Applied Catalysis B: Environmental 22 (1999) 135147

Effect of the alumina phase and its modification on Ni/Al2 O3 catalysts

for the hydrodechlorination of 1,2,4-trichlorobenzene
Y. Cesteros a , P. Salagre a , F. Medina b , J.E. Sueiras b,
a

Facultat de Qumica, Universitat Rovira i Virgili, Pl. Imperial Tarraco, 1, 43005 Tarragona, Spain
Escola Tcnica Superior dEnginyeria, Universitat Rovira i Virgili, Pl. Imperial Tarraco, 1, 43005 Tarragona, Spain
Received 5 February 1999; received in revised form 9 April 1999; accepted 10 April 1999

Abstract
Pure and mixed /-aluminas were prepared and modified (treated with HCl gas and aq HNO3 ) in order to be studied as
supports of nickel catalysts for the hydrodechlorination reaction of 1,2,4-trichlorobenzene in the gas phase. All the samples
were structurally characterized using XRD, BET, TPR, SEM and TPD techniques. The catalytic activities for the hydrodechlorination of 1,2,4 trichlorobenzene are higher for the catalysts containing the modified supports (especially those treated with
HNO3 ) and can be explained by the reduction degree (TPR), the structure (BET area, TPD and SEM) and the number and
type of catalytic active sites (H2 TPD). The activity can be related to the hydrogen available at the reaction temperature
(423523 K) while the selectivity towards benzene can be explained in terms of the hydrogen desorbed at lower temperatures
(350500 K) which competes with the aromatic compounds to be adsorbed on the surface of the catalyst. The selectivity
towards benzene is directly related to the activity for each catalyst. Nevertheless, the most selective catalyst towards benzene
is the one supported on -alumina (73% of selectivity at 523 K) which is not the most active. This may be correlated to the
hydrogen desorbed at low temperatures. 1999 Elsevier Science B.V. All rights reserved.
Keywords: Modified alumina; Supported nickel catalysts; Hydrodechlorination; 1,2,4-trichlorobenzene

1. Introduction
Catalytic hydrodehalogenation is becoming a topic
of increasing interest as a more efficient and ecological treatments of organic wastes than incineration,
especially for chlorinated aromatic compounds where
only harsh incineration conditions might presumably
avoid the formation of polychlorinated dibenzodioxins (PCDDs) or polychlorinated dibenzofurans
(PCDFs) at high temperature, although might not
Corresponding author. Tel.: +34-77-559787; fax: +34-77559597; e-mail: jsueiras@etse.urv.es

prevent recombinations to dioxins and furans again

on lowering the temperatures of the fumes emitted
[15].
There are quite a lot of data concerning catalytic
hydrodechlorination for the reaction of hydrogen with
chlorobenzene [1,614], but it is more difficult to find
information for the most complex polychlorinated
compounds. On the whole, this catalytic process has
been studied (in liquid or gas phase) using bulk and
supported noble-metal catalysts [630] or bimetallic
noble catalysts [3133].
Moreover, systems containing Ni are known
to be active catalysts in some hydrogenation

0926-3373/99/$ see front matter 1999 Elsevier Science B.V. All rights reserved.
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Y. Cesteros et al. / Applied Catalysis B: Environmental 22 (1999) 135147

reactions [3437] and so are probably useful for

hydrodehalogenation processes. Some catalysts of
Ni/kieselguhr have been used in the hydrodechlorination of chlorinated pesticides and biphenyls
[1,3839] in the liquid phase, although dechlorination of the parent substances was not complete.
Also, supported Ni/-Al2 O3 showed catalytic activity in the gas-phase hydrodechlorination reaction of chlorobenzene [40] and different catalysts
like Ni/C, NiMo/C or NiMo/Al2 O3 were tested in
the hydrodechlorination of ortho-dichlorobenzene
[4142], 1,2,3-trichlorobenzene [4344] and in
the treatment of complex mixtures of aromatic
compounds [4546]. In a previous study, we performed the hydrodechlorination of chlorobenzene
and ortho-dichlorobenzene on bulk nickel catalysts
[47].
Recently, -Al2 O3 modifications by rare earth oxides, alkali and alkaline earth metals [4849] have
shown that incorporating additives to the supports
changes the metal dispersion, the distribution of
acid sites, physical properties like surface area, pore
structure and mechanical strength as well as thermal stability and chemical properties of the resulting
catalyst. In this way, only in a few references, the
study of the hydrodechlorination process was focused
on modified aluminametal catalysts (usually noblemetal catalysts). That alumina modification consist of
adding other oxides such as TiO2 , ZrO2 or surface
halogenation by HCl in liquid or gas phases [5053].
These studies mainly conclude that modifying alumina makes the catalysts more resistent to the toxic
effect of the HCl produced during the hydrodechlorination reaction. Obviously, if we better understand
the support modification on catalytic behaviour, we
can choose or design a better catalyst for a specific
reaction.
In this work, we report the effect of using different
alumina phases (pure and mixed /) on the activity
and selectivity of Ni/Al2 O3 catalysts for the hydrodechlorination reaction of 1,2,4-trichlorobenzene
in the gas phase. We also compare the action of
the support modification with chlorinated and nonchlorinated acids (HCl gas and HNO3 solution) on the
behaviour of the catalysts. The samples were characterized by different techniques in order to correlate
the activity with the structural characteristics of the
catalysts.

2. Experimental
2.1. Catalysts preparation
Several aluminium hydroxide gels were prepared by
precipitating a dilute aluminium nitrate solution using
ammonia as precipitant agent according to the procedure reported elsewhere [5455]. The precipitated
materials were dried overnight in an oven at 120 C.
The supports characterized as /Al2 O3 , + -Al2 O3
and -Al2 O3 were obtained by calcining the gels in
air at 950 C for 1.5 and 6 h and designated as 1,2,3,
respectively.
These aluminas were modified in two ways:
1. Treatment with HCl gas at 250 C using Ar as
a carrier gas (1 ml/s flow rate) until there were
no structural modifications in the solid (2 h) [53].
The residual HCl was displaced with Ar. The HCl
modified samples are named as 1A, 2A and 3A.
2. Treatment with a HNO3 aqueous solution. The
aluminas were previously heated for 4 h at 500 C,
then adjusted at pH2 at 25 C for 2 h with a
solution of HNO3 and finally dried overnight at
120 C [7]. These HNO3 modified supports are
designated as 1B, 2B and 3B.
The catalysts were prepared by impregnating the
modified and non-modified aluminas with aqueous solutions of Ni(NO3 )2 6H2 O to obtain a final composition of 0.21 g Ni/g Al2 O3 . The samples were calcined
at 350 C and reduced under a H2 /Ar molar ratio of
5/95 at 350 C. The catalysts are designated as Ni/1,
Ni/1A, Ni/1B, etc. All the samples have been characterized by different techniques.
2.2. Air-free sampling
The catalysts were always handled under air-free
conditions after the reduction step. The catalysts were
transferred in degassed isooctane and under a hydrogen atmosphere at room temperature. The isooctane
surface-impregnated samples were further isolated
from the air either with a gold film for the SEM study
or with sticky tape for XRD monitoring, where a
glove box was used for mounting. Catalytic activity
was measured in situ, in the same reactor after reduction, where gas purges, positive gas pressures and
Schlenk techniques were used when necessary.

Y. Cesteros et al. / Applied Catalysis B: Environmental 22 (1999) 135147

2.3. X-ray diffraction (XRD)

Powder X-ray diffraction patterns of the different
samples were obtained with a Siemens D5000 diffractometer using nickel-filtered Cu K radiation. Samples
were dusted on double-sided sticky tape and mounted
on glass microscope slides. The patterns were recorded
over a range of 2 angles from 10 to 90 and crystalline phases were identified using the Joint Committee on Powder Difrraction Standards (JCPDS) files.
2.4. BET areas
BET areas were calculated from the nitrogen adsorption isotherms at 77 K using a Micromeritics
ASAP 2000 surface analyser and a value of 0.164 nm2
for the cross-section of the nitrogen molecule.
2.5. Temperature-programmed reduction (TPR)
Temperature-programmed reductions (TPR) were
carried out in a Perkin-Elmer TGA 7 microbalance
equipped with a 2731273 K programmable temperature furnace. The accuracy was 1 g. Each
sample (30 mg) was heated in a 5 vol% H2 /Ar flow
(80 cm3 /min) and N2 flow from 323 to 623 K at
15 K min1 .The difference between the weight lost in
the two experiments was taken as a measure of the
oxygen released by the solid as water in the reduction
process.
2.6. Scanning electron microscopy (SEM)
Scanning electron micrographs were obtained with
a JEOL JSM-35C scanning microscope operating at
an accelerating voltage in the range 1525 kV, work
distance (wd) of 14 mm and magnification values in
the range 40 00050 000.
2.7. Temperature-programmed desorption (TPD)
Temperature-programmed desorptions (TPD) were
obtained with a Fisons QTMD 150 gas desorption unit
equipped with a 2731273 K programmable temperature furnace and a mass spectrometer detector.
Precursors were reduced under the same conditions
as for preparing the catalysts. The samples were then

137

cooled at room temperature, evacuated at low pressures (<1 Pa ), heated at a rate of 10 K/min up to
800 K under vacuum and the hydrogen desorption was
detected with the mass spectrometer. In order to obtain the TPD spectra of benzene, chlorobenzene, 1,2dichlorobenzene and 1,2,4-trichlorobenzene, the samples were previously reduced and a mixture of the
aromatic compound/Ar with a molar ratio of 1/300
was passed through the catalysts at room temperature
for 30 min. The excess aromatic compound was then
evacuated at low pressure. The desorption of the aromatic compounds was recorded from 313 to 523 K at
5 K/min in a vacuum.
2.8. Hydrogen chemisorption
The hydrogen chemisorption was mesured with
a Micromeritics Pulse Chemisorb 2700 instrument.
Samples were previously reduced under the same
conditions as for preparing the catalysts. After reduction, the hydrogen on the nickel surface was removed
with 15 ml min1 of N2 for 30 min at 350 C. The
sample was subsequently cooled to room temperature
under the same N2 stream and H2 pulses (0.047 ml)
were injected until the eluted area of consecutive
pulses was constant. The nickel surface atoms were
calculated assuming a stoichiometry of one hydrogen
molecule adsorbed per two surface nickel atoms.
2.9. Catalytic activity determination
The gas phase hydrogenation of 1,2,4-trichlorobenzene was studied in a fixed-bed flow tubular reactor
(i.d. 1.1 cm and length 20 cm) operating in a differential mode and heated by an oven equipped with a
temperature control system. The reactor was filled
with catalyst (200 mg), previously ground and sieved
at 25-50 mesh. The catalytic reaction was tested at
1 bar pressure, space velocity of 60 000 h1 with a
reactant/H2 ratio of 1/1500 (high H2 flow rates were
used to favour 1,2,4-trichlorobenzene transport at
room temperature) and reaction temperatures ranged
from 423 to 523 K. The catalysts did not show external diffusion restrictions as observed from the
good linearity obtained when plotting conversion
against residence time for the different catalysts.
Reaction products were analyzed by an on-line gas-

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Y. Cesteros et al. / Applied Catalysis B: Environmental 22 (1999) 135147

Table 1
Characterization of supports
Sample

Crystalline phases (XRD) -Al2 O3

Surface area (m2 /g)
a
b

91

1Aa

2Aa

3Aa

1Bb

2Bb

3Bb

+ -Al2 O3 -Al2 O3 -Al2 O3 + -Al2 O3 -Al2 O3 -Al2 O3

+ -Al2 O3 -Al2 O3
-Al(OH)3 -Al(OH)3
56

23

90

56

23

91

57

23

These samples were treated with HCl.

These samples were treated with HNO3 .

chromatograph HP 5890 equipped with a packed

column and a flame ionization detector.
Conversions and selectivities were defined by the
following equations: Conversion (%) = (mol of 1,2,4trichlorobenzene consumed) 100/(mol of 1,2,4trichlorobenzene charged); Selectivity (%) = (mol
of one product of reaction) 100/(mol of 1,2,4trichlorobenzene consumed). Conversion and selectivity values given in the results, were measured when
a plateau was reached, that is about 2 h for all catalysts. The carbon mass balance of the reaction was
maintained.

3. Results and discussion

3.1. X-ray diffraction
Powder diffraction patterns of the supports (whose
crystalline phases are indicated in Table 1) showed
diffraction peaks at 2 angles and relative intensities
that can be indexed to a poorly crystallized -Al2 O3
phase and a more crystalline -Al2 O3 phase. The 2
angles (with the relative intensities in parentheses)
taken from the JCPDS files may be summarized as follows: 25.58 (75), 35.14 (90) , 37.78 (40), 43.36 (100),
52.55 (45), 57.52 (80), 66.55 (30), 68.2 (50) for the
-Al2 O3 phase and 31.14 (40), 32.78 (80), 36.96 (60),
39.49 (40), (45.55) (80), 60.02 (40), 62.26 (40), 66.76
(60), 67.30 (100) for the -Al2 O3 phase. As expected,
the longer the calcination time, the greater the most
stable -Al2 O3 phase.
There were no differences between the diffraction
patterns of HCl-treated and untreated aluminas. However, a new peak can be detected in samples 1B and
2B (-Al2 O3 and + -Al2 O3 modified with HNO3 ,
respectively), identified as a crystalline gibbsite phase
whose corresponding 2 angles from the JCPDS files
are: 18.28 (100), 20.30 (16).

It is known [54] that the most reactive aluminas

can be moisturized in solution to obtain different aluminium polyhydroxides. In this case, the presence of
gibbsite can be explained by the acid medium, which
favours the appearance of this aluminium hydroxide
over the others. The low reactivity of the -Al2 O3
phase impedes its evolution to -Al(OH)3 (gibbsite).
The results obtained from the diffraction powders
of the catalyst precursors and catalysts (see Table 2 for
catalysts) show, in all cases, the support phases, a NiO
phase and a Ni metallic phase (only in the catalysts). In
addition to these phases, there were also broad bands
identified as a NiCl2 phase with small particle size for
the catalyst precursors and catalysts whose supports
were treated with HCl gas (less amount for the catalysts because of the reduction process). The 2 angles (with the relative intensities in parentheses) from
the JCPDS files may be summarized as follows: 15.26
(100), 30.08 (30), 36.241 (79) for the NiCl2 phase;
37.29 (91), 43.30 (100), 62.91 (57), 75.43 (16) for the
NiO phase and 44.51 (100), 51.85 (42), 76.36 (21) for
the Ni phase. The new NiCl2 phase is a consequence
of the surface chorination produced on treating the alumina with the HCl gas. Other authors have previously
reported this effect [53,56], so even in the absence of
OH groups, a process involving halogenation of the
alumina surface may also occur.
3.2. BET areas
The BET areas of the supports and catalysts are
shown in Tables 1 and 2, respectively. As expected,
the surface areas are rather low when the amount
of -Al2 O3 phase in the support increases, after
impregnation-calcination of the alumina (pore blocking) and when the nickel is in the reduced form
because of a more compact Ni phase. There were no
great differences in the values of BET area when the
modified and non-modified aluminas were compared.

Y. Cesteros et al. / Applied Catalysis B: Environmental 22 (1999) 135147

139

Table 2
Characterization of catalysts
Ni/2

Ni/2Aa

Ni/3Aa

Ni/1Bb

Ni/1

Crystalline phases (XRD)

-Al2 O3 + -Al2 O3 -Al2 O3 -Al2 O3 + -Al2 O3 -Al2 O3 -Al2 O3

NiO, Ni NiO, Ni

Surface area (m2 /g)

77
Reduction degree () (TPR) 0.09
(H/Ni0 )c
0.16

43
0.19
0.06

Ni/3

Ni/1Aa

Sample

NiO, Ni
21
0.28
0.04

NiO, Ni
NiCl2
80
0.14
0.13

NiO, Ni
NiCl2
48
0.27
0.06

NiO, Ni
NiCl2
22
0.30
0.03

NiO, Ni
-Al(OH)3
73
0.25
0.09

Ni/2Bb

Ni/3Bb

+ -Al2 O3
NiO, Ni
-Al(OH)3
38
0.35
0.04

-Al2 O3
NiO, Ni
18
0.41
0.03

The supports were treated with HCl.

The supports were treated with HNO3 .
c H from chemisorption and reduced nickel from TPR.
b

However, catalysts whose supports were treated

with HCl have slightly higher surface areas than the
non-treated samples. This may be related to the small
NiCl2 particles detected by XRD. On the other hand,
the BET areas of the catalysts whose supports were
modified with HNO3 are slightly lower than those
which have non-treated supports probably because of
the greater amount of Ni phase. This is in agreement
with the values of the reduction degree obtained by
TPR (Table 2).
3.3. Temperature-programmed reduction
In order to study the reducibility of NiO supported
on several aluminas, the reduction degree (expressed
as W0 Wt /W0 Wf , where W0 is the weight of the
unreduced sample, Wt is the sample weight at temperature t, Wf represents the weight of the completely
reduced sample) has been calculated for the catalysts.
The reduction degree and the dispersion values obtained as H/Ni0 ratio (see Table 2) exhibit opposite
tendencies. The most reduced catalysts have the lower
dispersion, as expected. By comparing the extension
of reduction in the samples we can compare the differences of the nickel-support interaction.
Firstly, when the proportion of -Al2 O3 phase in the
support is higher, the degree of reduction increases for
all samples (with modified or non-modified supports).
This is because the greater amount of -Al2 O3 phase
decreases the interaction nickel-support [5758] due
to its low reactivity. This produces fewer interaction
species like NiAlx Oy and the reduction degree of NiO
increases.
Interestingly, catalysts with modified supports
present a higher reduction degree than those whose

supports have not been treated and the highest values were for the catalysts whose supports had been
modified with HNO3 . For samples treated with HCl,
the higher reduction degree is probably due to both
the presence of the small NiCl2 particles detected by
XRD and the electron-attractive action of the chloride species which may favour the reduction process
of the NiO dispersed between these species over the
chlorinated surface.
On the other hand, for the samples treated with
HNO3 , the reasons for the greater reducibility of the
NiO may be mostly due to the thermal treatment of
the alumina at 500 C prior to the HNO3 action. It
is known [59] that heating the alumina before introducing the Ni+2 reduces the interactions between the
nickel species and the support, thus making the reduction easier. Nitrate species were however, detected by
the IR technique in the alumina after treatment with
HNO3 and in the catalytic precursors at a characteristic vibrational frequency of 1399 cm1 . These species
(as the chloride species) may too promote the NiO reduction.
3.4. Scanning electron microscopy
This technique was used to monitor the morphology
of the NiO particles for the different catalytic precursors. In contrast to the well-defined octahedral particles observed for the bulk NiO compounds [47] (obtained by calcining Ni(NO3 )2 6H2 O), most aluminasupported NiO precursors that we prepared have an
amorphous surface. This could have something to do
with the dispersion of the NiO and its interaction with
the support to produce low reduction degrees. Only
for the catalyst precursor NiO/non-modified -Al2 O3

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Y. Cesteros et al. / Applied Catalysis B: Environmental 22 (1999) 135147

Fig. 1. Scanning electron micrograph taken from the surface of the catalyst precursor : NiO/non-modified -Al2 O3 (magnification 40 000).

Fig. 2. Temperature-programmed hydrogen desorption plots obtained for catalysts Ni/1, Ni/1A and Ni/1B.

Fig. 3. Temperature-programmed hydrogen desorption plots obtained for catalysts Ni/3, Ni/3A and Ni/3B.

we can distinguish a heterogeneous distribution of octahedral forms with sizes around 8000 (Fig. 1). It
seems that the Cl and NO3 species, respectively,
induce the formation of amorphous particles of NiO
for the modified--Al2 O3 catalytic precursors.

of hydrogen and some aromatic compounds (benzene, chlorobenzene, 1,2-dichlorobenzene and 1,2,4trichlorobenzene) were performed for catalysts Ni/1,
Ni/3, Ni/1A, Ni/3A, Ni/1B and Ni/3B which are
supported on -Al2 O3 and -Al2 O3 (modified and
non-modified).
In the study of hydrogen interaction with several
surfaces, the mechanisms of adsorptiondesorption of
hydrogen can become extremely complex [6079], especially over supported catalysts, where phenomena
related with the interaction between the active phase

3.5. Temperature-programmed desorption

To obtain information about structural surface differences among several alumina-supported nickel
catalysts, the temperature-programmed desorption

Y. Cesteros et al. / Applied Catalysis B: Environmental 22 (1999) 135147

141

Fig. 4. Temperature-programmed desorption plots of the aromatic compounds : Benzene (Bz), chlorobenzene (ClBz) 1,2-dichlorobenzene
(Cl2 Bz) and 1,2,4-trichlorobenzene (Cl3 Bz) obtained for catalyst Ni/1B.

and the support can interfere. The number and approximate population of the various adsorbed species depend on many factors: the method of catalyst preparation, the kind of support used and the experimental conditions of the measurement such as weight of
examined sample, flow rate of carrier gas, the use of
ultra-high vacuum (UHV) or the shape of reactor system which affect conditions for removal of desorbed
hydrogen.
Figs. 2 and 3 show the peaks observed in the
desorption of hydrogen for the catalysts mentioned
above. TPD-curves for catalysts Ni/1 and Ni/3 (supported on non-modified -Al2 O3 and -Al2 O3 , respectively), show a low-temperature broad peak below
600 K (maxima at 410420 K) and high-temperature
less intense peaks with maxima at 700800 K. This
agrees with the spectra of other authors for aluminasupported nickel catalysts [6768,71].
The low temperature region below 600 K could be
associated with three adsorption states of the hydrogen, as has been reported [71] from the resolution
of the TPD curve. Different authors have explained
the high-temperature peak in several ways: as a consequence of the decomposition of some hydrogencontaining Nialumina compounds (possibly Nihydroaluminate) formed during high temperature
(above 773 K) treatment of the catalyst [68,7071,74]
or because of the hydrogen spillover that also

takes place during this high temperature treatment

[60,72].
These arguments cannot be applied for our catalysts because we used milder experimental conditions
(623 K). In our case, a more probable explanation is
that this high-temperature peak is associated with another adsorption state of the hydrogen (presumably related to a different morphology and size of the nickel
particles) that we have also observed for bulk nickel
catalysts [47].
Modifying the supports -Al2 O3 and -Al2 O3 with
HNO3 (catalysts Ni/1B and Ni/3B, respectively),
greatly increases the intensity of the high-temperature
peaks but decreases those of low-temperature. Catalyst Ni/1B only shows two intense peaks (maxima at
707 K, 780 K) whereas catalyst Ni/3B has one very
intense peak (maximum at 690 K) and two weak
peaks (385 K, 470 K).
For the samples whose supports were modified with
HCl (catalysts Ni/1A and Ni/3A) behaviour is different
in function of the alumina phase: for catalyst Ni/1A,
whose support is -Al2 O3 , the hydrogen mainly desorbs at a much higher temperature (maximum 1000 K)
whereas the most intense peak of catalyst Ni/3A, supported on -Al2 O3 , is around 400 K.
The different hydrogen desorption profiles obtained
from the catalysts with modified supports may again
be related to the different morphologies, sizes and the

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Y. Cesteros et al. / Applied Catalysis B: Environmental 22 (1999) 135147

Fig. 5. Temperature-programmed desorption plots of the aromatic compounds : Benzene (Bz), chlorobenzene (ClBz) 1,2-dichlorobenzene
(Cl2 Bz) and 1,2,4-trichlorobenzene (Cl3 Bz) obtained for catalyst Ni/3B.

derived electronic properties of the catalytic surface

caused by the effects of the modification protocols on
the different alumina phases.
Moreover, the TPD spectra of benzene, chlorobenzene, 1,2-dichlorobenzene and 1,2,4-trichlorobenzene
show both an increase in the maximum of the desorption temperature (for all samples) when the number of chlorines in the aromatic ring increases and
slightly higher values for the catalysts supported on
-Al2 O3 than those supported on -Al2 O3 . We can
see two of them in Fig. 4 (catalyst Ni/1B) and Fig.
5 (catalyst Ni/3B). Another point which is worth emphasizing is the low desorption temperature of these
aromatic compounds in all cases. This gives an idea
of the low level of interaction with the catalyst. We
assume that the kind of support and the morphology
of the nickel particles have not significant influence
on the desorption of the aromatic compounds. No
carbonaceous deposit seems to be formed after TPD
since no hydrogen signal was obtained from the mass
detector.
From these data, we can conclude that in catalysts
Ni/1, Ni/3, Ni/1A and Ni/3A which exhibit higher
amounts of hydrogen desorbed at lower temperatures,
the aromatic compounds compete with this hydrogen
for the adsorption on the catalyst during the catalytic
reaction. Catalysts Ni/1B and Ni/3B (whose supports

were modified with HNO3 ) mainly show one type

of active site which chemisorbs high-temperature hydrogen that probably almost completely recovers the
surface of the catalyst during the hydrodechlorination process. We can also assume that the strongly
chemisorbed hydrogen of the peaks 4 and 5 is probably not associated to the nickel phase [7071] and do
not operate at the reaction temperatures used during
hydrodechlorination (423523 K).
In this way, some studies correlate the binding
strength of the chemisorbed hydrogen and the activity
for a specific reaction [71,80]. For example, there is
a quantitative correlation between the weakly bound
hydrogen (determined from hydrogen chemisorption
isotherms at room temperature) and the specific activity of supported-nickel catalysts for benzene hydrogenation at 323 K [80]. Another study [71] shows that
toluene hydrogenation activity on nickel/alumina catalysts at 393483 K is directly related to the amount
of hydrogen desorbed at low temperatures (<450 K).
In this case, the reaction rate shows a maximum at
approximately 443 K and the decrease in the reaction
rate above this temperature is caused by the decay of
this kind of hydrogen. It seems clear that the different
states of hydrogen could may be correlated to the
activity and selectivity for the hydrodechlorination
reaction.

Y. Cesteros et al. / Applied Catalysis B: Environmental 22 (1999) 135147

143

Table 3
Catalytic behaviour of non-modified alumina-supported nickel catalysts for the hydrodechlorination processa
Catalysts Ni/1
T (K)
C (%) Selectivity (%)

523
498
473
448
423

14
11
7
3
2

Bz

ClBz o-Cl2 Bz p-Cl2 Bz

60
39
26
14
7

25
51
62
79
93

15
10
12
7
0

Ni/2

Ni/3

C (%) Selectivity (%)

C (%) Selectivity (%)

18
13
6
4
2

Bz

ClBz o-Cl2 Bz p-Cl2 Bz

53
39
25
10
0

36
51
66
85
100

11
10
9
5
0

16
10
5
3
1

Bz

ClBz o-Cl2 Bz p-Cl2 Bz

73
59
38
18
0

27
41
62
82
100

C (%): conversion at plateau (2 h); T (K): reaction temperature; Bz: benzene; ClBz: chlorobenzene; o-Cl2 Bz: 1,2-diclhorobenzene;
p-Cl2 Bz: 1,4-diclhorobenzene.

Table 4
Catalytic behaviour of HCl modified alumina-supported nickel catalysts for the hydrodechlorination processa
Catalysts Ni/1A
Ni/2A
Ni/3A
T (K)
C (%) Selectivity
C (%) Selectivity
C (%) Selectivity
Bz
ClBz o-Cl2 Bz p-Cl2 Bz
Bz
ClBz o-Cl2 Bz p-Cl2 Bz
Bz
ClBz o-Cl2 Bz p-Cl2 Bz
523
498
473
448
423

20
15
12
5
2

46
33
29
11
0

44
57
61
84
100

10
10
10
5
0

24
16
9
4
2

61
43
31
9
6

27
46
59
65
94

12
11
10
6
0

16
11
6
3
2

52
48
45
27
0

38
42
47
68
100

10
10
8
5
0

C (%): conversion at plateau (2 h); T (K): reaction temperature; Bz: benzene; ClBz: chlorobenzene; o-Cl2 Bz: 1,2-diclhorobenzene;
p-Cl2 Bz: 1,4-diclhorobenzene.

Table 5
Catalytic behaviour of HNO3 modified alumina-supported nickel catalysts for the hydrodechlorination processa
Catalysys Ni/1B
T (K)
C (%) Selectivity

523
498
473
448
423

25
17
11
5
3

Bz

ClBz o-Cl2 Bz p-Cl2 Bz

36
20
12
7
0

47
62
76
93
100

17
18
12
0
0

Ni/2B

Ni/3B

C (%) Selectivity

C (%) Selectivity

Bz

ClBz o-Cl2 Bz p-Cl2 Bz

Bz

ClBz o-Cl2 Bz p-Cl2 Bz

40
25
11
7
0

2
2
0
0
0

56
32
10
2
0

2
4
5
6
0

47
30
15
7
3

44
58
71
93
100

14
15
18
0
0

66
43
31
13
7

33
50
64
65
78

9
14
21
27
22

C (%): conversion at plateau (2 h); T (K): reaction temperature; Bz: benzene; ClBz: chlorobenzene; o-Cl2 Bz: 1,2-diclhorobenzene;
p-Cl2 Bz: 1,4-diclhorobenzene.

3.6. Catalytic activity

Tables 3, 4 and 5 summarize the conversions and
product distributions at the plateau for the hydrodechlorination reaction of 1,2,4-trichlorobenzene
on catalysts 1018 under the conditions referred to
in Section 2. Fig. 6 plots turnover frequencies (TOF)
values against temperature for each catalyst. The TOF

for the catalysts were calculated from H2 chemisorption data as the number of converted molecules of
1,2,4-trichlorobenzene s1 divided by the total number of surface nickel atoms.
On the whole, the catalysts prepared with modified
supports are more active than those prepared with nonmodified supports and the most active are those whose
supports were treated with HNO3 .

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Y. Cesteros et al. / Applied Catalysis B: Environmental 22 (1999) 135147

Fig. 6. TOF values (s1 ) vs. temperature of reaction for the

alumina-supported nickel catalysts.

From Fig. 6 we can see that the sequence of TOF

values for the catalysts at 523 K is Ni/3B>Ni/2B>Ni/
1B>Ni/3A>Ni/3>Ni/2A>Ni/2>Ni/1A>Ni/1. This order could be explained by the amount and characteristics of the active reduced nickel phase on the surface,
which in these samples is a function of the reduction
degree (TPR), the particular structure of each catalyst
(BET area, XRD, SEM) and the different kinds of
active sites (H2 TPD).At low reaction temperatures
there are some changes in this sequence. This is
probably due to the self-poisoning suffered by the
catalysts during the induction time (2 h), the extent of
which is different for each one. This is caused by the
formation of NiCl2 from the reaction of the metallic
phase and the HCl produced during the hydrodechlorination [7,47]. The extent of the poisoning process
depends on the working temperature, with a more
regeneration of the metal phase at high temperatures.
For most catalysts, there were three reaction products: mainly benzene and 1,2-dichlorobenzene but
also some 1-4-dichlorobenzene. Only catalyst 12
(Ni/non-modified -alumina) just produced benzene
and 1,2-dichlorobenzene. There was small amount
of chlorobenzene were observed for catalysts Ni/2B
and Ni/3B at the higher reaction temperatures. It
is also important to remark that no other reaction
products, like cyclohexane, chlorocyclohexane or

metadichlorobenzene were detected as they had been

with Rh, Ru, Pt and Pd catalysts [7,15,31].
The selectivity of reaction is directly related to the
conversion for each catalyst. When the conversion
increases, the selectivity towards benzene increases.
However, the most selective catalyst towards benzene
was the one supported on non-modified -alumina
(sample Ni/3) with 73% for a conversion of 16%,
whereas the most active (sample Ni/3B) was the one
supported on HNO3 -modified -alumina with a conversion of 66% and a selectivity towards benzene of
56%. At low reaction temperatures (448 K), catalyst
Ni/3A (Ni/HCl modified -alumina) was the most selective towards benzene with 27% for a conversion of
3% and the main product was 1,2,-dichlorobenzene
for all catalysts.
Generally, if we compare all catalysts at similar conversion and temperature, we can conclude that the selectivity towards benzene increases following the sequence: support modified with HNO3 <modified with
HCl<unmodified as we can see for the catalysts Ni/1,
Ni/1A and Ni/1B at 448 K.
The appearance of chlorinated intermediates for all
the catalysts during the hydrodechlorination process
could be related to a mechanism of reaction by steps
(Fig. 7) [15,31]. The magnitude of the rate constants of
1,2,4-trichlorobenzene and dichlorobenzenes transformation might be attributed to the inductive and steric
effects which form the PhCln bonds, as proposed by
Coq et al. [31] derived from the rate equations used
for Pd catalysts [7]. In our work, these effects could
explain both the formation of larger amounts of 1,2dichlorobenzene than paradichlorobenzene and the no
observation of metadichlorobenzene. For the catalysts
with high selectivity towards benzene, there is probably an increase in the value of the k2 rate constant.
There is a very good correlation between the TPD
data and the activity of the catalysts. Then, for the
hydrodechlorination reaction studied in this work, the
activity is related to the amount of chemisorbed hydrogen available during the reaction process although
the most active catalysts are those whose sites desorb
the hydrogen at high temperatures between 600 and
700 K (Peak 3, see Figs. 2 and 3). If the reaction temperatures are lower, only the hydrogen which desorbs
at low temperature is available for the activity.
On the other hand, the selectivity towards benzene
seems to be related to the sites which desorb the hy-

Y. Cesteros et al. / Applied Catalysis B: Environmental 22 (1999) 135147

145

Fig. 7. Reaction sequences for the hydrodechlorination of 1,2,4-trichlorobenzene.

drogen at lower temperatures between 350 and 500 K

(peaks 1 and 2). At these temperatures there is a competition between the hydrogen and the aromatic compounds to be adsorbed on the surface of the catalysts. Adsorbed trichlorobenzene should be easier hydrodechlorinated. When the reaction temperature is
high (523 K) the catalysts which desorb hydrogen between 400 and 500 K (Peak 2) are more selective towards benzene whereas, according to the decrease in
the reaction temperature, those which desorb the hydrogen in high proportion between 350 and 400 K
(Peak 1), are more selective towards benzene.
Consequently, the hydrogen which desorbs at lower
temperatures is the most reactive since it is mostly able
to transform the 1,2,4-trichlorobenzene completely towards benzene whereas the hydrogen chemisorbed
at higher temperatures mostly transforms the 1,2,4trichlorobenzene to chlorinated intermediate products.
The conversion and selectivity for each catalyst depend on the amount of both kinds of hydrogen. This
is in agreement with the experimental data obtained
and it seems to confirm the structure sensitivity of this
reaction.
Interestingly, the catalyst which exhibits the highest selectivity towards benzene at 523 K (catalyst Ni/3
with 73%) is the catalyst whose precursor showed
large octahedral forms with a loss of definition after
the reduction process. The micrographs and the hydrogen TPD spectra of the samples suggest that the large
faces of the octahedra for catalyst Ni/3 are probably
one of the specific active sites directly related with

Peak 2 (Fig. 5). This could explain the high selectivity

of this catalyst.

4. Conclusions
Several /-aluminas have been prepared and modified by different treatments with HCl (gas) and HNO3
(aq) to obtain alumina-supported nickel catalysts.
All the samples were structurally characterized using
XRD, BET, TPR, SEM and TPD techniques.
XRD identifies the alumina support and the NiO and
Ni phases in the catalysts. There was also an amorphous NiCl2 phase in the HCl modified samples that
produces a small increase in the values of the surface
areas and a crystalline gibbsite phase in the samples
treated with HNO3 whose supports contain -alumina.
On the other hand, when the -alumina content increases, the surface area decreases.
TPR shows different reducibilities for the supportednickel samples. The reduction degree () is higher
both for the acid modified samples (with HCl or
HNO3 ) and for those which have a higher -alumina
content.
The catalytic activities for the hydrodechlorination
of 1,2,4 trichlorobenzene are higher for catalysts containing the modified supports (especially those treated
with HNO3 ) and could be explained in terms of the
reduction degree (TPR), the structure of each catalyst
(BET area, TPD and SEM) and the number and type
of active sites present (H2 TPD). The activity is related

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Y. Cesteros et al. / Applied Catalysis B: Environmental 22 (1999) 135147

to the hydrogen chemisorbed and avalaible at the reaction temperature while selectivity towards benzene
is probably related to the hydrogen desorbed at lower
temperatures (350500 K). The most selective catalyst
towards benzene is the one supported on -alumina
(whose precursor had a clear morphology of NiO octahedral particles) with 73% at 523 K.
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