Active carbon-supported nickel-palladium catalysts for hydrodechlorination of 1,2-dichloroethane and 1,1,2-trichloroethene

Article abstract of DOI:10.1007/s11164-015-1992-7

Norit active carbon-supported Ni-Pd catalysts were prepared, by incipient wetness impregnation, from the metal chlorides NiCl₂.6H₂O and PdCl₂. The catalysts were characterized by temperature-programmed reduction, X-ray diffraction, and scanning electron microscopy, and by temperature-programmed hydrogenation (TPH) of the catalysts after use. When the catalysts were used for gasphase hydrodechlorination (HDC) of 1,2-dichloroethane (1,2-DCA) and 1,1,2-trichloroethene (TCE), very high activity and stability at a relatively low reaction temperature (503 K) were observed. Hydrodechlorination of TCE led to formation of hydrocarbons as the main products. Use of Ni and Ni-Pd catalysts for hydrodechlorination of 1,2-DCA resulted in very high (~100 %) selectivity for ethene. TPH of the catalysts after use for HDC of 1,2-DCA and TCE revealed the presence of carbon and chlorine-containing deposits on the surfaces of the catalysts. Formation of the NiC_x fcc phase and the Ni3C hcp carbide phase were detected for the monometallic nickel and Ni95Pd05 catalysts.

Full text of DOI:10.1007/s11164-015-1992-7

Res Chem Intermed
DOI 10.1007/s11164-015-1992-7
Active carbon-supported nickel–palladium catalysts
for hydrodechlorination of 1,2-dichloroethane
and 1,1,2-trichloroethene
1
1
I. I. Kami n´ ska
•
´
A. Sr e˛ bowata
Received: 27 October 2014 / Accepted: 26 February 2015
The Author(s) 2015. This article is published with open access at Springerlink.com
ꢀ
Abstract Norit active carbon-supported Ni–Pd catalysts were prepared, by in-
cipient wetness impregnation, from the metal chlorides NiCl Á6H O and PdCl . The
2
2
2
catalysts were characterized by temperature-programmed reduction, X-ray diffrac-
tion, and scanning electron microscopy, and by temperature-programmed hydro-
genation (TPH) of the catalysts after use. When the catalysts were used for gas-
phase hydrodechlorination (HDC) of 1,2-dichloroethane (1,2-DCA) and 1,1,2-tri-
chloroethene (TCE), very high activity and stability at a relatively low reaction
temperature (503 K) were observed. Hydrodechlorination of TCE led to formation
of hydrocarbons as the main products. Use of Ni and Ni–Pd catalysts for hy-
drodechlorination of 1,2-DCA resulted in very high (*100 %) selectivity for
ethene. TPH of the catalysts after use for HDC of 1,2-DCA and TCE revealed the
presence of carbon and chlorine-containing deposits on the surfaces of the catalysts.
Formation of the NiC fcc phase and the Ni C hcp carbide phase were detected for
x
3
the monometallic nickel and Ni95Pd05 catalysts.
Keywords Ni–Pd catalysts Á Active carbon Á 1,2-Dichloroethane Á
1
,1,2-Trichloroethene Á Hydrodechlorination
Introduction
The continuous development of industry results in large amounts of harmful substances
in the atmosphere, water, and soil. Particular attention should be focused on the
chlorinated hydrocarbons, e.g. 1,2-dichloroethane (1,2-DCA) and 1,1,2-trichloroethene
(
TCE)—substances commonly used in industry as solvents, extractants, and degreasing
´
A. Sr e˛ bowata
asrebowata@ichf.edu.pl
&
1
Institute of Physical Chemistry, Polish Academy of Sciences, ul. Kasprzaka 44/52,
01224 Warsaw, Poland
123

´
I. I. Kami n´ ska, A. Sr e˛ bowata
agents. Because of their potential carcinogenic, mutagenic, and teratogenic effects on
living organisms, the danger is very serious [1–3]. Therefore, finding effective and
inexpensive methods for removal of these compounds is extremely important. One such
method is hydrodechlorination (HDC). Noble metals, for example palladium and
platinum are effective catalysts of HDC [4–6], but their high cost limits practical
application. Nickel, an inexpensive metal with very good catalytic properties in the
transformationofchlorinated compoundsinto value added products, canbe anattractive
alternative for Pd and Pt [7–20]. Depending on the type of the support different product
distributions are obtained. Application of supports with acidic properties, for example
theacidicformofBEAzeoliteorc-Al O , usuallyleadstoformationofvinylchlorideas
2
3
the main product of HDC of 1,2-DCA [15, 16]; TCE conversion usually leads to
hydrocarbons [20].
Microporous Sibunit carbon-supported Ni has proved to be an active, stable and
selective catalyst for conversion of 1,2-DCA to ethylene in the presence of
hydrogen at low reaction temperatures (503 K) [21].
The purpose of this study was to investigate the effect of addition of small
amounts of palladium on the catalytic behavior of Norit CNR 115 carbon-supported
nickel in HDC of 1,2-DCA and TCE, and the effect of nickel carbiding, and of fcc
NiC phase and hcp Ni C phase formation, on the properties of Ni–Pd systems. Use
x
3
of carbon obtained from a renewable raw material by use of a patented version of
the phosphoric acid process also has environmental advantages.
Materials and methods
Ni–Pd catalysts supported on active carbon
A commercial activated carbon, CNR115, produced from a renewable raw material
by use of a patented version of the phosphoric acid process [22] and supplied by
Norit, was used as support. Before preparation of the catalysts the carbon was
washed with redistilled water, only, and dried in an air at 393 K.
A series of nickel–palladium catalysts was prepared by incipient wetness co-
impregnation of active carbon with aqueous solutions of metal chlorides (PdCl and
2
NiCl Á6H O, both of analytical purity from POCh, Gliwice, Poland). The metal-
2
2
containing solution was added to an amount of support with the same total pore volume
as the volume of solution added. For each catalyst the nickel loading was 5 wt%
whereas the amounts of palladium were to furnish the specific atomic percentages
listed in Table 1. After impregnation, the catalyst precursors were dried for 24 h with
an infrared lamp then mixed by rotary motion of a beaker containing the precursor.
Catalyst characterization and tests of catalytic activity
Temperature-programmed reduction (TPR) of catalyst precursors (*180 mg) was
performed by use of a glass-flow system equipped with a Glow-Mac thermal
conductivity detector (TCD). TPR runs were performed in 10 % H –Ar at a flow
2
3 -1
rate of 25 cm min ; the temperature was ramped from 253 to 823 K at
1
23

Active carbon-supported nickel–palladium catalysts...
Table 1 Notation used for Ni, Ni–Pd, and Pd catalysts supported on Norit CNR115
a
Catalyst notation
Ni100
Ni95Pd05
Ni90Pd10
Ni85Pd15
Pd100
Metal content (wt%)
Ni
Pd
a
5.00
–
5.00
0.45
5.00
0.95
5.00
1.50
–
1.50
In catalysts notation NiXPdY means atomic percentages of nickel and palladium in supported metal
phase
-
0 K min . For calibration, known amounts of hydrogen were injected into the
1
1
hydrogen–argon flow (before and after each TPR run).
Hydrodechlorination of 1,2-DCA and TCE was performed in a glass-flow system
equipped with fritted disk on which the catalyst was placed. Before the reactions the
catalysts were dried in flowing Ar at 393 K for 0.5 h and reduced in flowing 10 %
H –Ar at 673 K for 3 h. After reduction, the catalysts were cooled to 503 K and
2
then placed in contact with the reaction mixture (flow of hydrogen ? argon ? DCA
1:1 and
3
-1
or TCE 42 cm min ; partial pressure ratios P /P
and P /P
H2 C2H4Cl2
H2 C2H3Cl3
3
:1, respectively).
X-ray diffraction (XRD) experiments were performed with a standard Rigaku
Denki diffractometer using Ni-filtered Cu-Ka radiation. Samples before and after
HDC of 1,2-DCA and TCE were scanned by a step-by-step technique, at 2h
intervals of 0.04ꢁ.
Scanning electron microscopy (SEM) was performed by use of Nova NanoSEM
NPE190 equipment operated at an acceleration voltage between 3 and 15 keV.
After reaction with 1,2-DCA and TCE the catalysts were investigated by
temperature-programmed hydrogenation (TPH). Progress of TPH runs, using 10 %
3
-1
-1
H –He at a flow rate of 25 cm min and ramping at 10 K min , was followed by
2
mass spectrometry (MA200, Dycor-Ametek, Pittsburgh, USA). Twelve masses were
monitored during the experiment, but the major changes were observed at m/z 28
and 29 (C H release), and m/z 36 and 38 (HCl liberation) only.
2
x
Results and discussion
Temperature-programmed reduction
The TPR profiles (Fig. 1) showed that complete reduction of Norit CNR115-
supported Ni–Pd precursors occurs at\740 K. It can be assumed that the pretreatment
conditions before testing of the catalysts (10 % H –Ar, 3 h at 673 K) are sufficient for
2
complete reduction of the nickel and palladium precursors to the metals. The
temperatures of maximum reduction of PdCl and NiCl are approximately 500 and
2
2
7
12 K, respectively. The TPR profiles for the bimetallic precursors contain two
noticeable reduction maxima, those of the palladium precursor (lower temperature)
and nickel precursor (higher temperature). Distinct and well separated peaks suggest
that interaction between the Ni and Pd precursors is insignificant. A slight effect of
alloying can be observed for Ni95Pd05, for which the temperature difference between
123

´
I. I. Kami n´ ska, A. Sr e˛ bowata
Fig. 1 Temperature programmed reduction (TPR) profiles of Norit CNR115-supported Pd–Ni catalysts
the reduction peaks of the nickel and palladium precursors is the least (110 K).
Simagina et al. [10] reported that even the most sophisticated methods used for
preparation of Ni–Pd catalysts do not guarantee preparation of homogeneous products.
The shift of maximum reducibility from 712 K (for NiCl ) to 640–653 K (for the
2
bimetallic precursors) might indicate that addition of palladium minimizes the
temperature of reduction of the nickel precursor. This can be explained by the presence
of dissociated hydrogen at pre-reduced palladium centers [10]. A similar effect is very
well known for Ni–Pd/Al O catalysts [23–25].
2
3
Hydrodechlorination of 1,2-dichloroethane and 1,1,2-trichloroethene
Figure 2 shows conversion as a function of time on stream (TOS) for HDC of 1,2-
DCA over Pd–Ni catalysts. The monometallic nickel catalyst had negligible
activity. Addition of palladium substantially increased the catalytic activity. The
highest conversion was obtained for Ni85Pd15 catalyst. Ethene was the desired
product of the reaction. Figure 3 shows the changes of selectivity for C H during
2
4
1
23

Active carbon-supported nickel–palladium catalysts...
Fig. 2 Changes of conversion as a function of time on stream for hydrodechlorination of 1,2-
dichloroethane over Pd–Ni catalysts
HDC of 1,2-DCA. According to earlier studies [21, 26], almost 100 % selectivity
for ethene was observed for Ni and Ni–Pd catalysts whereas 65 % selectivity to
ethene was observed for palladium as catalyst. This phenomenon is unparalleled in
the scientific literature. The excellent hydrogenation activity of palladium usually
leads to formation of saturated hydrocarbons as the main reaction products [26–28].
To the best of our knowledge, hydrodechlorination of 1,2-DCA on palladium
catalysts usually leads to the formation of ethane as the main product. Thus, the
6
6 % selectivity for ethene obtained with Pd100 was unexpected. The reason for
this uncommon catalytic behavior of palladium could be the specific properties of
the Norit support. Mercury porosimetry and SEM studies have shown that Norit
CNR115 has a highly developed porous structure which consists of large
macropores of diameter between 2 and 30 lm, mesopores of diameter between
3
-1
1
analysis of Norit active carbon has also revealed the presence of substantial numbers
0 and 40 nm, and a total pore volume of approximately 1.11 cm g . Careful
2
-1
of micropores and a specific surface area of 1863 m g . These specific properties
of Norit carbon probably promote excellent dispersion palladium species. Because it
has been found that the dispersion of the metallic active phase can affect both
activity and product distribution [29, 30], it is possible that very high dispersion of
palladium species on the carbon support (Table 2) is involved in formation of
ethene as the main product.
In HDC of TCE the catalysts resulted in substantially higher conversion (Fig. 4)
than during HDC of 1,2-DCA (Fig. 3). Negligible activity was observed for the
monometallic nickel catalyst (Fig. 4). However, addition of palladium to the nickel
catalyst led to a substantial increase of conversion (from 0.3 % for Ni100 to *50 %
for Ni85Pd15 and Pd100) at a rather low reaction temperature (503 K). The
synergistic effect was noticed for Ni85Pd15. The main products of HDC of TCE
were hydrocarbons, for example C H , C H , and C H (Table 3). In previous
2
4
2
6
3 6
studies [31–33], the largest amounts of ethene were obtained by use of Ni85Pd15
35 %) and Pd100 (60 %), the catalysts with the maximum Pd loading.
(
123

´
I. I. Kami n´ ska, A. Sr e˛ bowata
2 4
Fig. 3 Time on stream behavior. Selectivity to C H in hydrodechlorination of 1,2-DCA
Table 2 Estimated particle sizes and dispersion for Ni–Pd catalysts, from XRD measurements
Catalyst
Particle size estimated
from SEM (nm)
Particle size estimated
a
from XRD (nm)
Dispersion
b
(%)
c
Ni100
n.m.
31
17
18
20
2
3.0
6.0
Ni95Pd05
Ni90Pd10
Ni85Pd15
Pd100
15–20
7–12
7–13
5.5
5.0
c
n.m.
56.0
a
Average Ni diameter based on (1 1 1) XRD line broadening
Measured from XRD results
b
c
Not measured
Fig. 4 Changes of conversion as a function of time on stream in HDC of TCE over Pd–Ni catalysts
1
23

Active carbon-supported nickel–palladium catalysts...
Table 3 Results of TCE hydrodechlorination at 503 K (stationary state)
Catalyst
Selectivity (%)
Conversion (%)
a
C
2
H
4
C
3
H
6
C
3
H
3
Cl
CH
Cl
2 2
CHCl
3
Other products
Ni100
32.3
29.7
35.2
36.0
59.3
21.5
2.6
1.4
0.7
0.4
–
44.3
12.2
9.2
–
1.9
13.9
15.3
15.1
21.2
0.3
25.2
38.8
47.0
45.3
Ni95Pd05
Ni90Pd10
Ni85Pd15
Pd100
2.7
4.5
5.4
7.1
38.9
34.4
35.6
–
7.2
12.0
a
2 6
Other products, e.g. C H , 1,1-dichloroethane, 1,1-dichloroethene
Fig. 5 SEM images: a Norit CNR115, and catalysts after reduction: b Ni95Pd05, c Ni90Pd10,
d Ni85Pd15
It is worth noting here that there are few reports of catalytic conversion of TCE in
the gas phase at relatively low reaction temperature -503 K. HDC of TCE has
usually been performed in the temperature range 373–573 K [31], although good
results have been obtained at higher temperatures [31, 32]. Meshesha et al. [33]
123

´
I. I. Kami n´ ska, A. Sr e˛ bowata
Fig. 6 XRD profiles of Norit CNR115-supported Ni100 after reduction and after hydrodechlorination of
1,2-dichloroethane and 1,1,2-trichloroethene
Fig. 7 XRD profiles of Norit CNR115-supported Ni95Pd05 after reduction and after hydrodechlorination of
,2-dichloroethane and 1,1,2-trichloroethene
1
reported results for HDC of TCE at 573 K. During reaction for 270 min over Pd/
NiMgAl mixed oxide, strong deactivation was observed, and the maximum
selectivity of NiMgAl for ethylene was 55 %. Cu-hydrotalcite-derived catalysts [34]
and Pt/CeO [35] have very high activity at 573 K. At 473 K conversion by
2
0
.2 %Pt/CeO was approximately 5 %, and ethylene and ethane were obtained as
2
the main products. Therefore, in view of these literature data, our results obtained
for HDC of trichloroethene at a relatively low reaction temperature are rather
satisfactory. During reaction for *17 h we did not observe deactivation of
Ni95Pd05 and Ni90Pd10. Slight deactivation of Pd100 and Ni85Pd100 was
1
23

Active carbon-supported nickel–palladium catalysts...
Fig. 8 XRD profiles of Norit CNR115-supported Ni85Pd15 after reduction and after
hydrodechlorination of 1,2-dichloroethane and 1,1,2-trichloroethene
Fig. 9 XRD profiles of Norit CNR115-supported Pd100 after reduction and after hydrodechlorination of
1,2-dichloroethane and 1,1,2-trichloroethene
observed, however (Fig. 4); this could be because of palladium segregation to the
surface and/or formation of carbon-containing deposits on active metal species
during the HDC process.
X-ray diffraction and scanning electron microscopy measurements
XRD measurements were performed for catalysts after reduction and after HDC of
1
,2-DCA and TCE. The particle sizes and metal dispersion for catalysts after
123

´
I. I. Kami n´ ska, A. Sr e˛ bowata
Fig. 10 TPH profiles of post-reaction deposition of C
hydrodechlorination of 1,2-dichloroethane
2
H
x
(m/z 28) on Ni–Pd catalysts after
reduction were estimated from XRD profiles (Table 2) and SEM images (Fig. 5).
Metal particles size obtained by use of SEM and XRD are not fully compatible. In
general, SEM measurements resulted in smaller particle sizes than those estimated
by use of XRD (Table 2).
XRD spectra for Ni100, Ni95Pd05, Ni85Pd15, and Pd100 are shown in Figs. 6,
, 8 and 9, respectively. Comparison of the XRD profiles of the reduced and spent
7
catalysts showed that carbiding occurred during reaction with 1,2-DCA and TCE.
Formation of NiC solution (fcc phase) and Ni C (hcp phase) were observed
x
3
(
Figs. 6, 7 and 8). This was much more apparent for the catalysts after HDC of TCE
(
NiC solution only), in agreement with the literature [10]. This phenomenon could
presence of hcp Ni C reflections) than of 1,2-DCA (presence of the fcc phase of
3
x
be explained by higher TCE conversion (Fig. 4), although the presence of the
double bond (C=C) in the molecular structure of TCE could also be of crucial
importance. The presence of Ni C was usually observed in nickel samples subjected
3
to such typical carbiding agents as ethene and other unsaturated hydrocarbons [22,
3
6]. XRD results (Figs. 6, 7 and 8) confirmed that 1,1,2-trichloroethene and/or HDC
of TCE products are also efficient carbiding agents. Our results are in agreement
with those obtained for Sibunit carbon-supported and alumina-supported nickel
catalysts in HDC of 1,2-DCA, in which transformation of nickel to fcc NiCx
solution and/or even to the hcp Ni C carbide phase were observed [22, 26, 37]. This
3
phenomenon strongly affected product distribution in HDC of 1,2-DCA [22].
1
23

Active carbon-supported nickel–palladium catalysts...
Fig. 11 TPH profiles of post-reaction deposition of HCl (m/z 36) on Ni–Pd catalysts after
hydrodechlorination of 1,2-dichloroethane
2 x
Fig. 12 TPH of post-reaction deposition of C H (m/z 28) on Ni–Pd catalysts after hydrodechlorination
of 1,1,2-trichloroethene
123

´
I. I. Kami n´ ska, A. Sr e˛ bowata
Fig. 13 TPH profiles of post-reaction deposition of HCl (m/z 36) on Ni–Pd catalysts after
hydrodechlorination of 1,1,2-trichloroethene
Selectivity for ethylene decreased at the expense of increasing selectivity for vinyl
chloride, in contrast with results obtained from catalytic conversion of 1,2-DCA and
TCE on Norit-supported Pd–Ni catalysts. As in previous studies [26], we could not
exclude transformation of Pd100 to PdC solution; the very high dispersion of Pd
x
made identification of the PdC form impossible, however (Fig. 9). Nevertheless,
x
palladium carbiding does not substantially affect the catalytic behavior of Pd100 or
this phase variation occurs at an initial stage of the reaction.
Temperature-programmed hydrogenation measurements
TPH measurements showed that carbonaceous species were deposited on the Ni–Pd
catalysts during HDC of 1,2-DCA (Figs. 10, 11) and TCE (Figs. 12, 13); this
resulted in blocking of the active metal sites. Deposits containing chlorine were also
observed after HDC of 1,2-DCA. A rather high temperature (600 K) was needed for
hydrogenation of carbon and chlorine-containing species, suggesting strong
interaction of these deposits with the surfaces of the catalysts.
Conclusions
•
Active carbon (Norit)-supported Ni–Pd catalysts are active and stable in HDC of
,2-DCA and TCE at a relatively low reaction temperature (503 K).
1
1
23

Active carbon-supported nickel–palladium catalysts...
•
Very high selectivity (*100 %) for the desired reaction product, ethene, was
observed in HDC of 1,2-DCA. The main products from HDC of TCE were
hydrocarbons (C H , C H , C H ).
2
4
2
6
3 8
•
•
•
Addition of palladium to the nickel resulted in a substantial increase in the
activity of the catalysts.
TPH measurements showed that carbon and chlorine-containing species were
deposited on the catalysts during reaction with 1,2-DCA and TCE.
During HDC of 1,2-DCA and TCE, the carbon from substrates permeated the
metal phase, which led to formation of the fcc NiC phase and the hcp carbide
x
Ni C phase.
3
Acknowledgments This work was funded by the National Science Centre in Poland (Research Project
SONATA based on decision DEC-2011/03/D/ST5/05516).
Open Access This article is distributed under the terms of the Creative Commons Attribution License
which permits any use, distribution, and reproduction in any medium, provided the original author(s) and
the source are credited.
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