Documente Academic
Documente Profesional
Documente Cultură
1994,33, 277-284
277
Hydrogenation of 2-ethyl-5,6,7,8-tetrahydroanthraquinone
is a key step in the industrial production
of hydrogen peroxide via anthraquinone with the process named all-TETRA. This reaction on
palladium-supported catalysts is very fast; consequently, the chemical regime can hardly be achieved
and kinetics is always masked by mass-transfer limitations. Nevertheless, it is possible to demonstrate
that the reaction occurs with a zero- and first-order kinetics with respect to hydrogen and to the
organic reagent, respectively. These reaction orders can be explained on the basis of reasonable
reaction mechanisms described and discussed in this paper. Kinetics has been studied by performing
runs in two different laboratory reactors: a semibatch and a continuous stirred tank reactor. In
particular, the continuous reactor has been used for studying catalyst deactivation. Two types of
catalyst poisoning have been recognized, a reversible one, related to the presence of water, and a
permanent, not yet explained one. A kinetic expression is given also for deactivation. The kinetic
parameters obtained from the experimental runs have been verified by simulating the behavior of
an industrial reactor also considering catalyst deactivation.
Introduction
In the process named all-TETRA (see Powell, 1968;Kirk
and Othmer, 1981; Ulmanns, 1989) for the industrial
production of hydrogen peroxide, the hydrogenation of
2-ethyl-5,6,7,8-tetrahydroanthraquinone
(THEAQ) is a
fundamental step. In fact, reactions occurring in the
process are the following:
II
?H
OH
(THEAQ)
(THEAOH,)
OH
0
(THEAQ)
+ Universita di Napoli.
* Ausimont SPA-CERIOS.
w
Automatic
3500 1
I-
2ooo
1500-
.:::I
(s)
0.013 cm
178 m2/g
149 m2/g
2.25 g/cm3
0.77 g/cm3
0.80 cm3/g
%JHr
(5)
I
500
40
180
120
60
time
3 20
so0
240
700 rmn/
(5)
Figure 4. Kinetic N ~ Sperformed at different catalyst concentrations. Catalyst hold-up is reported on the plot in gIcm3. Temperature=% 'C, speed = loo0 rpm, [THEAQ1=0.88 x lo-' mollcms,
PH,=1 atm, V~=300
ems. Symbols correspond to experimentaldata;
lines are obtained by calculations.
10
0
0
100
200
300
4w
500
l / m (cm Yg)
Figure 6. Trend of pHJ" against l/m at different stirring ratea.
Temperature=%C,[THEAQI =O.&?X l ( r m o l l c m s , p ~ ~ l a t m .
vL=300 cm3.
300
*.-'
200
d
d
,.*."
60
120
loo"d",,'./
o,<p'--po
,
.
"""
180
240
_1
JOO
JBO
120
480
$40
time (SI
Figure 5. Kinetic runs performed at different catalyst concentrations. Catalyst hold-upisreportedon tbeploting/cms.Temperature
= 70 "C, speed = loo0 rpm, [THEAQl = 4.7 X l(r moVcms,PH, =
1atm, VL=ZOOems.Symbols correspondto experimentaldata; lines
are obtained by dculationa.
NM
r = q p k , C s = reaction rate
(5)
(6)
r=Tqgqi
p,/H
sP1 m
(7)
k ~ a ~
Rearranging the expression, we have
p H p (8)
I
1-6
01
0
100
2QO
300
400
I
500
l / m (cm Yg)
(10)
If (~H,CH,)'/~
>> 1, then
1lm (cm3 /gr)
r = mk[THEAQI
(12)
In order to interpret kinetic runs, we must consider both
mass-transfer and reaction steps, that is,
NGL= kLaL[@%//H)
- Cll
(13)
NH = ksas(Cl - C,)
(14)
r = smk[THEAQl
(15)
Ramachandranand Chaudari (1983) described the way to
calculate the overall effectiveness factor for a zero-order
reaction. In our case, as the THEAQ concentration is
always much higher than the hydrogen one, it is reasonable
to consider the THEAQ concentration constant for a very
small time and to assume, therefore,
k[THEAQI = ko -,
pseudo-zero-order constant (16)
Thus, the model developed by Chaudary and Ramachandran can directly be applied to o w reaction system, too.
Moreover, in o w experiments the calculated effectiveness factor was always less than 1. Calculations have been
made with the relation (see Chaudari and Ramacbandran,
1980)
(17)
where w is the overall effectiveness factor for a system
completely dominated by external diffusion. In this case;
~~~
700
lo00
2000
1000
0.10
0.07
0.11
0.28
0.08
0.27
50
1.4
0.78
0.13
0.75
70
3.0
0.32
0.12
Parameters obtained by regression on experimental data. * Parameters obtained by physical measurements (&) or by calculations
(ks).
50
50
and
1.4
1.4
Ks (cmls)
0'25
0.2
q
-
70C
0.15.
50'C
0.1
- (4'/6)1[1-
F(r])= r] - qD{[1
r = qmk,
(22)
Batch runs can be simulated by integrating the following
differential equations:
d V&
-- VMVLk,as(C,- Cs) = r"
dt
30C
0.05
goo
1000
1500
2000
2500
rpm
(24)
k , = k[THEAQ] = k[THEAQl0(1- X)
(28)
where [THEAQI O is the initial anthraquinone concentration and X is its conversion.
In order to make calculations, we need to know the
following parameters: PL = kLuL and Bs = ksas and their
dependence on temperature as well as stirring rate; De,
hydrogen solubility H , kinetic constant k, and their
dependence on temperature.
BL values have been determined in two distinct ways.
The first way is based on the measurement of the evolution
of the interface area with the stirring speed using the sulfite
method as suggested from Link and Vacek (1981) and as
DH,= 1.05 X
exp(-1520/T) (cm2/s)
(30)
5~
0
0
60
120 180 240 300 360 420 480 540 600 660 720 780
time (day)
tcme (P)
rl
0.01
0.02
0.03
0.04
0.05
m (dem5
glL
NL/h of H2adsorbed
30
25
20
I:
15
10
--
40m
20
0
8 10 12 14 16 10 20 22 24 26 28 30
time (day)
ki (cm3/(molday))
6.5 x 103
4)
- free active sites at time t
6 ( t )= UO
(33)
(34)
(35.
k = k,6
(36)
Initially 6 = 1, then the evolution with time of 6
corresponding to the evolution of k can be interpreted for
the reversible poisoning with the relation
kf (day')
2.75 X 1 t 2
Kd (atm mol/cm3)
3.9 x 104
Conclusions
Kinetics and mass transfer in the hydrogenation at the
oxygen of anthraquinones commonly used in industry, such
as THEAQ, EAQ, and their mixtures, have been studied
in the presence of palladium catalyst.
We observed that palladium is a very active catalyst of
this reaction; therefore, mass-transfer limitations strongly
affect reaction rates. In particular, internal diffusion
limitations are often operative, despite the very small size
of catalyst particles used in the experiments (see Figure
12). In order to separate all the possible contributions to
the reaction rates, kinetic law must be identified and
kinetic and mass-transfer parameters must be estimated.
For this purpose, we have shown that the hydrogenation
of anthraquinones on palladium is a zero-order reaction
with respect to hydrogen and first order with respect to
the anthraquinone. The kinetic law has been derived from
both direct and indirect observations. The kinetic constants, reported in Table 2, have been determined by
comparing the activities obtained from different kinds of
reactor, semibatch or continuous, and have been verified
by simulating a continuous industrial plant.
(cm3/s)
(cm3/s)
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