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
0926-3373/99/$ see front matter 1999 Elsevier Science B.V. All rights reserved.
PII: S 0 9 2 6 - 3 3 7 3 ( 9 9 ) 0 0 0 4 1 - 7
136
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.
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-
138
Table 1
Characterization of supports
Sample
91
1Aa
2Aa
3Aa
1Bb
2Bb
3Bb
23
90
56
23
91
57
23
139
Table 2
Characterization of catalysts
Ni/2
Ni/2Aa
Ni/3Aa
Ni/1Bb
Ni/1
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
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
140
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
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
142
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.
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
60
39
26
14
7
25
51
62
79
93
15
10
12
7
0
Ni/2
Ni/3
18
13
6
4
2
Bz
53
39
25
10
0
36
51
66
85
100
11
10
9
5
0
16
10
5
3
1
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
36
20
12
7
0
47
62
76
93
100
17
18
12
0
0
Ni/2B
Ni/3B
C (%) Selectivity
C (%) Selectivity
Bz
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.
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 .
144
145
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
146
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.
References
[1] R.B. LaPierre, L. Guczi, W.L. Kranich, A.H. Weiss, J. Catal.
52 (1978) 230.
[2] H.R. Buser, Chemosphere 8 (1979) 415.
[3] B.F. Hagh, D.T. Allen, Chem. Eng. Sci. 45 (1990) 2695.
[4] H.M. Freeman, R.A. Olexsey, J. Air. Poll. Control. Assoc.
36 (1986) 67.
[5] B.F. Hagh, D.T. Allen, Innovative Hazardous Waste Treatment
Technology, vol. 1, H.M. Freement, Technomic, Lancaster,
PA, 1990.
[6] P.N. Rylander, Catalytic Hydrogenation over Platinum Metals,
Academic Press, New York, 1967, Chap. 24.
[7] B. Coq, G. Ferrat, F. Figueras, J. Catal. 101 (1986) 434.
[8] K. Kawakami, K. Kusunoki, Kagaku Kogaku Ronbunshu 1
(1975) 559.
[9] H. Kammerer, L. Horner, H. Beck, Chem. Ber. 91 (1958)
1376.
[10] E.R.A. Peeling, D.K. Shipley, Chem. Ind. (1958) 362.
[11] M. Kraus, V. Bazant, Catalysis, vol. 2, Elsevier, New York,
1973, p. 1073.
[12] E.J. Creyghton, M.H.W. Burgers, J.C. Jansen, H. vanBekkum,
Appl. Catal. A: Gen. 128(2) (1995) 275.
[13] P. Dini, J.C.J. Bart, N. Giordano, J. Chem.Soc., Perkin Trans.
2 14 (1975) 1479.
[14] S. Kovenklioglu, V. Cao, D. Shah, R.J. Farrauto, E.N. Balko,
AIChE J. 38 (1992) 1003.
[15] N. Balko, E. Prybylski, F. von Trentini, Appl. Catal. B:
Environ. 2 (1993) 1.
[16] F. Hagh, D.T. Allen, AIChE J. 36(5) (1990) 773.
[17] B. Coq, A. Tijani, R. Dutartre, F. Figueras, J. Mol. Catal. 79
(1993) 253.
[18] B. Coq, J.M. Cognion, F. Figueras, D. Tournigant, J. Catal.
141 (1993) 21.
[19] R. Ohnisshi, W. Wang, M. Ichikawa, Appl. Catal. 113 (1994)
29.
[20] J.R. Kosak, US Patent 3 546 297, 1970.
[21] Y. Hirai, K. Miyata, US Patent 4 070 401, 1973.
[22] J.R. Kosak, US Patent 3 145 231, 1969.
[23] B. Coq, A. Tijani, F. Figueras, J. Mol. Catal. 68 (1991) 331.
[24] B. Coq, A. Tijani, F. Figueras, J. Mol. Catal. 71 (1992) 317.
[25] B. Coq, R. Dutartre, F. Figueras, T. Tazi, J. Catal. 122 (1990)
438.
[26] B. Coq, A. Bittar, R. Dutartre, F. Figueras, Appl. Catal. 60
(1990) 33.
[27] B. Coq, G. Ferrat, F. Figueras, React. Kinet. Catal. Lett. 27
(1985) 157.
147