Catalytic conversion of trichloroethylene on nickel containing beta zeolites into value added products

Article abstract of DOI:10.1016/j.catcom.2014.08.023

Nickel containing BEA zeolites, NiSiBEA and NiHAlBEA, with 2 wt% of Ni were prepared by a two-step postsynthesis method and conventional wet impregnation. The calcination of NiSiBEA and NiHAlBEA at 773 K for 3 h in air led to the formation of C-NiSiBEA and C-NiHAlBEA. After reduction at 873 K for 3 h in flowing 10% H₂/Ar, red-C-NiSiBEA and red-C-NiHAlBEA were obtained and investigated as the catalysts in hydrodechlorination of trichloroethylene at 503 K. Comparative study performed on red-C-NiSiBEA and red-C-NiHAlBEA showed very high stability of the catalyst prepared by a two-step postsynthesis method and strong deactivation of the catalyst prepared by conventional wet impregnation during ~ 17 h of reaction. Application of both catalysts resulted in high selectivity to unsaturated hydrocarbons that are the most desired products in HDC processes. TPH of the catalysts after kinetic run have shown that the main cause of deactivation of NiHAlBEA is the formation of carbonaceous species during hydrodechlorination of trichloroethylene.

Full text of DOI:10.1016/j.catcom.2014.08.023

Catalysis Communications 57 (2014) 107–110
Contents lists available at ScienceDirect
Catalysis Communications
journal homepage: www.elsevier.com/locate/catcom
Short Communication
Catalytic conversion of trichloroethylene on nickel containing beta
zeolites into value added products
a,⁎⁎
⁎
A. Śrębowata
, R. Baran b,c,d, D. Lisovytskiy a, I.I. Kamińska a, S. Dzwigaj b,c,
a
Institute of Physical Chemistry, PAS, Kasprzaka 44/52, PL-01224 Warszawa, Poland
Sorbonne Universités, UPMC Univ Paris 06, UMR 7197, Laboratoire de Réactivité de Surface, F-75005 Paris, France
CNRS, UMR 7197, Laboratoire de Réactivité de Surface, F-75005 Paris, France
b
c
d
AGH University of Science and Technology al. A. Mickiewicza 30, 30-059 Krakow, Poland
a r t i c l e i n f o
a b s t r a c t
Article history:
Nickel containing BEA zeolites, NiSiBEA and NiHAlBEA, with 2 wt% of Ni were prepared by a two-step postsynthesis
method and conventional wet impregnation. The calcination of NiSiBEA and NiHAlBEA at 773 K for 3 h in air led to
the formation of C-NiSiBEA and C-NiHAlBEA. After reduction at 873 K for 3 h in flowing 10% H2/Ar, red-C-NiSiBEA
and red-C-NiHAlBEA were obtained and investigated as the catalysts in hydrodechlorination of trichloroethylene
at 503 K. Comparative study performed on red-C-NiSiBEA and red-C-NiHAlBEA showed very high stability of the
catalyst prepared by a two-step postsynthesis method and strong deactivation of the catalyst prepared by con-
ventional wet impregnation during ~17 h of reaction. Application of both catalysts resulted in high selectivity
to unsaturated hydrocarbons that are the most desired products in HDC processes. TPH of the catalysts after ki-
netic run have shown that the main cause of deactivation of NiHAlBEA is the formation of carbonaceous species
during hydrodechlorination of trichloroethylene.
Received 19 February 2014
Received in revised form 21 July 2014
Accepted 8 August 2014
Available online 23 August 2014
Keywords:
Nickel
Beta zeolites
Trichloroethylene
Hydrodechlorination
© 2014 Elsevier B.V. All rights reserved.
1. Introduction
chloroethene were observed as the main products. Till now, gas-phase
catalytic hydrodechlorination of trichloroethylene on nickel containing
Trichloroethylene (TCE) is one of the most popular chloroorganic
compound widely used in the chemical industry. However, because of
its carcinogenicity, TCE is a hazardous pollutant for the natural environ-
ment and human health and must be removed from waste gases and
wastewater. Application of catalytic hydrodechlorination (HDC) as a
method of conversion of chloroorganic compounds gives the chance for
the transformation of trichloroethylene into value added products like
unsaturated hydrocarbons (ethene and propene) or 1,1-dichloroethene
[1,2]. They are widely used in chemical industry in polymerization, oxi-
dation, halogenation, alcylation, fabrication of semiconductor device
etc. [3–7]. Both ethene and propene are the most important starting
products in petrochemical industry, but they exist in nature too. Ethene
is an important plant hormone and propene is naturally produced by
vegetation of plants. Therefore, they are used in the artificial process of
fruit ripening [8,9].
catalysts has not been extensively investigated yet [12].
The aim of our study was to investigate the effect of preparation way
on catalytic behavior of nickel containing beta zeolites in conversion of tri-
chloroethylene. To the best of our knowledge this is the first report on the
hydrodechlorination of TCE over nickel — BEA zeolites, prepared by con-
ventional wet impregnation (NiHAlBEA) and two-step postsynthesis
method (NiSiBEA).
2. Experimental section
2.1. Materials
Nickel containing zeolites (with 2 Ni wt%) were prepared by two-
step postsynthesis method (NiSiBEA) and conventional wet impregna-
tion (NiHAlBEA) using SiBEA and HAlBEA as a supports and aqueous so-
lution of Ni(NO3)2·6H2O as a nickel precursor. All the preparation
details are described in our earlier work [13]. Both NiSiBEA and
NiHAlBEA were calcined in air (100 K h−1) at 773 K for 3 h under static
condition and labeled as C-NiSiBEA and C-NiHAlBEA respectively. Then,
a portion of C-NiSiBEA and C-NiHAlBEA were reduced at 873 K for 3 h in
flowing 10% H2/Ar to obtain red-C-NiSiBEA and red-C-NiHAlBEA, re-
spectively, where C — stands for calcined and red — for reduced. These
catalysts after kinetic run were labeled as spent-red-C-NiSiBEA and
spent-red-C-NiHAlBEA, respectively.
Catalytic conversion of TCE can be effectively carried out on noble
metals such as Pd and Pt and on bimetallic systems containing PdCu
or PdNi [1,2,10,11]. Depending on the catalyst, ethane, ethene, propene,
⁎
Corresponding author.
⁎⁎ Correspondence to: A. Śrębowata, Institute of Physical Chemistry, PAS, Kasprzaka 44/52,
PL-01224 Warszawa, Poland. Tel.: +48 1 22 343 3215.
E-mail addresses: asrebowata@ichf.edu.pl (A. Śrębowata), stanislaw.dzwigaj@upmc.fr
(S. Dzwigaj).
http://dx.doi.org/10.1016/j.catcom.2014.08.023
1566-7367/© 2014 Elsevier B.V. All rights reserved.

108
A. Śrębowata et al. / Catalysis Communications 57 (2014) 107–110
2.2. Techniques
removed by hydrogen from spent catalysts. Progress of TPH runs,
using a 20% H2/He flow (25 cm3 min−1) at a 10 K min−1 ramp, was
Nickel containing beta zeolites were investigated by chemical analy-
sis, powder X-ray diffractograms (XRD), diffuse reflectance UV–vis (DR
UV–vis), X-ray Photoelectron Spectroscopy (XPS), temperature-pro-
grammed reduction (TPR), oxygen and CO chemisorption.
followed by mass spectrometry (MA200, Dycor-Ametek, Pittsburgh).
3. Results and discussion
Hydrodechlorination of TCE (analytical reagent from POCh, Gliwice,
Poland, purity N99.5%) lasted in glass - flow system equipped with frit-
ted disk to place a catalyst charge, described with details earlier [13].
Portion of red-C-NiSiBEA or red-C-NiHAlBEA were cooled to 503 K,
and then contacted with the reaction mixture. The mass of the catalysts
was 100 mg. A typical run was carried out ~17 h. Hydrogen and argon
were purified by MnO/SiO2, and the C2HCl3/H2 ratio was 1:3 (with the
total flow of 42 cm3 min−1). All reactions were followed by gas chroma-
tography (HP 5890 Series II with FID, a 5% Fluorcol/Carbopack B column
(10 ft) from Supelco). The results of GC analysis were elaborated using
HP ChemStation.
HRTEM investigations were carried out using FEI TITAN Cubed elec-
tron microscope operated at an acceleration voltage of 300 keV and
equipped with an energy dispersive X-ray (EDX) EDAX spectrometer.
The samples were prepared by dispersing in pure alcohol using ultra-
sonic cleaner and putting a drop of this suspension on carbon films on
copper grids and purified with plasma cleaner.
As we reported earlier [13], the two-step postsythesis method led to
formation of the NiSiBEA zeolites with the nickel mainly incorporated
into framework position as isolated pseudo-tetrahedral Ni(II) species
and the conventional wet impregnation led to the formation of
NiHAlBEA with the nickel incorporated into framework and extra-
framework positions as pseudo-tetrahedral and octahedral Ni(II) spe-
cies respectively.
These different ways of zeolites preparation strongly influenced cat-
alysts properties, especially metal particles size distribution. Red-C-
NiSiBEA catalyst obtained from NiSiBEA by its calcination at 773 K and
then reduction at 873 K for 3 h in flowing 10% H2/Ar contains very
small nickel nanoparticles with an average size of 1.5 nm, well dispersed
in zeolite structure. In contrast, red-C-NiHAlBEA catalyst obtained from
NiHAlBEA by its calcination at 773 K and then reduction at 873 K for 3 h
in flowing 10% H2/Ar contains Ni(0) with larger size of nanoparticles
(average size of 5 nm) (Fig. 1).
Both NiSiBEA and NiHAlBEA zeolites are characterized by similar BEA
zeolite structure as shown by similar XRD patterns (results not shown)
and their further calcination and reduction did not affect crystallinity of
After kinetic runs, nickel catalysts were investigated by a tempera-
ture-programmed hydrogenation (TPH) to detect species that can be
Fig. 1. HRTEM results and nickel particle size distribution for red-C-NiHAlBEA (a) and red-C-NiSiBEA (b).

A. Śrębowata et al. / Catalysis Communications 57 (2014) 107–110
109
22.47
22.46
red-C-NiSiBEA with formation of Ni ions that can migrate and incorpo-
rate into zeolite framework.
Fig. 3 and Table 1 show the results of hydrodechlorination of trichlo-
roethylene on parent BEA zeolites and nickel-containing BEA zeolites
with different Si/Al ratio. Red-C-SiBEA shows only a negligible activity
which is in agreement with our earlier study observed during conver-
sion of 1,2-dichloroethane [13]. Addition of 2 wt.% of nickel to
dealuminated BEA (SiBEA) leads to formation of the active catalyst in
hydrodechlorination of tichloroethylene. Time on stream behavior
shows the most spectacular changes of the total conversion of TCE dur-
ing the first two hours of reaction with red-C-NiSiBEA. After this time,
the activity is stabilized on the value characteristic for steady state con-
ditions (Fig. 3). For red-C-NiSiBEA the summary selectivity toward
unsaturated hydrocarbons (ethylene and propylene — the most impor-
tant starting products in the petrochemical industry, manufacturing of
plastics) is close to 55% and additionally 1,1-dichloroethylene (the com-
pound used for production of certain plastics, and also in semiconductor
device fabrication) as the main product is formed (Table 1). Red-C-
HAlBEA with Si/Al ratio of 17 shows small, but about 5 times higher con-
version than this obtained on red-C-SiBEA. Both, red-C-HAlBEA and red-
C-NiHAlBEA were deactivated as a function of time much stronger than
red-C-NiSiBEA. The difference in catalytic behavior of two parent red-C-
SiBEA and red-C-HAlBEA zeolites and nickel containing red-C-NiSiBEA
and red-C-NiHAlBEA zeolites could be related to the presence of acidic
sites and the ration between the amounts of Brønsted and Lewis acidic
sites, as it was reported earlier [12,13]. It seems that the presence of
big amounts of strong Brønsted acidic sites is responsible for the activity
of red-C-HAlBEA catalyst with more than 90% of selectivity toward eth-
ylene (desired product of HDC of TCE). The presence of small nickel
nanoparticles in red-C-NiHAlBEA leads to the formation of olefins (eth-
ylene and propylene) as the main products (Table 1) and additionally
1,1-dichloroethylene as the effect of the presence of Lewis acidic sites.
Our results are in agreement with the earlier studies of
hydrodechlorination of trichloroethane [12,14,15], where Lewis acidic
sites were suggested to be involved in the reaction leading to 1,1-
dichloroethylene as the major reaction product. For nickel containing
zeolites, the selectivity towards 1,1-dichloroethylene increased propor-
tionally to amounts of Lewis acidic sites. Maximally 45% of selectivity
was obtained for red-C-NiSiBEA with the most amounts of Lewis acidic
centers (Table 1).
spent-red-C-NiHAlBEA
red-C-NiHAlBEA
22.41
22.54
spent-red-C-NiSiBEA
red-C-NiSiBEA
10
20
30
40
2θ
(0)
Fig. 2. XRD patterns of red-C-NiSiBEA, spent-red-C-NiSiBEA, red-C-NiHAlBEA and spent-
red-C-NiHAlBEA.
these materials, as reported earlier [13]. Additional investigations of the
catalysts after kinetic run have shown that after hydrodechlorination of
TCE the crystal structure of BEA is still preserved. Furthermore, compar-
ison investigations of the zeolites catalysts after reduction and reaction
(Fig. 2) have shown that for catalyst based on NiHAlBEA only negligible
shift of the main diffraction peak is observed (from 2θ = 22.46 for red-
C-NiHAlBEA to 2θ = 22.47 for spent-red-C-NiHAlBEA). However, for the
catalyst prepared by two-step postsynthesis method significant shift of
the main diffraction peak is observed (from 2θ = 22.54 for red-C-
NiSiBEA to 2θ = 22.41 for spent-red-C-NiSiBEA). It suggests that proba-
bly upon reaction test the oxidation of nickel nanoparticles occurs on
From the practical point of view, very important is the separation of
the value added products of hydrodechlorination of TCE. From tradi-
tional methods of hydrocarbons separation particularly noteworthy is
low-temperature distillation. In the case of ethylene /propylene separa-
tion this method is integrated with cascaded ethylene/propylene refrig-
eration system or even cryogenic distillation [16]. Economically,
attractive method of separation is the chemical affinity based technolo-
gy like π-complexation of the silver and copper ions [17]. Additionally,
for separation of olefins from 1,1-dichloroethylene we can use rectifica-
tion column, and absorbers for trapping of HCl. All of the above solutions
can be used for separation of HDC TCE products.
It should be noted here that there are only few reports showing the
catalytic conversion of trichloroethylene in the gas phase at a rather low
reaction temperature — 503 K. Generally, hydrodechlorination of TCE
were carried out at the temperature range of 373–573 K [18], but the
desirable results were observed at higher temperatures [18,19]. For ex-
ample, Meshesha et al. [11] showed results of hydrodechlorination of
TCE at 573 K. During 270 min of reaction over Pd/NiMgAl mixed
oxide, strong deactivation was observed, and the selectivity to ethylene
for NiMgAl was maximally 55%. Reactions with Cu-hydrotalcite-derived
catalysts [20] and Pt/CeO2 [2] have shown very high activity of the cat-
alysts at 573 K. At the temperature of 473 K the conversion for 0.2% Pt/
CeO2 was about 5% and ethylene and ethane were obtained as the main
products [2]. In view of the literature data our results obtained for
hydrodechlorination of trichloroethylene in a relatively low reaction
temperature are satisfactory. It is worth noting here that rather rarely
Fig. 3. Time on stream behavior during hydrodechlorination of trichloroethene, TCE con-
version at the temperature of 503 K.

110
A. Śrębowata et al. / Catalysis Communications 57 (2014) 107–110
Table 1
Representative kinetic data of trichloroethylene conversion over red-C-NiSiBEA and red-C-NiHAlBEA catalysts: reaction rates, turnover frequencies (TOFs), overall conversions, products
selectivities after 1000 min of reaction at 503 K.
Catalysts
Activity/TOF (μmol/gcat)/(s−1)
Conversion (%)
Selectivity (%)
C2H4
C3H6
1,1-C2H2Cl2
Othersa
red-C-SiBEA
0.020/nc
0.530/0.002
0.080/nc
0.2
6.8
1.0
2.6
2.00
34.9
93.1
51.5
25.8
20.1
6.90
25.5
–
72.2
–
red-C-NiSiBEA
red-C-HAlBEA
red-C-NiHAlBEA
45.0
–
–
0.200/0.003
23.0
–
a
Mainly C2 and C3 hydrocarbons and chlorohydrocarbons like: C3H8, C2H3Cl, and CH3Cl.
catalytic runs were carried out for more than 3–5 h [2,10,11,20]. Our ex-
periments were carried out for ~17 h, and during this time we did not
observe deactivation for red-C-NiSiBEA catalyst but deactivation for
red-C-HAlBEA and red-C-NiHAlBEA was observed (Fig. 3). It can be re-
lated to the particular properties of Ni-containing zeolites that are
often recommended as the catalysts for light olefin oligomerization pro-
cesses [21,22]. The application of a relatively low reaction temperature
(503 K) in our catalytic test decreases the ability of nickel containing ze-
olites to creation huge amounts of oligomers or coke and provides the
formation olefins as the main products. Obviously, we cannot complete-
ly rule out the carburization process, because we suppose that this phe-
nomenon is responsible for the deactivation of red-C-NiHAlBEA in TCE
hydrodechlorination. On the other hand, during hydrodechlorination
strong surface chlorination is also observed [23], which is responsible
for NiCl2 formation, deactivation and metal sintering [13,23]. To confirm
our suppositions, temperature-programmed hydrogenation (TPH) in-
vestigations were used to detect the main reason of deactivation of cata-
lysts. During TPH of the spent-red-C-NiSiBEA and spent-red-C-NiHAlBEA
after hydrodechlorination of trichloroethylene particular attention has
been focused on the changes of the m/z 15 and m/z 36 corresponding
to elimination of carbonaceous species and HCl from used catalysts, re-
spectively. Fig. 4a and b show that during conversion of trichloroethylene
on the catalysts are deposited species containing both carbon and chlo-
rine. Comparison of the results obtained for spent-red-C-NiSiBEA and
spent-red-C-NiHAlBEA (Fig. 4a and b) shows that more carbonaceous
and chlorine species were formed on the catalyst prepared by
conventional wet impregnation than on the catalyst prepared by two-
step postsynthesis method. A very high temperature needed for purifica-
tion of the catalysts indicates that the carbon deposits were strongly
bound to zeolite materials.
4. Conclusions
Red-C-NiSiBEA, red-C-HAlBEA and red-C-NiHAlBEA are active cata-
lysts of hydrodechlorination of trichloroethene at a relatively low reac-
tion temperature (503 K).
The small size of nickel nanoparticles present in red-C-NiSiBEA
and red-C-NiHAlBEA is responsible for the conversion of trichloroethylene
toward value added products (ethylene, propylene and 1,1-
dichloroethylene) with higher selectivity.
Catalytic stability of catalysts and product distribution depends on
the presence of Lewis and Brønsted acidic sites and their related amount.
During catalytic processes both carburization and chlorination take
place, but these phenomena have important effect only on catalytic be-
havior of HAlBEA-based catalysts.
Acknowledgments
Project funded by the Foundation for Polish Science “Parent Bridge
Programme” POMOST/2011-4/11 co-financed by the EU European Re-
gional Development Fund (AŚ, SD). Special thanks for Dariusz Łomot
from IPC PAS for the TEM measurement.
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(a) methane evolution (m/z 15) and HCl evolution (m/z 36).