Chemical Engineering Science 54 (1999) 2799}2806

Kinetic and catalytic aspects in the hydrogen peroxide

production via anthraquinone
E. Santacesaria *, M. Di Serio , A. Russo , U. Leone
, R. Velotti

Dipartimento di Chimica, Universita` di Napoli Federico II, Via Mezzocannone, 4-80134 Napoli, Italy

Ausimont Spa, Cerios, Bussi (Pescara), Italy

Abstract
The kinetic and catalytic aspects involved in the hydrogen peroxide production via anthraquinone (method all-tetra) have been
examined considering three of the four main production steps, i.e., hydrogenation of 2-ethyltetrahydroanthraquinone catalyzed by
palladium-supported catalysts, oxidation of the product obtained in the "rst step, and reconversion of the deteriorated molecules for
the regeneration of active quinones. For each reaction considered, a mechanism and a kinetic law are suggested with the numerical
values of the related parameters.  1999 Elsevier Science Ltd. All rights reserved.
Keywords: Anthraquinone; Hydrogen peroxide; Hydrogenation; Oxidation; Reconversion

1. Introduction

2. Results

The production of hydrogen peroxide via anthraquinone with the method named all-tetra occurs in four
steps, i.e.: (1) hydrogenation of 2-ethyltetrahydroanthraquinone (THEAQ) in a slurry reactor (Santacesaria et al.,
1988, 1994); (2) oxidation of the product obtained (THEAQH ) in a gas}liquid reactor (Santacesaria et al., 1987);

(3) extraction of hydrogen peroxide with an acid aqueous
solution; and (4) regeneration of active quinones from
chemically deteriorated molecules and puri"cation of the
solution on a packed bed tubular reactor (Ulmann, 1994;
Sandelin et al.,1994). In the present work, we will brie#y
summarize the results previously obtained in the kinetic
studies of step (1) and (2) and already published (Santacesaria et al., 1988,1987, 1994). More details on this subject
can be found in the mentioned literature. Step (4) will be
examined in more detail, because very few papers have
been published on this topic (Sandelin et al.,1994), despite
its importance for the management of industrial plants.

2.1. Examination of the problems involved in the xrst step:

hydrogenation of THEAQ
In the mentioned process all-tetra (Ulmann, 1994),
hydrogen peroxide is produced subjecting a mixture
of 30% 2-ethylanthraquinone (EAQ) and 70%
THEAQ dissolved in an appropriate mixture of solvents
to cyclic reduction and oxidation as in the following
scheme:

* Corresponding author. Fax: 39 81 5527771; e-mail: santacesaria

@chemna.dichi.unina.it.

0009-2509/99/$ } see front matter  1999 Elsevier Science Ltd. All rights reserved.
PII: S 0 0 0 9 - 2 5 0 9 ( 9 8 ) 0 0 3 7 7 - 7

(1)

2800

E. Santacesaria et al. /Chemical Engineering Science 54 (1999) 2799}2806

(2)
Hydrogenation is usually kept below 70% of conversion.
In this way, only THEAQ is hydrogenated because of the
presence of the following equilibrium (Berglin and
ShoK oK n,1983)
EAQH #THEAQ A EAQ#THEAQH ,



(3)

completely shifted to the right.

Hydrogenation on palladium is a very fast reaction
occurring in few minutes in a laboratory semibatch reactor. Therefore, kinetic data are normally a!ected by internal di!usion limitation. For these reasons, kinetic runs
can be performed only measuring the rates of hydrogen
consumption for di!erent catalyst hold-up and di!erent
stirring rates. The results obtained are similar to those
reported in Figs. 1 and 2 and clearly show an apparent
zero-order kinetics for hydrogen; from the shape of the
curves of hydrogen consumption during time, declining
at the end of the run, a "rst-order kinetic law can be
assumed for THEAQ. This behaviour suggests
a Rideal}Eley mechanism for THEAQ hydrogenation:
THEAQ#2 HpPTHEAQH #2p.


(4)

The zero order observed for hydrogen can be explained

considering the great a$nity of the element for palladium. It is reasonable to suppose that the dissociative
adsorption equilibrium constant for hydrogen on

Fig. 1. Example of kinetic run performed at 503C. Catalyst concentration"10 g/cm, speed"1000 rpm, [THEAQ]"0.88;10}4 mol/
cm, p "1 atm, < "300 cm.
&
*

Fig. 2. Trend of p /H against 1/m at 503C, speed"700 rpm, p "1

& P
&
atm, [THEAQ]"0.88;10\ mol/cm, < "300 cm. Elaboration of
*
initial reaction rates of di!erent kinetic runs.

palladium is very high. The kinetic behaviour of this

hydrogenation can well be described following the approach suggested by Chaudari and Ramanchandran
(1980, 1983) to calculate the overall e!ectiveness factor g.
The reaction rate was
r "gk [THEAQ].
&
&

(5)

In order to evaluate g we need to know the following

parameters: b "k a , b "k a , D , H, and their de*
* * 1
Q 1 C
pendence on temperature. All these parameters have
been determined independently of the kinetic runs and
only the kinetic parameter k has been determined from
&
the experimental runs. For a fresh palladium catalyst it
turned out to be 1.4 (cm/s g) at 503C, and 3.0 (cm/s g) at
703C.
In all the runs examined, g was always quite low
(0.02}0.15) suggesting that only a thin shell of the catalyst
particles is normally operative. In the industrial plant,
the palladium-supported catalyst is normally subjected
to progressive deactivation. As a consequence, fresh catalyst must be added during plant line operation to avoid
a loss of productivity. We recognized two types of catalyst poisoning: a reversible one due to the adsorption of
water on palladium catalytic sites, and an irreversible
and much slower one probably due to the condensation
of anthraquinone molecules with aromatic rings partially
hydrogenated on the surface of the catalyst. As catalyst
poisoning occurs very slowly, it must be studied in a continuous reactor. We created a continuous laboratory
micropilot plant to study reversible poisoning. Hydrogenation was performed in a continuous stirred tank
reactor keeping the catalyst con"ned inside the reactor
with a closely woven wire net on the bottom. Observing
that deactivation was a!ected by water concentration
and hydrogen pressure, we supposed that reversible

E. Santacesaria et al. /Chemical Engineering Science 54 (1999) 2799}2806

poisoning occurs through the following reaction:

(6)

Reversible poisoning is responsible for an about 30%

catalyst activity loss in 1 or 2 days of operation. Irreversible poisoning is much slower; to study it, we interpreted
the activity data of the industrial plant. By de"ning h(t) as
the fraction of active sites at time t, h (t) as the fraction of

available sites, i.e., of not permanently poisoned sites, and
as the fraction of the sites occupied by water, we can put
the actual kinetic constant of hydrogenation proportional to h, that is k "k h, k being the kinetic constant
&
! !
of the fresh catalyst. The evolution with time of h should
be

1 h*p
dh
& .
"!k'C h 1!
B 5
k C h
dt
CB 5
For the evolution of h we assumed:

dh
"!k''h .
B 
dt

2801

activity simulation when catalyst poisoning is neglected

as well as the agreement with our model.
The necessity to add fresh catalyst to keep the catalytic
activity in the industrial reactor constant is the most
relevant consequence of catalyst poisoning. Similarly, we
need to add EAQ to keep the optimal ratio EAQ/THEAQ constant, which is altered by the slow hydrogenation
process for the aromatic rings of EAQ and THEAQ.
These reactions do not a!ect the kinetic studies performed in laboratory reactors for the hydrogenation of
anthraquinones to oxygen, but cannot be neglected in the
simulation of big-sized continuous industrial plants for
long-time operations. Ring hydrogenation reactions are

(7)
. (9)
(8)

Initially, h"h "1.The parameter appearing in the


poisoning model has been determined by "tting experimental data and resulted: k'"6.5;10 (cm mol day),
B
k''"2.75;10\(day\) and k "3.9;10 (atm mol/
B
CB
cm). By integrating these two equations, the evolution
with time has been simulated for the catalytic activity in
an industrial plant operating 30 days. It is interesting to
observe that during the 30 days industrial run, fresh
catalyst must be added in order to keep the catalytic
activity constant up to about 200% of the initial amount.
In Fig. 3, it is possible to appreciate the evolution of the

H EAQH is inactive to produce H O . Other second


 
ary reactions occur giving anthrones and dianthrones
(Ulmann, 1994). A simpli"ed reaction scheme can be
proposed of the type (Santacesaria et al., 1984)
 THEAQH2 &&

 H8EA9H2.
EAQH2 &&

#2H


#2H

(10)


others
&&
By observing experimental kinetic runs (Santacesaria
et al., 1984), the formation of H EAQH is strongly


inhibited from EAQ. This behaviour agrees with a dual
site mechanism for the ring hydrogenation; the kinetic
relations used to simulate the three reactions examined
were:

Fig. 3. Simulation of an industrial reactor. The dashed line corresponds

to the simulation of anthraquinone conversions with a model neglecting deactivation. The continuous line interpolating experimental points
is the simulation achieved by considering the occurrence of catalyst
deactivation. The heavy continuous line corresponds to the percent of
increasing catalyst hold up in the plant.

mk b [EAQ]p
& 
&
r "
,
& (1#b [EAQ]#b [THEAQ])



(11)

mk b [THEAQ]p
& 
&
r "
,
& (1#b [EAQ]#b [THEAQ])



(12)

r "mk [EAQ]? .
&
&

(13)

Reaction (3) contributes to the loss of EAQ for less than

5%, a results about 1.

2802

E. Santacesaria et al. /Chemical Engineering Science 54 (1999) 2799}2806

Table 1
Kinetic parameters obtained by mathematical regression on
experimental data
k "(17.27$2.3) exp((!4147.6$323)/R) (mol/g atm h)
&
k "(3.7$0.41);10 exp((!11839$816)/R) (mol/g atm h)
&
k "(7.6$0.82);10 exp((!11488$923)/R) (mol/g h)
&
b "(4.8$0.54);10\ exp((4759$415)/R) (dm/mol)

b "26.5$2.3 (dm/mol)


The kinetic parameters for the same palladium-supported catalyst used in the previously mentioned kinetic
runs are collected in Table 1.
2.2. Examination of the problems involved in the second
step: THEAQH oxidation

THEAQH oxidation is normally performed at indus
trial level in bubble column continuous reactors with air
and with the working solution #owing countercurrent.
Air #ow rates are high enough to keep the liquid phase
well mixed. The reaction occurs with a second-order
kinetic law of the type (Santacesaria et al., 1987)
r "k [THEAQH ][O ].
(14)




The kinetics has been studied using two di!erent types of
reactors such as a continuous Levenspiel-type reactor
(Levenspiel and Godfrey, 1974), with a variable liquid
interface obtained using #oatings to avoid the formation
of foams, and a laboratory semibatch gas}liquid reactor
operating at variable stirring rates to produce a high
gas}liquid interphase area. The Levenspiel reactor allowed to classify the reaction as moderately slow, that is,
the enhancement factor is equal to about 1. In this
condition, the oxygen mass transfer and reaction can be
considered as consecutive steps and experimental data
can easily be interpreted. The kinetic parameters obtained were (Santacesaria et al., 1987)
k "(1.14$0.08);10 exp(!(14213$1036)/RT)

(cm/mol s).
(15)
The mass transfer and oxygen solubility parameters were
determined independently.
The kinetic law and related parameters have successfully been tested simulating the bubble column of both
a pilot and di!erent industrial plants, the values of the
gas}liquid interphase area in the examined bubble columns were somewhat uncertain as the working solution
tended to give copious foam at the top of the reactor.
From the experimental viewpoint, it is interesting to
observe that in the runs performed in the laboratory
semibatch reactor no induction time has been observed,
that is, steady-state conditions for the involved radicals
are readily achieved. Moreover, a second-order kinetic

law of the type previously seen requires a particular

reaction mechanism in which the hydrogen bond is directly transferred to the oxygen molecule, as suggested by
Etienne and Fellion (1954) to explain the mechanism of
dihydrophenazine autoxidation.
2.3. Examination of the problems involved in the fourth
step: regeneration of active quinones and puri,cation of the
working solution
We have seen that during the hydrogenation step,
secondary products are formed owing to the hydrogenation of aromatic rings. Normally, THEAQH is ob
tained from EAQ and THEAQH forms H EAQH . By



analysis we have also seen small amounts of partially
hydrogenated intermediates such as 2-ethylhexahydroanthraquinone H EAQH and 2-ethyldihydroanthra

quinone H EAQH . EAQH and THEAQH can also




give tautomerization to oxanthrone followed by the
formation of anthrone and dianthrone (Ulmann 1994)

(16)

By-products can also be formed in the oxidation step,

mainly epoxides of the type (Ulmann's, 1994):

(17)

All these secondary products are formed as a consequence of very slow reactions not a!ecting the laboratory
kinetic studies but they accumulate in the big-sized industrial plants and their reaction gives place to less
soluble condensation products probably responsible for
the permanent poisoning of the palladium-supported
catalyst. Besides adding fresh EAQ to compensate the
loss of active quinones, we therefore need to regenerate
deteriorated molecules as much as possible and to purify
the working solution from the formed tars and the acidity
developed during the autoxidation step. Alkali supported
on alumina or on silica}alumina with high surface area
are normally used as catalysts and adsorbents in this
reconversion step (Ulmann, 1994). The operation can be

E. Santacesaria et al. /Chemical Engineering Science 54 (1999) 2799}2806

2803

done on both the oxidized and reduced working solutions by feeding one of the mentioned solutions at about
100}1503C on a packed bed tubular reactor. The main
reactions promoted by the alkaline catalyst are:

being

1. THEAQ dehydrogenation, mainly occurring in the

oxidized solution with the following stoichiometry:

However, the most adsorbed active anthraquinone was

THEAQH owing to the possibility of giving hydrogen

bonds with the oxygens and hydroxyls of the solid surface. Exhausted alumina catalysts contain about 12% of
organic compounds but only 2.4% of them are active
quinones. Therefore, alkaline alumina catalysts have the
e!ect of purging and regenerating the working solution
developing three fundamental actions:

Tar(on solid)%
[Quinone]
a"
:5.
[Tar]
Quinones(on solid)%

(20)

1. promotion of the three mentioned regenerating reactions,

2. neutralization of the free acidity of the solution,
3. depuration of the working solution by adsorbing preferentially tar.
(18)
2. Epoxide reconversion, mainly occurring in a reduced solution with the following stoichiometry:

(19)

Other minor components can be reconverted to active

quinones, for example H EAQ can give THEAQ with

a reaction similar to the previous one. Other convertible
not identi"ed quinones contribute to the reconversion,
but the stoichiometry is not known and the contribution
of each substance is very small, while the overall e!ect of
these minor components is not negligible. So, we can
consider reactions of the type

A secondary negative e!ect is the promotion of the

hydrolysis of one of the solvent components with a consequent autopoisoning e!ect. All the occurring phenomena have been studied separately at laboratory level
to identify the kinetic and equilibrium expressions which
will be used in a mathematical model for simulating the
reconversion industrial section.
In this paper, we report the preliminary results obtained in the kinetic study of the two main reconverting
reactions: THEAQ dehydrogenation and epoxide reconversion.
Kinetic runs of THEAQ dehydrogenation have been
performed at 100 and 1403C in batch conditions by
withdrawing and analysing small samples of the reacting mixture at di!erent times. Reactions have been performed using 100 cm of aromatic hydrocarbons
(C }C ) in which 2 g of THEAQ were dissolved. The
 
catalyst was alumina (250 m/g) containing about 4% of
supported NaOH.
It is reasonable to assume that reaction (18) occurs
through di!erent steps and we suggest

(3) Other convertible productsPactive quinones.

Apart from promoting the mentioned reactions, the alkaline catalyst neutralizes the free acidity of the working
solution and induces the hydrolysis of 2-methylcycloacetate (one of the solvents) giving acetic acid and the
corresponding alcohol. The acetic acid formed in this
way contributes to poisoning catalyst by neutralization.
At last, tar is adsorbed preferentially on the support with
respect to the active quinones, the evaluated selectivity

(21)

2804

E. Santacesaria et al. /Chemical Engineering Science 54 (1999) 2799}2806

Table 2
Kinetic parameters obtained by mathematical regression on
experimental data
k "(9.7$0.61);10 exp((!19840$1813)/R ) (dm/mol h)

k "(3.6$0.25);10 exp((!23795$2013)/R) (dm/mol h)

"(6.1$0.41);10\ exp((3381$312)/R) (dm/mol)
b
2&#/&

(22)
because H EAQ is always present in small amounts in

the working solution. As the slow reactions occur on the
surface between adsorbed molecules:
r "k h
h
(23)
 2&#/ &#/

From the experimental evidence, it results that THEAQH is the most strongly adsorbed molecule, therefore,

b
[THEAQ]
2&#/
h
"
(24)
2&#/ 1#b
[THEAQH ]
2&#/&

and

Fig. 4. Kinetic runs of THEAQ dehydrogenation performed in batch

conditions. "1003C, catalyst concentration"100 g/dm, < "100 cm,
*
[THEAQ]"8.3;10\ mol/dm. Symbols correspond to experimental data: EAQ, THEAQ, THEAQH ; lines are obtained by

calculations.

b
[H EAQ]
&#/ 
h
"
.
(25)
&#/ 1#b
[THEAQH ]

2&#/&

By considering the "rst step in equilibrium, it results in
k [THEAQ]
.
(26)
[H EAQ]" 

[THEAQH ]

By introducing all the terms in Eq. (23), we obtain
k [THEAQ]

r "
,
(27)
 (1#b
[THEAQH ])[THEAQH ]
2&#/&


k .
where k "k b
b

 2&#/ &#/ 
However, we observed that two di!erent basic sites are
operative, one related to the supported alkali and the
other existing on the surface of the support. The latter
sites give place to adsorption phenomena which are negligible if compared with those shown by supported alkali,
therefore, for the activity of these sites, we can give
a simpler kinetic equation of the type
[THEAQ]
r "k [THEAQ][H EAQ]"k
,
(28)



 [THEAQH ]

where k "k k .

 
Experimental kinetic runs can now easily be simulated by
integrating the equations:
d[THEAQ]
"!3(r #r )


dt

Fig. 5. Kinetic runs of THEAQ dehydrogenation performed in batch

conditions. "1403C, catalyst concentration"100 g/dm, < "
*
100 cm, [THEAQ]"8.3;10\ mol/dm. Symbols correspond to experimental data: EAQ, THEAQ, THEAQH ; lines are obtained

by calculations.

d[THEAQH ]
 "2(r #r )


dt
d[EAQ]
"r #r .


dt

(29)

E. Santacesaria et al. /Chemical Engineering Science 54 (1999) 2799}2806

Fig. 6. Kinetic runs of epoxide reconversion performed in batch conditions. "1003C, catalyst concentration"100 g/dm, < "100 cm,
*
[THEAQH ]"8.0;10\ mol/dm, [Epoxide]"1.9;10\ mol/dm.

Symbols correspond to experimental data: THEAQH , Epoxide,

THEAQ; lines are obtained by calculations.

The evolution with time of experimental runs is [THEAQ]#[THEAQH ] and [EAQ], because THEAQ and

THEAQH are di$cult to be determined separately;

however, by introducing the mass balance equations for
each experimental point, the evolution with time of all
the species can be evaluated and simulated. The kinetic
parameters obtained are reported in Table 2, while in
Figs. 4 and 5 the agreement obtained with the developed
kinetic model can be appreciated. From the results of the
mass balance we also noted that the equilibrium of
H EAQ formation is almost completely shifted to the

left.
The kinetics found has also been tested in experimental
runs performed using 2-methylcycloexilacetate(2MCEA) as a solvent at 1403C taking the hydrolysis of the
solvent and the consequent poisoning of the catalyst into
account. Results were very similar.
Epoxide reconversion has been studied by dissolving
about 0.5 g of epoxide and about 0.2 g of THEAQ in
100 cm of the same previously mentioned aromatic solvent in the presence of 4 g of the same alumina catalyst
promoted with alkali. Kinetic runs have been performed

2805

Fig. 7. Kinetic runs of epoxide reconversion performed in batch conditions. "1403C, catalyst concentration"100 g/dm, < "100 cm,
*
[THEAQH ]"8.5;10\ mol/dm, [Epoxide]"2.9;10\ mol/dm.

Symbols correspond to experimental data: Epoxide, EAQ,
THEAQH , THEAQ; lines are obtained by calculations.


Table 3
Kinetic parameters obtained by mathematical regression on
experimental data
k "(2.54$0.18);10\ exp((!2512$186)/R) (dm/mol h)

k "(1.9$0.13) exp((!5295$488)/R) (dm/mol h)

b "(3.5$0.26) exp((2708$255)/R) (dm/mol)
&b "(1.9$0.14);10\ exp((5092$482)/R) (dm/mol)
1

at 100 and 1403C. Other solvents, such as 2-MCEA and

2,5 dimethyl-4-eptanol, have been used, too. We suggest
that the reaction occurs between the epoxide molecule of
the solution and an adsorbed molecule of THEAQH

(Rideal}Eley mechanism)
Therefore,
r "k h
[EPOX],

 2&#/&

(30)

where

b
[THEAQH ]
2&#/&

"
2&#/& 1#b
[THEAQH ]#b
[THEAQ]#b [H O]#b [Sol]
2&#/&

2&#/
&- 
1

(31)

b and [Sol] are di!erent according to the solvent

1
applied.
Hence,
r "
 1#b

k [THEAQH ] [EPOX]


.
[THEAQH ]#b
[THEAQ]#b [H O]#b [Sol]
2&#/&
1

2&#/
&- 

(32)

2806

E. Santacesaria et al. /Chemical Engineering Science 54 (1999) 2799}2806

In this case, too, two types of sites are operative, the same
already seen for THEAQ dehydrogenation. The basic sites
of the support give negligible adsorption e!ects, therefore,
r "k [THEAQH ][EPOX] .
(33)



The evolution with time of the di!erent involved molecular species can easily be followed by integrating the
following di!erential equations:
d[EPOX]
"!(r #r )


dt

k
&
k
*
k

k
1
K
CB
m
P
&
r
&

d[THEAQH ]
 "!(r #r )


dt
d[THEAQ]
"2(r #r )


dt
d[H O]
 "r #r .


dt

k
&

r
&
(34)

The best "tting of the experimental data have been obtained with the parameters collected in Table 3, where
b is related to 2,5-dimethyl-4-eptanol.
1
3. Conclusions
The most relevant kinetic and catalytic phenomena
occurring in the hydrogen peroxide production via
anthraquinone have been described. For the hydrogenation and oxidation steps, it has been shown that
laboratory results can usefully be extrapolated to interpret the performance of industrial plants. The same work
is in progress to describe the reconversion section.

r
&
r
G
r
MV
t

THEAQH aromatic ring hydrogenation rate


constant, mol g\ atm\ h\
rate constant of EAQH degradation, cm

g\ h\
gas-liquid mass-transfer coe$cient, cm/s
kinetic constant of ethyl-anthraquinone oxidation, cm mol\ s\
liquid-solid mass-transfer coe$cient, cm/s
equilibrium constant for the reversible catalyst
poisoning, atm mol\ cm\
catalyst hold-up, g cm\
partial pressure of H , atm

reaction rate of EAQH aromatic ring hydro
genation, mol dm\ h\
reaction rate of THEAQH aromatic ring hy
drogenation, mol dm\ h\
reaction rate of EAQH2 degradation,
mol dm\ h\
rate of i reaction, (i"1,4)
reaction rate of ethyl-anthraquinone oxidation,
mol cm\ s\
time, s
temperature, K

Greek letters
a
g
h
h*
h
G
h


reaction order for the gaseous reagent

overall e!ectiveness factor
fraction of active sites at time t
fraction of sites reversibly poisoned by water
fraction of catalyst sites occupied by i
fraction of available sites, i.e., of not permanently
poisoned sites, initially equal to 1

References
Acknowledgements
Ausimont SpA is acknowledged for the "nancial support.
Notation
a
*
a
1
b
G
C

D
C
H
k'
B
k''
B
k
G
k
&

speci"c gas}liquid interface area, cm\

speci"c liquid}solid interface area, cm\
adsorption equilibrium constant of i species, cm
or dm/mol
water concentration, mol/cm
e!ective di!usion coe$cient, cm/s
Henrys parameter of the gaseous reagent solubility, cm mol\ atm\
rate constant of reversible catalyst poisoning,
cm mol\ day\
rate constant of irreversible catalyst poisoning/day
rate constant of i reaction (i"1,4)
EAQH aromatic ring hydrogenation rate con
stant, mol g\ atm\ h\

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