
6.0
1.8
5.6
1.6
0.9 MPa
DM
Propen-2-ol-1
4.4
2.3
6.8
1.8
5.7
1.2
5.2
1.0
12.2
1.4
15.9
2.8
8.4
1.8
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PROZOROV et al.
FUNDING
targeted introduction of catalytic poisons into the sys-
tem. This can be attributed to the different reactivities
of not only individual adsorbed hydrogen forms but
also the hydrogen acceptor.
This work was performed as the project part of State
Task no. 3.1371.2017/4.6.
The authors of [8] demonstrated the possibility of
calculating the rate constants using individual active
sites of the nickel surface using a complex of kinetic
and adsorption calorimetric experimental data and
calculated the rate constants for the reduction of mul-
tiple carbon bonds involving three adsorbed hydrogen
forms at atmospheric pressure. The authors used a
model of a surface with discrete heterogeneity [14, 15]
to calculate the relative amounts of molecular and
atomic hydrogen on the surface of a bulk nickel cata-
lyst; the adequacy of this model was later confirmed in
a direct experiment [16]. We may assume that an
increase in the hydrogen pressure in the system does
not lead to the formation of fundamentally different
adsorbed hydrogen forms; this factor only alters the
ratio of the forms without changing their reactivity. In
the future, regional rates can be used to recalculate the
number of individual hydrogen forms on the surfaces
of catalysts and their contribution to the reduction of
DM and propen-2-ol-1 at a hydrogen pressure of
0.9 MPa.
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CONCLUSIONS
Introducing a sulfide ion into a reaction system
allows us to modify the surfaces of supported nickel
catalysts in order to ensure not only a differentiation of
rates, which is of fundamental importance in deter-
mining the reactivity of hydrogen characterized by dif-
ferent adsorption energies, but also variation in cata-
lyst susceptibility, depending on the steric factor. The
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ACKNOWLEDGMENTS
This work was performed on equipment at the shared
resource center of the Ivanovo State University of Chemis-
try and Technology and the Lobachevsky State University
of Nizhny Novgorod. The theoretical part was coordinated
with plan no. 19-03-460-07 of the activities of the Scientific
Council of the Russian Academy of Sciences for physical
chemistry in 2019.
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Translated by M. Timoshinina
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