Documenti di Didattica
Documenti di Professioni
Documenti di Cultura
Dedicated to Professor Dr. Manfred Baerns on the occasion of his 65th birthday
The catalytic properties of Pd and Pt supported on woven glass fibers (GF) were investigated in the three-phase hydrogenation of
nitrobenzene (NB). Over all catalysts, a 100 % yield of aniline was attained. The catalytic activity for the best catalysts was two
times higher than the activity of commercial Pt/C catalyst traditionally used for liquid±phase hydrogenation. The intrinsic
reaction kinetics were studied and a reaction scheme is suggested. The direct formation of aniline from NB was observed over Pd/
GF with traces of intermediates. Four intermediate products were detected during aniline formation over Pt/GF:
nitrosobenzene, phenylhydroxylamine, azoxybenzene, and azobenzene. The Eley-Rideal kinetic model fits the experimental
data well. The parameters of the model were determined as a function of initial NB concentration and hydrogen pressure. Pt and
Pd supported on GF in woven fabrics are suggested as suitable materials for reactors with a structured catalytic bed in multi-
phase reactor performance.
Chem. Eng. Technol. 23 (2000) 3, Ó WILEY-VCH Verlag GmbH, D-69469 Weinheim, 2000 0930-7516/00/0303-0251
0930-7516/00/0303-000251 $ 17.50+.50/0
$ 17.50+.50/0 251
Full Paper
samples
252 Ó WILEY-VCH Verlag GmbH, D-69469 Weinheim, 2000 0930-7516/00/0303-000252 $ 17.50+.50/0 Chem. Eng. Technol. 23 (2000) 3
Full Paper
(HOB), which is presented in the scheme, was not observed It is interesting to note that the activities of Pd and Pt
over GF catalysts. catalysts supported on glass fiber of the same type (Pd/EGF ±
HCOONa and Pt/EGF ± H2) are nearly identical and two
NB NO2 times higher than that of a commercial Pt/C catalyst (No. 8
Johnson-Matthey, 5 % Pt/C, type 18).
The activity of both Pd and Pt catalysts was observed to
depend on the support used. The Pd catalyst Pd/EGF b ±
NSB N O
AOB HCOONa showed ten times higher activity compared to the
N Pd/EGF a - HCOONa catalyst. The surface modification
+
N -
O with titania TiO2 or aluminia Al2O3 led to a considerable loss
H2 of activity, probably due to the strong metal±support
H2 AB interactions.
PHA HN
OH
N For the Pt/GF catalysts the preparation method (calcination
N
in a flow of H2 or air) strongly influences the catalytic activity
H2
H2 HOB (see Tab. 2 Pt/EGF b ± H2 and Pt/EGF b ± Air). It can be
NH assumed that the degree of the Pt reduction was higher for the
H2
AN NH2 HN pretreatment in hydrogen flow than for the catalyst calcined in
air.
Figure 3. Reaction scheme for the selective hydrogenation of nitrobenzene [4].
Figure 4. Measured and interpolated concentration profiles as a function of time Eq. (5) is obtained for a constant hydrogen pressure and the
over Pt/EGF b ± H2 catalysts (mCat = 0.4 g; pH2 = 7 bar). term k' refers to k' = k.cH2. In order to determine the modified
Chem. Eng. Technol. 23 (2000) 3, Ó WILEY-VCH Verlag GmbH, D-69469 Weinheim, 2000 0930-7516/00/0303-000253 $ 17.50+.50/0 253
Full Paper
254 Ó WILEY-VCH Verlag GmbH, D-69469 Weinheim, 2000 0930-7516/00/0303-000254 $ 17.50+.50/0 Chem. Eng. Technol. 23 (2000) 3
Full Paper
Acknowledgment Subscripts
The financial support provided for this work by the Swiss AB azobenzene
National Foundation and the Max-Buchner-Forschungsstif- AN aniline
tung is gratefully acknowledged. The authors also would like AOB azoxybenzene
to thank Prof. G. Emig and Prof. V. Barelko for fruitful GF glass fiber
discussions. HOB hydrazobenzene
Received: July 12, 1999 [CET 1140]
Me catalytic active metal (palladium or platinum)
NB nitrobenzene
NSB nitrosobenzene
Symbols used PHA phenylhydroxylamine
Pd palladium
ck [mol.l±1] concentration of component k Pt platinum
ki [gMe±1.s±1] rate constant for catalyst i Air pretreatment with air
ki' [mol.gMe±1.s±1.l±1] modified rate constant for catalyst i H2 pretreatment with hydrogen
KNB,i [l.mol±1] equilibrium constant of adsorption 0 initial rate or initial concentration
of nitrobenzene for catalyst i
mMe [g] mass of catalytic active metal
nk [mol] amount of component k References
pH2 [bar] partial pressure of hydrogen
[1] Hatzlantonlou V.; Andersson B.; Schöön N. H., Ind. Eng. Chem. Process
r [mol. gMe±1.s±1.l±1] rate constant Des. Dev. 25 (1986) pp. 964-970.
r0 [mol. gMe±1.s±1.l±1] initial rate constant [2] Kiwi-Minsker L.; Yuranov I.; Höller V.; Renken A., Chem. Eng. Sci. 54
(1999) pp. 4785±4790.
t [s] or [min] time
[3] Neyestanaki A.K.; Lindfors L.-E., Combust. Sci. and Techn. 110±111
(1995) pp. 303ff.
[4] Ertl G.; Knötzinger H.; Weitkamp J., Handbook of Heterogeneous
Catalysis, Wiley-VCH, Weinheim 1997, Vol.V.
Greek symbols [5] Tong S. B.; O'Driscoll F. K.; Rempel G. L., Can. J. Chem. Eng. 56 (1978),
pp. 340±345.
a glass fiber manufacturer Steklovokno, Belarus
b glass fiber manufacturer Vetrotex, France
stoichiometric coefficient
_______________________
Chem. Eng. Technol. 23 (2000) 3, Ó WILEY-VCH Verlag GmbH, D-69469 Weinheim, 2000 0930-7516/00/0303-000255 $ 17.50+.50/0 255