The catalytic activity of microporous and mesoporous NiCoBeta zeolite catalysts in Fischer–Tropsch synthesis

Article abstract of DOI:10.1007/s11164-020-04343-0

Two kinds of microporous and mesoporous NiCoBeta zeolite catalysts were prepared. The effect of bimetallic zeolite preparation method, dealumination degree, the presence of micropores in the support structure and the effect of nickel addition on the activity and selectivity of cobalt-based microporous and mesoporous dealuminated and non-dealuminated zeolite catalysts in Fischer–Tropsch synthesis were determined. These catalysts were obtained by sequential impregnation (Ni_3.0Co₂₀AlBeta and Ni_3.0Co₂₀SiBeta) and co-impregnation (co-Ni_3.0Co₂₀AlBeta and co-Ni_3.0Co₂₀SiBeta). The study showed that the presence of Ni leads to a lower cobalt oxide reduction temperature and an increase in CO conversion. Nickel–cobalt zeolite systems showed high activity and selectivity throughout the lifetime of the reaction. The use of a two-step post-synthesis method and the promotion of cobalt systems with nickel allow to obtain active, selective, and stable zeolite catalysts for Fischer–Tropsch synthesis.

Full text of DOI:10.1007/s11164-020-04343-0

Research on Chemical Intermediates (2021) 47:397–418
https://doi.org/10.1007/s11164-020-04343-0
The catalytic activity of microporous and mesoporous
NiCoBeta zeolite catalysts in Fischer–Tropsch synthesis
Karolina A. Chalupka1 · Renata Sadek1,2 · Lukasz Szkudlarek1 ·
Pawel Mierczynski1 · Waldemar Maniukiewicz1 · Jacek Rynkowski1 ·
Jacek Gurgul3 · Sandra Casale2 · Dalil Brouri2 · Stanislaw Dzwigaj2
Received: 24 October 2020 / Accepted: 28 November 2020 / Published online: 18 January 2021
© Springer Nature B.V. 2021
Abstract
Two kinds of microporous and mesoporous NiCoBeta zeolite catalysts were pre-
pared. The efect of bimetallic zeolite preparation method, dealumination degree,
the presence of micropores in the support structure and the efect of nickel addi-
tion on the activity and selectivity of cobalt-based microporous and mesoporous
dealuminated and non-dealuminated zeolite catalysts in Fischer–Tropsch synthe-
sis were determined. These catalysts were obtained by sequential impregnation
(Ni3.0Co20AlBeta and Ni3.0Co20SiBeta) and co-impregnation (co-Ni3.0Co20AlBeta
and co-Ni3.0Co20SiBeta). The study showed that the presence of Ni leads to a lower
cobalt oxide reduction temperature and an increase in CO conversion. Nickel–cobalt
zeolite systems showed high activity and selectivity throughout the lifetime of the
reaction. The use of a two-step post-synthesis method and the promotion of cobalt
systems with nickel allow to obtain active, selective, and stable zeolite catalysts for
Fischer–Tropsch synthesis.
Keywords Fischer–Tropsch synthesis · Beta zeolite · Bimetallic Ni–Co catalysts ·
XPS
Electronic supplementary material The online version of this article (https://doi.org/10.1007/s1116
4-020-04343-0) contains supplementary material, which is available to authorized users.
*
*
Karolina A. Chalupka
karolina.chalupka@p.lodz.pl
Stanislaw Dzwigaj
stanislaw.dzwigaj@sorbonne-universite.fr
Extended author information available on the last page of the article
Vol.:(0123456789)
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K. A. Chalupka et al.
Introduction
Fischer–Tropsch synthesis is one of the most important reactions in ecological fuel
production. For many years, the researchers were searching and still they are looking
for solutions for optimizing Fischer–Tropsch synthesis (FTS) and designing of FTS
catalysts. Scientists are focused on controlling the product selectivity and resistance
to carbon deposition formation because it is a serious problem in FTS process and
causes deactivation of catalysts which leads to decrease in the activity and selec-
tivity of used catalysts. The activity of catalysts in FTS depends on their composi-
tion, preparation methods, conditions of catalysts activation (reduction temperature,
reduction medium etc.) [1, 2]. The performance of FTS catalysts plays a crucial role
in its industrial applications [3]. All metals from group VIII of periodic table have
some activity in the C\C coupling reaction during FTS and the highest activity pre-
sent Fe, Co, Ni and Ru [4–6]. It is important to say that only Fe- and Co-based cata-
lysts are used for industrial processes due to their high activity, selectivity, and low
cost [7, 8]. Other active metals like Ni and Ru have been applied only as promoters
for iron- and cobalt-based catalysts [9–11].
The supported cobalt catalysts are the most popular catalyst for FTS process, and
they are widely used because they can work at low temperature. Moreover, they pos-
sess high activity and selectivity to longer chain hydrocarbons, and very high resist-
ance to water. However, they have also some disadvantages like they will lead to a
complex and expensive downstream processing unit to make further processing such
as isomerization and cracking. For this reason, the catalysts with binary or ternary
cobalt metal alloy are seemed to be promising in simultaneously increasing the spe-
cifc selectivity of certain hydrocarbon fractions [12, 13], and possessing relative
lower FT activation energy [14, 15]. Moreover, to the active metal alloy, support is
also found to be important to the resultant product distribution [16].
It was proved that bimetallic catalysts exhibited higher activities and enhanced
selectivity to heavy hydrocarbons compared with pure metal catalysts. The ratio of
metals constituting the bimetallic catalysts is the key factor which strongly infu-
ences their properties [17]. Van Helden et al. [18] showed in nickel–cobalt systems
that in the case of low Ni contents (Co/Ni>3), increasing the amount of this metal
does not change the selectivity to methane and C5+ hydrocarbons. However, at
higher nickel concentrations, there is a signifcant decrease in the amount of heavier
hydrocarbons formed which may be related to a lower concentration of CHx species
on the alloy surfaces or to an increase in the surface concentration of hydrogen.
It was found that a certain kind of catalyst containing Ni could be developed to
obtain the co-production of methane and gasoline. FTS reaction catalyzed by this
catalyst would increase the selectivity of its gas product and thus provide substitutes
for both natural gas and crude oil [19].
Many literature data prove that zeolite-cobalt containing catalysts may be
promised catalysts for FTS and the Si/Al ratio and structural type of zeolite may
allow to control the distribution of forming product in this process and may lead
to obtain light synthetic oil or fuel fraction [3, 20]. The present work was under-
taken to study the performance of bimetallic catalyst of Co and Ni supported on
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The catalytic activity of microporous and mesoporous NiCoBeta…
399
two types of Beta zeolites (microporous (Mi) and mesoporous (Me) Beta zeolite).
It was expected to gain higher activity than for monometallic cobalt Beta zeolite
catalysts. The particular emphasis is placed on determination of the best preparation
method (sequential impregnation and co-impregnation) of NiCoBeta zeolites and on
investigation of dealumination process of Beta zeolites to maximize the benefts of
bimetallic Co–Ni catalysts. In this work the physicochemical properties and activity
of Me–Ni3.0Co20Beta and Mi–Ni3.0Co20Beta zeolites were studied. This is a second
part of investigations related to activity and possible application in FTS of bimetallic
NiCoBeta zeolites. The frst part was recently published on Me–Ni3.0Co10Beta and
Mi–Ni3.0Co10Beta systems [21].
Methods and materials
Samples preparation
The NiCoBeta catalysts based on two diferent kinds of BEA zeolite, microporous
and mesoporous, were prepared by two various method: classical wet impregnation
and two-step post-synthesis method developed earlier by Dzwigaj et al. [22–36].
The parent microporous and mesoporous TEABeta zeolites were divided into three
parts and modifed in a diferent way. In the Scheme 1 the consecutive steps of cata-
lysts preparation are presented.
The frst parts were calcined at 550 °C for 15 h to obtain organic free mesoporous
(Me)-HAlBeta (Scheme 1a) and microporous (Mi)-HAlBeta zeolites (Scheme 1b).
The second and third parts of parent zeolites were obtained by post-synthesis
method by treating with nitric acid (HNO3) with diferent concentration and stirring
at 80 °C for 4 h to prepare partially (concentration of HNO3—6 mol L−1) and com-
pletely (concentration of HNO3—13 mol L−1) dealuminated supports. These sup-
ports were marked as Me-HAlSiBeta, Me-SiBeta (Scheme 1a) and Mi-HAlSiBeta,
Mi-SiBeta (Scheme 1b). Such prepared carriers were impregnated by cobalt nitrate
(Co(NO3)2 · 6 H2O) for 24 h to obtain cobalt Beta zeolites (contained 20 wt% of
cobalt) with diferent Si/Al ratio and then in sequential impregnation the CoBeta
samples were treated by nickel nitrate (Ni(NO3)2 · 6 H2O). The next steps were water
evaporation and calcination at 500 °C for 3 h. In this way, the six various catalysts
were prepared and were labelled as Me–Ni3.0Co20AlBeta, Me–Ni3.0Co20AlSiBeta,
Me–Ni3.0Co20SiBeta (Scheme 1a) and Mi–Ni3.0Co20AlBeta, Mi–Ni3.0Co20AlSiBeta
and Mi–Ni3.0Co20SiBeta (Scheme 1b).
Part of each fraction of the obtained catalytic systems was activated in situ
under atmospheric pressure in the fow of the mixture 95 vol% H2 and 5 vol% Ar at
400 °C, which led to the formation of Red-Ni3.0Co20AlBeta, Red-Ni3.0Co20AlSiBeta
and Red-Ni3.0Co20SiBeta.
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400
K. A. Chalupka et al.
(a)
Me-TEABeta
Si/Al = 18
Calcination
Dealumination
550 °C, 15 h
HNO3, 6mol/L, 80°C, 4 h HNO3, 13mol/L, 80°C, 4 h
Me-HSiBeta
Me-HAlSiBeta
(Si/Al = 349)
Me-
(Si/Al = 490)
HAlBeta
.
Impregnation ofCo(NO3)2 6H20, RT, 24 h
Me-Co20AlSiBeta
Me-Co20AlBeta
Me-Co20SiBeta
.
Impregnation ofNi(NO3)2 6H20,RT, 24 h
Me-Ni3.0Co20AlSiBeta
Me-Ni3.0Co20AlBeta
Me-Ni3.0Co20SiBeta
(b)
Mi-TEABeta
Si/Al = 18
Calcination
Dealumination
550 °C, 15 h
HNO3, 6mol/L, 80°C, 4 h HNO3, 13mol/L, 80°C, 4 h
Mi-HSiBeta
Mi-HAlSiBeta
(Si/Al = 881)
Mi-HAlBeta
(Si/Al = 1516)
.
Impregnation ofCo(NO3)2 6H20, RT, 24 h
Mi-Co20AlSiBeta
Mi-Co20AlBeta
Mi-Co20SiBeta
.
Impregnation ofNi(NO3)2 6H20,RT, 24 h
Mi-Ni3.0Co20AlSiBeta
Mi-Ni3.0Co20AlBeta
Mi-Ni3.0Co20SiBeta
Scheme 1 Preparation method of a mesoporous and b microporous systems
Methods of samples characterization
The metal content and the Si/Al ratio of tested catalysts were measured by the X-ray
Fluorescence (XRF) SPECTRO X-LabPro apparatus at room temperature.
The XRD patterns of catalysts were obtained on PANalytical X’Pert Pro dif-
fractometer using Cu Kα radiation (λ=154.05 pm) in 2θ range of 5–90° in ambi-
ent atmosphere. The phase transformation of catalysts during reduction process at
300 and 400 °C was also determined. These measurements were taken in situ by
using the same apparatus equipped with an Anton Paar XRK900 reactor chamber.
Approximately 150 mg of sample was packed in the glass ceramic (Macor) XRD
sample holder. The reagent gas used in the experiment was a mixture of 5 vol% H2
and 95 vol% Ar. The sample was heated at a nominal rate of 5 °C min−1. The X-ray
source was a copper long fne focus X-ray difraction tube operating at 40 kV and
30 mA. The patterns were collected in the 2θ range of 5–80° (step 0.0167°, 50 s per
step).
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The catalytic activity of microporous and mesoporous NiCoBeta…
401
The X-ray Photoelectron Spectroscopy (XPS) measurements were carried out
with a hemispherical analyzer (SES R4000, Gammadata Scienta). The unmonochro-
matized Al Kα (1486.6 eV) X-ray source with the anode operating at 12 kV and
15 mA current emission was applied to generate core excitation. The energy resolu-
tion of the system, measured as a full width at half maximum (FWHM) for Ag 3d5/2
excitation line, was 0.9 eV (pass energy 100 eV). The spectrometer was calibrated
according to ISO 15472:2001. The base pressure in the analysis chamber was about
2×10–9 mbar during the experiment. The powder samples were pressed into indium
foil and mounted on a dedicated holder. All spectra were collected at pass energy of
100 eV (with 25 meV step) except survey scans which were collected at pass energy
of 200 eV (with 0.25 eV step). The area of sample analysis was about 3 mm2.
Intensities were estimated by calculating the integral of each peak (CasaXPS
2.3.15), after subtraction of the Shirley-type background, and ftting the experi-
mental curve with a combination of Gaussian and Lorentzian lines of variable pro-
portions (70:30). The Co 2p and Ni 2p core excitations were deconvoluted with a
relative intensity ratio of 2p3/2 and 2p1/2 lines fxed to 2:1. The samples were weak
conductive; thus all binding energy values were charge-corrected to the carbon C 1 s
excitation which set at 285.0 eV.
The temperature-programmed reduction with hydrogen (TPR-H2) of cobalt-based
catalysts (c.a. 0.08 g) was carried out in the U-shaped tubular quartz microreactor.
The fow of reducing mixture of 5% H2 in Ar was 25 mL min−1. The measurement
was taken in the temperature range of 30–900 °C with the ramp rate of 10 °C min−1.
The consumption of hydrogen was monitored by thermal conductivity detector
(TCD).
Transmission electron microscope (TEM) images were carried out using
JEM–100 CX II ELECTRON MICROSCOPE JEOL. Before the TEM measure-
ment, all reduced samples were ultrasonically dispersed in a pure ethanol and a drop
of obtained suspension was deposited on a carbon flms on copper grids.
The temperature-programmed desorption of ammonia (NH3-TPD) studies were
performed in a quartz reactor. Prior the measurement, the sample was pretreated at
500 °C in the He fow for 30 min. Next, the reactor was cooled down to 100 °C and
in this temperature the adsorption of gaseous ammonia was carried out for 15 min.
For removal of the physisorbed ammonia from the zeolite surface, the tested systems
were fushed with helium fow at 100 °C for 15 min. NH3-TPD studies were per-
formed in the temperature range of 40–500 °C. The amount of adsorbed ammonia
was detected by thermal conductivity detector. Additionally, in order to check the
impact of metal reduction on the acidity of the sample, it was subjected to hydrogen
fow at 400 °C for 1 h before performing the adsorption of gaseous ammonia.
The catalytic test
Before the Fischer–Tropsch synthesis, all tested samples were pretreated at 400 °C
in the H2 fow for 1 h. The reaction was performed at 30 atm and 260 °C. The fow
of reactant gas mixture (H2/CO=2) was 60 cm3 min−1. For each measurement,
0.5 g sample was loaded in the reactor. The stabilization of reaction conditions
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K. A. Chalupka et al.
was carried out for 15 h. Gas products were analyzed by GC gas chromatograph
(Shimadzu GC-14) equipped with thermal conductivity detector and two columns:
measuring—Carbosphere 7A and comparative—molecular sieves 7B. The param-
eters of operating chromatograph were as follows: column temperature −45 °C,
detector temperature −120 °C and injector temperature −120 °C. The following for-
mulas were used to calculate the conversion of CO (KCO) and selectivity to CO2
(
)
(
)
SCO , CH4 SCH , and liquid products (SLP):
2
4
S
− S
COin
COari
KCO
=
⋅ 100%
S
COin
X
CH i ⋅ 100%
4
SCH
=
∕F
4
X
CH4out
X
⋅ KCO
CH4s
XCH out
=
4
100%
X
CO i ⋅ 100%
2
SCO out
=
∕F
2
X
CO2out
X
⋅ KCO
CO2s
XCO out
=
2
100%
SAr i
F =
SAr s
(
)
SLP = 100 − S
+ S
CO2
CH4
where: KCO—conversion of CO, SCO —the area of the CO peak before reaction,
in
SCO —the area of the CO peak after reaction, SCH —CH4 selectivity, SCO —CO2
ari
4
2
selectivity, XCH i—the area of the peak of obtained CH4, XCO i—the area of the peak
4
2
of obtained CO2, XCH out—the area of the theoretical CH4 peak (when all CO is con-
4
verted to CH4), XCO out—the area of the theoretical CO2 peak (when all CO is con-
2
verted to CO2), cXCH s—the area of the standard CH4 (when only CH4 is tested),
4
XCO s—the area of the standard CO2 (when only CO2 is tested), F—contraction
2
coefcient, SAr i—the area of the Ar peak during reaction, SAr s—the area of the Ar
peak before reaction, SLP—liquid products selectivity.
Liquid products were analysed by GC MS (6890 N Network GC System with
a Zebron Phase ZB-1MS capillary column—a length of 30 m, an internal diam-
eter of 0.25 mm linked with a 5973 Network Mass Selective Detector mass
spectrometer with a 7683 Series Injector autosampler. The chromatographic
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The catalytic activity of microporous and mesoporous NiCoBeta…
403
analysis was performed in the temperature range 70–250 °C with temperature rise
rate of 8 °C min−1. The initial and fnal temperatures were held for 3 and 30 min,
respectively.
Results and discussion
The determination of phase composition by XRD technique
XRD patterns for nickel and cobalt modifed zeolites are shown in Fig. 1. For
all samples, the difraction lines at 2θ of approximately 7.8° and 22.4° are deter-
mined, which are characteristic for Beta zeolite and indicate the coexistence of
two isomorphs of this material. The presented research shows that the crystal
structure of the Beta zeolite is preserved, both after the dealumination process as
well as the introduction of metal ions (Ni and Co) into the Beta zeolite structure
[37, 38]. The characteristic refections of NiCo2O4 and/or Co3O4 (2θ=36.69°,
44.56°, 64.94°) appeared in the NiCoBeta patterns. The appearance of the lines at
2θ of approximately 59.16° is related to the presence of NiO. In addition, for the
Me–Ni3.0Co20AlBeta, Mi–Ni3.0Co20AlBeta, and Mi–co–Ni3.0Co20SiBeta systems,
refexes associated with the presence of NiO are observed, Co3O4 and/or NiCo2O4
[39–42].
The reduction of the nickel–cobalt systems did not cause a signifcant decrease
in the intensity of difraction peaks characteristic for the Beta zeolite, what sug-
gests that the crystal structure of the support was not destroyed during the reduction
Fig. 1 XRD patterns obtained for Mi–Ni3.0Co20Beta (a) and Me–Ni3.0Co20Beta (b) catalysts prepared
by sequential and co-impregnation method after calcination process (Filled Triangle—Co3O4, Filled
Square—NiO, Multiplication—NiCo2O4)
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404
K. A. Chalupka et al.
process and it confrms high stability of the obtained systems (Fig. 2). The XRD dif-
fractograms of the catalysts show additional lines at 2θ=44.41° and 75.56°, which
can be assigned to the presence of the alloy Ni–Co and/or NiO and/or CoO [40,
43]. Due to the almost identical difraction patterns of cobalt and nickel oxides,
it is impossible to distinguish them clearly using the XRD method for such weak
refexes.
XPS results
The X-ray photoelectron spectra of Ni3Co20Beta samples have been analysed numer-
ically in the BE regions of Si 2p, Al 2p, O 1s, C 1s, Ni 2p and Co 2p.
All Si 2p spectra are well ftted by three doublets with the spin–orbit splitting of
0.61 eV (see Supporting Information). Relative intensities of these components do
not depend on the porosity of zeolite matrix. The most intense components (>91%)
with Si 2p3/2 BE values of 103.5–104.1 eV are related to the presence of tetrahe-
dral Si(IV) [44–46]. It is worth mentioning that these values are slightly larger than
reported earlier for BEA, MFI and MOR zeolites elsewhere [44–48]. There is a
visible increase in area of low-BE component (Si 2p3/2 BE of 101.4–101.9 eV) in
AlBEA samples, but it is still below 5%. Such low BE is characteristic for silicon
in lower than 4+ oxidation state. One can fnd that the dealumination process can
slightly infuence the silicon matrix.
Fig. 2 XRD patterns obtained for Mi–Ni3.0Co20Beta (a) and Me–Ni3.0Co20Beta (b) catalysts prepared
by sequential and co-impregnation method after reduction process (Filled diamond—Ni0, Filled circle—
Co0, Filled Star—Ni–Co alloy)
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The catalytic activity of microporous and mesoporous NiCoBeta…
405
The binding energy of all Al 2p3/2 peaks is close to 75.0 eV which is related to
Al3+ species (Al2O3 BE=74.9 eV [49]).
The O 1s region can reasonably be decomposed into four components: (i) a
main peak located at 533.0–533.4 eV assigned to oxygen in the zeolite framework
(Si–O–Si bonds) [50–52]; (ii) two peaks at 529.9–531.4 eV due to oxygen–metal
bonds; (iii) a peak at BE higher than 534.6 eV assigned to adsorbed water, OH
groups and/or oxygen of organic contaminants. According to our earlier paper
[53], we can identify Co–O bonds with BE ~529.9 eV and Ni–O bonds with BE
~531.3 eV. The component with BE=531.3 eV is related to NiCo2O4 (531.2 eV
[54]) or Ni(OH)2 (531.1 eV [55]).
The C 1s core lines generally consist of three peaks at 285.0 eV (organic con-
taminants), 286.0–286.2 eV (C–O groups) and >289 eV (C=O groups).
Two nickel species have been identifed in Ni 2p XPS spectra of all zeolites under
study (see Supporting Information). The components with lower BE of Ni 2p3/2
(854.2–854.6 eV) origin from the octahedral Ni2+ species found in NiCo2O4 and
Ni(OH)2. In contrast, NiO has much lower BE ~853.7 eV and cannot be considered
here. The higher BE species (856.0–856.5 eV) are related to the surface Ni3+ oxy-
hydroxides [21, 56, 57]. The latter species are dominating in Ni 2p spectra having
more than two times larger area than Ni2+ components. It is worth mentioning that
metallic component has not been found in our zeolites.
The Co 2p XPS spectra obtained for microporous and mesoporous Ni3Co20Beta
zeolites are presented in Fig. 3. The main parameters of the ftted components are
presented in Table 1. The Co 2p core level spectra are characterized by two doublet
components (Co 2p3/2 and 2p1/2) and respective shake-up satellites. The main struc-
tures come from the charge-transfer (CT) states 2p53d8L−1 (L—ligand), whereas
Fig. 3 The Co 2p XPS spectra recorded for Mi–Ni3.0Co20Beta (a) and Me–Ni3.0Co20Beta (b) samples
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406
K. A. Chalupka et al.
Table 1 The BE values (eV) and relative areas of components (%) of Co 2p3/2 core excitations obtained
for Ni3Co20BEA samples. The spin–orbit splitting ΔSO (eV) of each doublet is also listed
Sample
A
B
ΔSO
Satellites
Mi–Ni3Co20AlBEA
Mi–Ni3Co20SiBEA
Me–Ni3Co20AlBEA
Me–Ni3Co20SiBEA
779.6 (34.4)
779.8 (28.6)
779.6 (34.6)
779.5 (32.0)
780.8 (65.6)
781.3 (71.4)
780.8 (65.4)
780.7 (68.0)
15.1 15.5
15.2 15.6
15.1 15.5
15.0 15.3
783.1 788.5
783.0 787.8
782.9 788.6
782.2 788.0
the satellites refect non-CT 2p53d7 states. Latter ones overlap the main lines, which
complicates the analysis of spectra shapes, but still they provide some additional
arguments useful in characterization of the cobalt chemical environment. It is worth
noting that binding energy values of the Co 2p peaks are not always sufcient in
identifying the chemical environment of cobalt, since relatively small shifts are
reported to. In such case, the distance between two peaks in the doublet (spin–orbit
splitting ΔSO) and the satellite structure are also very informative.
At frst glance, the spectra obtained for micro- and mesoporous zeolites are quite
similar (Fig. 3), consisting of two Co 2p3/2 components at c.a. 779.6 eV and c.a.
780.8 eV binding energies. Their relative intensity ratio does not depend on the
development of specifc surface area and is close to 1:2, respectively (Table 1). The
occurrence of strong satellite lines as well as their BE positions is characteristic of
Co(II) in the high-spin state [58, 59]. This fnding is also supported by the Co 2p
spin–orbit splittings ΔSO of 15.0–15.6 eV belonging to the range characteristic for
Co(II). The minor component with BE c.a. 779.6 eV can be identifed as coming
from Co(II) species in octahedral surroundings. The well-known cobalt oxides in
bulk-like form are reported with only slightly larger values: 780.0–780.9 eV for
CoO, 779.4–780.1 eV for Co3O4 and 780.0–780.3 eV for Co(OH)O [56, 60, 61].
Thus, we associate low-BE component with the extra-framework oxides in the form
of large clusters or oligonuclear complexes. The dominant component with Co 2p3/2
binding energy c.a. 780.8 eV can be identifed as coming from tetrahedral Co(II)
species embedded into the zeolite matrix [62]. Some more detailed analysis proved
that the shape of Mi–Ni3Co20SiBEA spectrum difers from the others. It is espe-
cially well visible in the shape of Co 2p1/2 line (Fig. 3). In this case, one can fnd a
BE shift of both Co 2p components to slightly larger values. These can be related
to the degree of cations dispersion as well as to the nature of their interactions with
the zeolite matrix in which they are embedded. The higher BE for Co(II) might also
refect the occurrence of highly isolated species in this case.
The atomic ratios of cobalt and nickel with respect to silicon for all samples
have also been determined and listed in Supporting Information. Data was calcu-
lated from the integral intensities of Co 2p, Ni 2p and Si 2p lines with consideration
for atomic sensitivity factors. One can fnd out that Co/Si and Ni/Si ratios for Mi-
Ni3Co20AlBEA sample are roughly two times higher comparing to other samples;
nevertheless nominal amounts of metals were initially at the same level.
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The catalytic activity of microporous and mesoporous NiCoBeta…
407
The reducibility of Me–Ni3.0Co20Beta and Mi–Ni3.0Co20Beta catalysts
Figure 4 shows TPR—H2 profles for all samples, where peaks with maximum in
the temperature range of 288–390 °C can be seen. Similarly, to CoxBeta systems,
in the case of bimetallic systems, a multi-stage reduction process is visible [63,
64]. The frst peak with a maximum at 288–334 °C may be related to the reduc-
tion of the Co3O4 phase and/or NiO localized in the extra-framework positions to
CoO and Ni0, respectively. In addition, peaks with a maximum temperature range
of 336–383 °C are found and it could be assigned to the reduction of CoO to Co0.
In case of Me–Ni3.0Co20SiBeta, Mi–Ni3.0Co20AlBeta, Me–co–Ni3.0Co20AlBeta and
Mi–co–Ni3.0Co20SiBeta samples, the third reduction peak is observed with the max-
imum at the temperature of 358–388 °C. Its presence is associated with the reduc-
tion of CoO and/or Ni complexes in octahedral coordination [65–68]. Moreover,
only for dealuminated samples one can fnd a high-temperature peak (>730 °C). Its
appearance can be attributed to the reduction of hardly reducible cobalt aluminates
and/or silicates and/or pseudotetrahedral Co(II) species placed in the zeolite frame-
work [41, 65, 69].
Fig. 4 TPR profles for Me–Ni3.0Co20Beta (a) and Mi–Ni3.0Co20Beta (b) catalysts prepared by sequential
impregnation and co-impregnation
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K. A. Chalupka et al.
The small amount of nickel addition to the cobalt-modifed Beta zeolites leads
to decrease in the reduction temperature of extra-framework cobalt oxides (reduc-
tion temperature is 50 °C lower than in the case of monometallic catalysts) [63,
64]. A similar efect of nickel on reducibility was observed by Rytter et al. [70] for
Co/Al2O3 with small addition of nickel catalysts. The authors concluded that the
decrease in reduction temperature may be related to the spillover efect or to the
formation of a solid solution between the diferent phases of the cobalt and nickel
oxides and support.
Morphology of bimetallic Me–Ni3.0Co20Beta and Mi–Ni3.0Co20Beta catalysts
determined by TEM‑EDS
TEM characterizations of the four catalysts via TEM images (Fig. 5) pointed
out morphological diferences characteristic for the two types of supports.
The mesoporous samples (Red-Me-co-Ni3.0Co20SiBEA and Red-Me-co-
Ni3.0Co20AlBEA) include heterogeneous grains in size ranging from 200 nm to more
than 1 μm. However, they all have a similar morphology, substantially cubic with a
large porosity at the center of each grain. The microporous samples have a less regu-
lar morphology comprising grains of various sizes ranging from 50 to 200 nm. All
supports are decorated by 10–150 nm nanoparticles, but their dispersion is much
better for the mesoporous supports. On the other hand, some agglomerates of nano-
particles as large as 300 nm are well seen for the microporous supports.
The EDX analyzes performed on all samples indicate the presence of Ni and Co
elements within the zeolite support. In order to quantify the chemical composition
of the nanoparticles for this study, we proceeded to subtract this contribution in the
calculations by taking as reference the silicon peak. Thus, for the mesoporous sup-
port, the Co/Si ratio is on average twice as high as that for the microporous support
(4% against 2%).
The EDX study of mesoporous samples, Red-Me-co-Ni3.0Co20SiBEA and Red-
Me-co-Ni3.0Co20AlBEA reveals the presence of two groups of particles (Fig. 6).
The frst group is composed of the particles of large sizes (20–170 nm), which are
Fig. 5 TEM micrographs of the Red-Mi-co-Ni3.0Co20SiBEA (a) and Red-Me-co-Ni3.0Co20SiBEA (b)
catalysts with microporous and mesoporous structure
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The catalytic activity of microporous and mesoporous NiCoBeta…
409
Fig. 6 Co content (at.%) versus nanoparticles diameter (nm) in the case of the mesoporous Red-Me-co-
Ni3.0Co20SiBEA (a) and Red-Me-co-Ni3.0Co20AlBEA (b) samples
Fig. 7 Co content (at.%) versus nanoparticles diameter (nm) in the case of the microporous Red-Mi-co-
Ni3.0Co20SiBEA (a) Red-Mi-co-Ni3.0Co20AlBEA (b) samples
homogeneous in chemical composition with an average of the Co content around 85
at. % inside nanoparticles on both supports. The second group are small particles
(<20 nm) whose compositions vary while remaining mainly enriched in Co element.
For microporous Red-Mi-co-Ni3.0Co20SiBEA and Red-Mi-co-Ni3.0Co20AlBEA
catalysts, the materials have very distinct behavior. In the case of microporous Red-
Mi-co-Ni3.0Co20SiBEA (Fig. 7a), the chemical composition remains homogeneous
with a Co content around 88 at. % on all particles measured regardless of their size
(10–100 nm). However, for the microporous sample Red-Mi-co-Ni3.0Co20AlBEA
(Fig. 7b), two groups of nanoparticles are again distinguished. The frst one consists
of large particles (20–100 nm) which are homogeneous in chemical composition
with an average Co content around 88 at. % for both supports. The second group are
small particles (<20 nm) whose compositions vary with an obvious enrichment in
Ni as the size of the studied particles decreases, being able even to reach 95 at. % in
Ni content.
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K. A. Chalupka et al.
The acidic properties of bimetallic Me–Ni3.0Co20Beta and Mi–Ni3.0Co20Beta
catalysts determined using TPD‑NH3 method
TPD-NH3 profles of nickel–cobalt samples are shown in Fig. 8. For all systems one
can distinguish two peaks with maxima in the temperature ranges of 194–232 °C
corresponding to weak acid centers, and 405–490 °C corresponding to strong acid
centers [65, 71]. Removal of strong acid sites during the dealumination process
shifts the low- and high-temperature peaks towards lower temperatures [21, 63,
64]. In addition, the removal of aluminum from the support structure leads to the
decreasing of intensity of the low-temperature peak, which is clearly visible in the
Ni3.0Co20SiBeta samples and co-Ni3.0Co20SiBeta. Introduction of 3 wt% of Ni into
the Mi–Co20Beta system leads to a shift of the low-temperature peak towards higher
temperatures which is most likely related to the formation of new Lewis acid centers
[65]. In the case of Me–Ni3.0Co20Beta and Me-co-Ni3.0Co20Beta samples, an oppo-
site behavior is observed.
TPD-NH3 profles of reduced bimetallic systems are shown in Fig. 9. There are
three peaks in the temperature ranges 176–226 °C, 362–379 °C and 418–555 °C
for SiBeta support, which can be attributed to weak, medium and strong acid cent-
ers, respectively. It can also be seen that the reduction of the co-Ni3.0Co20Beta and
Ni3.0Co20Beta systems resulted in increasing of intensity of the high-temperature
Fig. 8 TPD profles for Me–Ni3.0Co20Beta and Mi–Ni3.0Co20Beta catalysts prepared by sequential
impregnation (a) and co-impregnation (b) after calcination
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The catalytic activity of microporous and mesoporous NiCoBeta…
411
peak, independently of porosity of supports. The same phenomenon was observed
by Stanton et al. [72] who related it to the formation of metallic acid sites.
Table 2 presents the quantitative results of temperature-programmed ammonia
desorption. It can be seen that the samples obtained with the two-step post-synthesis
method have much smaller number of acid centers than the corresponding samples
obtained as a result of wet impregnation. This phenomenon is related to the removal
of aluminum atoms from the zeolite structure during the dealumination process.
Comparison of the TPD-NH3 results of CoxBeta [63, 64] with bimetallic systems
shows that adding nickel to monometallic samples changes their acidity [63, 64]. In
the case of Mi–Ni3,0Co20AlBeta, Me-Ni3.0Co20AlBeta, Mi-co-Ni3.0Co20AlBeta and
Me-co-Ni3.0Co20AlBeta, the introduction of nickel increased the amount of adsorbed
ammonia indicates the formation of additional adsorption centers.
The reduction of bimetallic systems led to an increase in their acidity, suggest-
ing the formation of new Lewis and/or Brønsted acid centers. However, in the case
of Me–Ni3.0Co20AlBeta, a decrease in the amount of adsorbed ammonia is visible,
indicating a reduction in the number of Lewis Co(II) acid centers and the formation
of Co nanoparticles.
Fig. 9 TPD profles for Me–Ni3.0Co20Beta and Mi–Ni3.0Co20Beta catalysts prepared by sequential
impregnation (a) and co-impregnation (b) after reduction
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K. A. Chalupka et al.
Table 2 The amount of
adsorbed ammonia calculated
based on TPD data
Sample
After the calci- After the reduction
nation
Total amount
Total amount of
of NH3 (μmol
NH3 (μmol g−1
)
g−1
)
Mi–Ni3.0Co20AlBeta
Mi-co-Ni3.0Co20AlBeta
Mi–Ni3.0Co20SiBeta
Mi-co-Ni3.0Co20SiBeta
Me–Ni3.0Co20AlBeta
Me-co-Ni3.0Co20AlBeta
Me–Ni3.0Co20SiBeta
Me-co-Ni3.0Co20SiBeta
1455
1664
734
1817
1855
1126
893
1894
1841
928
750
2057
1257
522
1069
1453
Catalytic activity of bimetallic Me–NiCoBeta and Mi–NiCoBeta catalysts
in Fischer–Tropsch synthesis
The conversion of CO and selectivity towards methane, carbon dioxide and liquid
products in the presence of the mesoporous and microporous Red-Ni3.0Co20Beta and
Red-co-Ni3.0Co20Beta catalysts are shown in Figs. 10 and 11.
For Red-Mi–Ni3.0Co20SiBeta and Red-Me–Ni3.0Co20SiBeta catalysts, pre-
pared by sequential impregnation the selectivity towards liquid products is high
(67.6–68.9%), but with signifcantly lower CO conversion (80.4–81.0%) than
for monometallic cobalt zeolite catalysts [63, 64] and bimetallic nickel–cobalt
zeolite catalysts with lower amount of cobalt (Ni3.0Co10Beta) which activity
was described in our earlier work [21]. In the case of samples obtained by co-
impregnation, the most active catalysts are Red-Mi-co-Ni3.0Co20SiBeta and Red-
Me-co-Ni3.0Co20SiBeta. They show very high CO conversion and selectivity to
liquid products of 75.1–99.9%. Both Red-Mi-co-Ni3.0Co20AlBeta and Red-Me-co-
Ni3.0Co20AlBeta show lower CO conversion (18.5–26.7%), but a comparable selec-
tivity to liquid hydrocarbons (73.8–82.8%). This phenomenon was also observed
for co-Ni3.0Co10Beta samples described in our frst paper related to bimetallic Beta
zeolite catalysts for FTS [21]
It is worth mentioning that all bimetallic samples, except for Red-Me-
Ni3.0Co20SiBeta and Mi-co-Ni3.0Co20AlBeta, show higher CO conversion than
Red-CoxBeta monometallic catalysts [63, 64]. Similar observation was noticed by
Wang et al. [73] for Co/HZSM-5 catalysts promoted with Ni and Ru. The authors
linked this phenomenon with the increase in the degree of CO hydrogenation,
which is a consequence of the creation of more available Co0 active sites. Moreo-
ver, after 24 h of reaction in the presence of Red-co-Ni3.0Co20SiBeta and Red-
Mi-co-Ni3.0Co20AlBeta the formation of carbon dioxide (IV) is not observed.
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The catalytic activity of microporous and mesoporous NiCoBeta…
413
Fig. 10 Conversion of CO ( ) and selectivity to C1–C4 ( ), CO2 ( ) and liquid products ( ) after Fis-
cher–Tropsch synthesis (T=260 °C, p=30 atm, t=24 h) over a Red-Mi-Ni3.0Co20AlBeta, b Red-Me-
Ni3.0Co20AlBeta, c Red-Mi-Ni3.0Co20SiBeta, d Red-Me-Ni3.0Co20SiBeta (prepared by sequential impreg-
nation)
In the case of the remaining catalysts, the selectivity to carbon dioxide is about
8.2–6.5%. The addition of nickel causes the decrease in selectivity towards liquid
products, at the same time leads to an increase in the selectivity towards meth-
ane. This may be related to the good ability of this metal to break C–C bonds
[73]. The same tendency was observed by Shimura et al. [74] on Ni/Co /HZSM-5
catalysts.
The catalytic activity of all Ni3.0Co20Beta and co-Ni3.0Co20Beta catalysts
remained stable and on the same level as the bimetallic Beta zeolite catalysts with
lower Co content studied in our previous work [21]. According to Ritter et al. [70],
the high stability of nickel–cobalt systems may be due to the spillover efect which
reduces active phase re-oxidation, sintering and carbon formation on the catalyst
surface. In addition, the authors also pointed out that the presence of Ni on the sur-
face of the cobalt system may hinder the formation of graphite carbon which also
delays catalyst deactivation.
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414
K. A. Chalupka et al.
Fig. 11 Conversion of CO ( ) and selectivity to C1–C4 ( ), CO2 ( ) and liquid products ( ) after Fis-
cher–Tropsch synthesis (T=260 °C, p=30 atm, t=24 h) over a Red-Mi-co-Ni3.0Co20AlBeta, b Red-
Me-co-Ni3.0Co20AlBeta, c Red-Mi-co-Ni3.0Co20SiBeta, d Red-Me-co-Ni3.0Co20SiBeta (prepared by co-
impregnation)
Conclusion
For Red-Mi–Ni3.0Co20SiBeta and Re–Me–Ni3.0Co20SiBeta samples obtained during
sequential impregnation, the increase in selectivity towards liquid products was noted
but also signifcantly decrease in CO conversion in contrary to samples prepared by
co-impregnation for which the high selectivity and CO conversion was found.
It is also worth mentioned that dealumination process, the same as for monome-
tallic CoBeta catalysts and bimetallic Ni3.0Co10Beta catalysts, improves their activ-
ity in FTS. It may be related to decreasing the acidity, stronger interactions of Co
species with structure of Beta zeolites and formation of new acidic and active sites.
The presented studies showed that the use of a two-step post-synthesis method
and the promotion of cobalt systems with nickel allow to obtain active, selective,
and stable zeolite catalysts for Fischer–Tropsch synthesis. These promising results
encourage to continue this study, and to undertake further attempts to improve
the catalytic properties of the described zeolite materials in the Fischer–Tropsch
process.
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The catalytic activity of microporous and mesoporous NiCoBeta…
415
Memory with Prof. Michel Che
With the present contribution we would like to pay a tribute to Prof. Michel Che
and our long-lasting friendship and collaboration with more than 45 publication by
adding yet another chapter on nickel-cobalt zeolite catalysts applied for the Fischer-
Tropsch synthesis. The challenge was to prepare cobalt systems promoted with nickel
allow to obtain active, selective, and stable catalysts for Fischer—Tropsch synthesis.
Photo: Professor Michel Che with Profs Helmut Knözinger, Konstantin Hadjiivanov
and Stanislaw Dzwigaj (from left to right) during 23rd Annual Conference of Aca-
demia Europaea organized on September 22nd 2011 in UNESCO Headquarters,
Paris.
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Authors and Afliations
Karolina A. Chalupka1 · Renata Sadek1,2 · Lukasz Szkudlarek1 ·
Pawel Mierczynski1 · Waldemar Maniukiewicz1 · Jacek Rynkowski1 ·
Jacek Gurgul3 · Sandra Casale2 · Dalil Brouri2 · Stanislaw Dzwigaj2
Renata Sadek
renata.sadek90@gmail.com
Pawel Mierczynski
pawel.mierczynski@p.lodz.pl
Waldemar Maniukiewicz
waldemar.maniukiewicz@p.lodz.pl
Jacek Rynkowski
jacek.rynkowski@p.lodz.pl
Jacek Gurgul
ncgurgul@cyf-kr.edu.pl
Sandra Casale
sandra.casale@sorbonne-universite.fr
Dalil Brouri
dalil.brouri@sorbonne-universite.fr
1
Institute of General and Ecological Chemistry, Lodz University of Technology, Zeromskiego
116, 90-924 Lodz, Poland
2
Laboratoire de Réactivité de Surface, Sorbonne Universite-CNRS, UMR 7197, 4 Place Jussieu,
Case 178, 75252 Paris, France
3
Jerzy Haber Institute of Catalysis and Surface Chemistry, Polish Academy of Sciences,
Niezapominajek 8, 30239 Krakow, Poland
1 3