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, Università 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 anthra- 2.1. Examination of the problems involved in the xrst step:
quinone with the method named all-tetra occurs in four hydrogenation of THEAQ
steps, i.e.: (1) hydrogenation of 2-ethyltetrahydroanthra-
quinone (THEAQ) in a slurry reactor (Santacesaria et al., In the mentioned process all-tetra (Ulmann, 1994),
1988, 1994); (2) oxidation of the product obtained (THE- hydrogen peroxide is produced subjecting a mixture
AQH ) in a gas}liquid reactor (Santacesaria et al., 1987); of 30% 2-ethylanthraquinone (EAQ) and 70%

(3) extraction of hydrogen peroxide with an acid aqueous THEAQ dissolved in an appropriate mixture of solvents
solution; and (4) regeneration of active quinones from to cyclic reduction and oxidation as in the following
chemically deteriorated molecules and puri"cation of the scheme:
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 (Santa-
cesaria 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 (1)
its importance for the management of industrial plants.

* 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
2800 E. Santacesaria et al. /Chemical Engineering Science 54 (1999) 2799}2806
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 ,
 
completely shifted to the right.
Hydrogenation on palladium is a very fast reaction
occurring in few minutes in a laboratory semibatch reac-
tor. Therefore, kinetic data are normally a!ected by in-
ternal 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.
 been determined independently of the kinetic runs and
The zero order observed for hydrogen can be explained
considering the great a$nity of the element for pallad-
ium. It is reasonable to suppose that the dissociative
adsorption equilibrium constant for hydrogen on
Fig. 1. Example of kinetic run performed at 503C. Catalyst concentra-
tion"10 g/cm, speed"1000 rpm, [THEAQ]"0.88;10}4 mol/
cm, p "1 atm, < "300 cm.
& *
(2)
(3)
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 ap-
proach 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
(4)
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 cata-
lyst must be added during plant line operation to avoid
a loss of productivity. We recognized two types of cata-
lyst 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 con-
tinuous reactor. We created a continuous laboratory
micropilot plant to study reversible poisoning. Hydro-
genation 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 2801

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. Irrevers-
ible 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
 simulation of big-sized continuous industrial plants for
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 propor-
tional to h, that is k "k h, k being the kinetic constant
& ! !
of the fresh catalyst. The evolution with time of h should
be
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/THE-
AQ 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 per-
formed in laboratory reactors for the hydrogenation of
anthraquinones to oxygen, but cannot be neglected in the
long-time operations. Ring hydrogenation reactions are

 
dh 1 h*p
"!k'C h 1! & . (7)
dt B 5 k C h
CB 5
For the evolution of h we assumed: . (9)

dh
"!k''h . (8)
dt B 

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


poisoning model has been determined by "tting experi-
mental 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 H EAQH is inactive to produce H O . Other second-
cm). By integrating these two equations, the evolution    
ary reactions occur giving anthrones and dianthrones
with time has been simulated for the catalytic activity in
(Ulmann, 1994). A simpli"ed reaction scheme can be
an industrial plant operating 30 days. It is interesting to
proposed of the type (Santacesaria et al., 1984)
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.  THEAQH2 &&

EAQH2 &&
 H8EA9H2. (10)
#2H #2H
In Fig. 3, it is possible to appreciate the evolution of the  


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:

mk b [EAQ]p
r " &  & , (11)
& (1#b [EAQ]#b [THEAQ])
 
mk b [THEAQ]p
r " &  & , (12)
& (1#b [EAQ]#b [THEAQ])
Fig. 3. Simulation of an industrial reactor. The dashed line corresponds  
to the simulation of anthraquinone conversions with a model neglect-
r "mk [EAQ]? . (13)
ing 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 Reaction (3) contributes to the loss of EAQ for less than
increasing catalyst hold up in the plant. 5%, a results about 1.
2802 E. Santacesaria et al. /Chemical Engineering Science 54 (1999) 2799}2806

Table 1 law of the type previously seen requires a particular

Kinetic parameters obtained by mathematical regression on reaction mechanism in which the hydrogen bond is dir-
experimental data ectly transferred to the oxygen molecule, as suggested by
k "(17.27$2.3) exp((!4147.6$323)/R¹) (mol/g atm h) Etienne and Fellion (1954) to explain the mechanism of
& dihydrophenazine autoxidation.
k "(3.7$0.41);10 exp((!11839$816)/R¹) (mol/g atm h)
&
k "(7.6$0.82);10 exp((!11488$923)/R¹) (mol/g h)
&
b "(4.8$0.54);10\ exp((4759$415)/R¹) (dm/mol) 2.3. Examination of the problems involved in the fourth

b "26.5$2.3 (dm/mol)
 step: regeneration of active quinones and puri,cation of the
working solution

The kinetic parameters for the same palladium-sup- We have seen that during the hydrogenation step,
ported catalyst used in the previously mentioned kinetic secondary products are formed owing to the hydrogen-
runs are collected in Table 1. ation of aromatic rings. Normally, THEAQH is ob-

tained from EAQ and THEAQH forms H EAQH . By
  
2.2. Examination of the problems involved in the second analysis we have also seen small amounts of partially
step: THEAQH oxidation hydrogenated intermediates such as 2-ethylhexahydro-
 anthraquinone H EAQH and 2-ethyldihydroanthra-
 
quinone H EAQH . EAQH and THEAQH can also
THEAQH oxidation is normally performed at indus-    
 give tautomerization to oxanthrone followed by the
trial level in bubble column continuous reactors with air
and with the working solution #owing countercurrent. formation of anthrone and dianthrone (Ulmann 1994)
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 (16)
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 al-
lowed to classify the reaction as moderately slow, that is, By-products can also be formed in the oxidation step,
the enhancement factor is equal to about 1. In this mainly epoxides of the type (Ulmann's, 1994):
condition, the oxygen mass transfer and reaction can be
considered as consecutive steps and experimental data
can easily be interpreted. The kinetic parameters ob-
tained were (Santacesaria et al., 1987) (17)

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 success-
fully 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 col-
umns 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
All these secondary products are formed as a conse-
quence of very slow reactions not a!ecting the laboratory
kinetic studies but they accumulate in the big-sized in-
dustrial 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
done on both the oxidized and reduced working solu-
tions 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:
1. THEAQ dehydrogenation, mainly occurring in the
oxidized solution with the following stoichiometry:
(18)
2. Epoxide reconversion, mainly occurring in a re-
duced solution with the following stoichiometry:
(19)
Other minor components can be reconverted to active
quinones, for example H EAQ can give THEAQ with
 It is reasonable to assume that reaction (18) occurs
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
(3) Other convertible productsPactive quinones.
Apart from promoting the mentioned reactions, the alka-
line catalyst neutralizes the free acidity of the working
solution and induces the hydrolysis of 2-methylcyc-
loacetate (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
2803
being
Tar(on solid)% [Quinone]
a" :5. (20)
[Tar] Quinones(on solid)%
However, the most adsorbed active anthraquinone was
THEAQH owing to the possibility of giving hydrogen

bonds with the oxygens and hydroxyls of the solid sur-
face. 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:
1. promotion of the three mentioned regenerating reac-
tions,
2. neutralization of the free acidity of the solution,
3. depuration of the working solution by adsorbing pref-
erentially tar.
A secondary negative e!ect is the promotion of the
hydrolysis of one of the solvent components with a con-
sequent autopoisoning e!ect. All the occurring phe-
nomena 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 ob-
tained in the kinetic study of the two main reconverting
reactions: THEAQ dehydrogenation and epoxide recon-
version.
Kinetic runs of THEAQ dehydrogenation have been
performed at 100 and 1403C in batch conditions by
withdrawing and analysing small samples of the reac-
ting mixture at di!erent times. Reactions have been per-
formed 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.
through di!erent steps and we suggest
(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)/R¹ ) (dm/mol h)


k "(3.6$0.25);10 exp((!23795$2013)/R¹) (dm/mol h)

b "(6.1$0.41);10\ exp((3381$312)/R¹) (dm/mol)
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 THE-
AQH is the most strongly adsorbed molecule, therefore,

b [THEAQ] Fig. 4. Kinetic runs of THEAQ dehydrogenation performed in batch
h " 2&#/ (24) conditions. ¹"1003C, catalyst concentration"100 g/dm, < "100 cm,
2&#/ 1#b [THEAQH ] *
2&#/&  [THEAQ]"8.3;10\ mol/dm. Symbols correspond to experi-
mental data: 䊏 EAQ, 䊉 THEAQ, 䉱 THEAQH ; lines are obtained by
and 
calculations.
b [H EAQ]
h " &#/  . (25)
&#/ 1#b [THEAQH ]
2&#/&  
By considering the "rst step in equilibrium, it results in
k [THEAQ]
[H EAQ]"  . (26)
 [THEAQH ]

By introducing all the terms in Eq. (23), we obtain
k [THEAQ]
r "  , (27)
 (1#b [THEAQH ])[THEAQH ]
2&#/&  
where k "k b b k .
  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 neg-
ligible if compared with those shown by supported alkali, Fig. 5. Kinetic runs of THEAQ dehydrogenation performed in batch
therefore, for the activity of these sites, we can give conditions. ¹"1403C, catalyst concentration"100 g/dm, < "
*
a simpler kinetic equation of the type 100 cm, [THEAQ]"8.3;10\ mol/dm. Symbols correspond to ex-
perimental data: 䊏 EAQ, 䊉 THEAQ, 䉱 THEAQH ; lines are obtained

[THEAQ] by calculations.
r "k [THEAQ][H EAQ]"k , (28)
    [THEAQH ]

where k "k k .
   d[THEAQH ]
 "2(r #r )
Experimental kinetic runs can now easily be simulated by  
dt
integrating the equations:
d[THEAQ] d[EAQ]
"!3(r #r ) "r #r . (29)
dt   dt  
 E. Santacesaria et al. /Chemical Engineering Science 54 (1999) 2799}2806 2805

Fig. 6. Kinetic runs of epoxide reconversion performed in batch condi-

tions. ¹"1003C, catalyst concentration"100 g/dm, < "100 cm,
* Fig. 7. Kinetic runs of epoxide reconversion performed in batch condi-
[THEAQH ]"8.0;10\ mol/dm, [Epoxide]"1.9;10\ mol/dm.
 tions. ¹"1403C, catalyst concentration"100 g/dm, < "100 cm,
Symbols correspond to experimental data: 䊏 THEAQH , 䊉 Epoxide, *
 [THEAQH ]"8.5;10\ mol/dm, [Epoxide]"2.9;10\ mol/dm.
䉱 THEAQ; lines are obtained by calculations. 
Symbols correspond to experimental data: 䊏 Epoxide, 䊉 EAQ,
䉱 THEAQH , 䉲 THEAQ; lines are obtained by calculations.

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

THEAQH are di$cult to be determined separately;
 Table 3
however, by introducing the mass balance equations for Kinetic parameters obtained by mathematical regression on
each experimental point, the evolution with time of all experimental data
the species can be evaluated and simulated. The kinetic k "(2.54$0.18);10\ exp((!2512$186)/R¹) (dm/mol h)
parameters obtained are reported in Table 2, while in 
k "(1.9$0.13) exp((!5295$488)/R¹) (dm/mol h)

Figs. 4 and 5 the agreement obtained with the developed b "(3.5$0.26) exp((2708$255)/R¹) (dm/mol)
&-
kinetic model can be appreciated. From the results of the b "(1.9$0.14);10\ exp((5092$482)/R¹) (dm/mol)
1
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 at 100 and 1403C. Other solvents, such as 2-MCEA and
runs performed using 2-methylcycloexilacetate(2- 2,5 dimethyl-4-eptanol, have been used, too. We suggest
MCEA) as a solvent at 1403C taking the hydrolysis of the that the reaction occurs between the epoxide molecule of
solvent and the consequent poisoning of the catalyst into the solution and an adsorbed molecule of THEAQH

account. Results were very similar. (Rideal}Eley mechanism)
Epoxide reconversion has been studied by dissolving Therefore,
about 0.5 g of epoxide and about 0.2 g of THEAQ in
100 cm of the same previously mentioned aromatic sol- r "k h [EPOX], (30)
  2&#/&
vent in the presence of 4 g of the same alumina catalyst
promoted with alkali. Kinetic runs have been performed where

b [THEAQH ]
h " 2&#/&  (31)
2&#/& 1#b [THEAQH ]#b [THEAQ]#b [H O]#b [Sol]
2&#/&  2&#/ &-  1
b and [Sol] are di!erent according to the solvent
1
applied.
Hence,

k [THEAQH ] [EPOX]
r "   . (32)
 1#b [THEAQH ]#b [THEAQ]#b [H O]#b [Sol]
2&#/&  2&#/ &-  1
2806 E. Santacesaria et al. /Chemical Engineering Science 54 (1999) 2799}2806

In this case, too, two types of sites are operative, the same k THEAQH aromatic ring hydrogenation rate
& 
already seen for THEAQ dehydrogenation. The basic sites constant, mol g\ atm\ h\
of the support give negligible adsorption e!ects, therefore, k rate constant of EAQH degradation, cm
& 
g\ h\
r "k [THEAQH ][EPOX] . (33)
   k gas-liquid mass-transfer coe$cient, cm/s
*
The evolution with time of the di!erent involved molecu- k kinetic constant of ethyl-anthraquinone oxida-

lar species can easily be followed by integrating the tion, cm mol\ s\
following di!erential equations: k liquid-solid mass-transfer coe$cient, cm/s
1
K equilibrium constant for the reversible catalyst
d[EPOX] CB
"!(r #r ) poisoning, atm mol\ cm\
dt   m catalyst hold-up, g cm\
d[THEAQH ] P partial pressure of H , atm
 "!(r #r ) & 
  r reaction rate of EAQH aromatic ring hydro-
dt & 
genation, mol dm\ h\
d[THEAQ] r reaction rate of THEAQH aromatic ring hy-
"2(r #r ) & 
dt   drogenation, mol dm\ h\
r reaction rate of EAQH2 degradation,
d[H O] &
 "r #r . (34) mol dm\ h\
dt   r rate of i reaction, (i"1,4)
G
The best "tting of the experimental data have been ob- r reaction rate of ethyl-anthraquinone oxidation,
MV
tained with the parameters collected in Table 3, where mol cm\ s\
b is related to 2,5-dimethyl-4-eptanol. t time, s
1 ¹ temperature, K

3. Conclusions Greek letters

The most relevant kinetic and catalytic phenomena
occurring in the hydrogen peroxide production via
anthraquinone have been described. For the hydrogen-
ation and oxidation steps, it has been shown that
laboratory results can usefully be extrapolated to inter-
pret the performance of industrial plants. The same work
is in progress to describe the reconversion section.
a reaction order for the gaseous reagent
g overall e!ectiveness factor
h fraction of active sites at time t
h* fraction of sites reversibly poisoned by water
h fraction of catalyst sites occupied by i
G
h fraction of available sites, i.e., of not permanently

poisoned sites, initially equal to 1

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