I n d . E n g . C h e m . Res.

1987,26, 155-159 155

Kinetic Aspects in the Oxidation of Hydrogenated

2-Ethyltetrahydroanthraquinone
E. Santacesaria*
C.N.P.M., Centro Nazionale Propulsione ed Energetica, 20133 Milano, Italy
R. Ferro and S. Ricci
Montefluos S.p.A. Company, 20133 Milano, Italy
S. CarrP
Dipartimento di Chimica Fisica Applicata del Politecnico, 20133 Milano, Italy

In this paper the kinetic aspects of the oxidation of hydrogenated 2-ethyltetrahydroanthraquinone

have been examined. This reaction occurs with molecular oxygen in gas-liquid reactors and is a
key reaction in the industrial production of hydrogen peroxide. I t has been observed that reaction
rates are strongly affected by mass transfer of oxygen across the liquid film. The mass-transfer
coefficient of oxygen has been experimentally evaluated in absorption-desorption runs by employing
an amperometric membrane electrode. Kinetic runs have been carried out in three types of reactors:
a Levenspiel reactor with very low interfacial area, a CSTR reactor, and a well-stirred batch reactor
with very high interfacial area. The kinetic regime has been determined and corresponds to a slow
to moderately fast reaction with a Hatta number in the range 0.2-0.4 and enhancement factor of
about 1. A second-order kinetic law has been proven to be reliable for interpreting the kinetic data.

In the process &-TETRA (Powell, 1968; Ullmann, 1969)
for the industrial production of hydogen peroxide, 2-
ethyltetrahydroanthraquinone (THEAQ), is subjected to
cyclic reduction and oxidation as in the following scheme:
0 OH
*H2-
rates. Therefore, in this paper mass-transfer effects have
been carefully considered. In particular, the mass-transfer
rates of oxygen in the working solution have been exper-
imentally measured, in transient conditions, for deter-
mining the related coefficient. Kinetics have been studied
by employing two different types of CSTR reactors and
(1) have been verified in a batch reactor.

0 OH
OH 0 employed three types of gas-liquid reactors: a slightly
*02- W H 2 0 2 (2)
OH 0 The use of the first type of reactor, characterized by a very
A mixture of 70% THEAQ and 30% 2-ethylanthraquinone
(EAQ) dissolved in a suitable solvent is usually worked up
in industry, as reported by Ullmann (1969). Also EAQ is
reduced by hydrogen to EAQH2, but it readily reacts, as
described by Berglin and Shoon (1983), to give
EAQHz + THEAQ THEAQHz + EAQ (3)
This equilibrium is almost completely shifted to the right.
However, in order to avoid secondary reactions, only
60-70% of the mixture of anthraquinone is reduced in the
hydrogenation step. Therefore, only THEAQHz is in-
volved in the successive oxidation step.
No paper has been published, in the past, dealing with
the kinetic aspects of the above described oxidation re-
action. This reaction can be classified as an autoxidation
in agreement with James and Weissberger (1938). How-
ever, with respect to other well-studied autoxidations, in
this case, reaction rates depend on oxygen concentration.
This behavior seems to be common to other autoxidable
substances that form stable radicals as,for example, phenol
(Denisov, 1980). The oxidation of THEAQHz with mo-
lecular oxygen is usually performed, on a large scale, in
gas-liquid reactors in which gas-liquid interfaces are
maximized. This fact clearly denotes that oxygen mass
transfer plays an important role in limiting the reaction
*To whom correspondence must be addressed.
0SSS-5SS5/S7/2626-0155$01.50/0
Experimental Section
(A) Method, Apparatus, and Reagents. In order to
study the kinetics of the oxidation of THEAQHz,we have
modified Levenspiel reactor (Levenspiel and Godfrey,
1974), a CSTR reactor, and a well-stirred batch reactor.
small interfacial area, had the scope to individuate the
operative kinetic regime and to estimate the mass-transfer
coefficient of molecular oxygen in the presence of the re-
action. The second type of reactor has been employed for
determining the chemical kinetic constant, while the third
type has been employed for testing the reliability of both
the kinetic model and the parameters. Mass-transfer rates
of oxygen in the solution have been independently mea-
sured in transient conditions by the classic amperometric
membrane electrode suggested by Clark (1959). The em-
ployed electrode was from Ingold Co. The response of this
electrode to the oxygen concentration was fast enough to
allow accurate measurements of the oxygen mass-transfer
coefficient also by neglecting the time constant of the
electrode, very small in respect to the duration of the run.
Two types of runs were performed that are characterized
by absorption or desorption of oxygen in the solvent of
anthraquinones, that is, a mixture of aromatics. The liquid
was gently stirred in order to avoid increase of the inter-
facial area by cavitation. The current signal, proportional
to the oxygen concentration, was recorded during the time.
In the absorption runs, oxygen was fed upon the surface
of the liquid purged with nitrogen. On the contrary, in
the desorption runs, nitrogen was fed upon the surface of
the liquid saturated with oxygen. The presence of an-
thraquinone, in the oxidized form, has been tested and
does not affect significantly mass-transfer rates and oxygen
solubility. The measurements, therefore, were performed
0 1987 American Chemical Society
156 Ind. Eng. Chem. Res. Vol. 26, No. 1, 1987

-
to the gasvolumetric
burette
o-\\ y

in

0
U

1 out

0
Figure 1. Scheme of the slightly modified Levenspiel reactor.
Floatings have been employed in order to avoid formation of foams.
(1)and (3) correspond to the inlet and the outlet, respectively, of the
thermostating fluid, while (2) and (4) are the inlet and outlet of the Figure 2. Scheme of the employed continuous gas-liquid reactor.
working solution. ( 5 ) is connected to a gas volumetric buret. In the same scheme is also represented in detail the stirrer used in
the kinetic runs. (1)and (3) are the inlet and outlet, respectively,
in the solvent of anthraquinones. of the thermostating fluid, while (2) and (4) are the inlet and outlet
The solubility of oxygen in the working solution has been of the working solution. ( 5 ) is connected with a gas volumetric buret.
evaluated by the method suggested by Nitta et al. (1983).
All kinetic runs have been performed, at 50 "C, on a
mixture of EAQ-THEAQ not fully reduced (60-70%) or
in the presence of fully reduced THEAQ. The composition
of the mixture was about 30% EAQ and 70% THEAQ in
moles, while the concentration of THEAQ was kept below
0.3 M.
The employed Levenspiel reactor is represented in 30 t /

Figure 1. In this reactor the interfacial area was changed
by using floatings in order to avoid the formation of foams.
The reactor, having a total volume of 3 L, was filled with
1650 cm3 of liquid and was operated as a continuous re-
actor for the liquid and as a batch reactor for the gas. Pure
oxygen and mixtures of nitrogen with oxygen were em-
ployed in the kinetic runs.
The CSTR reactor, used in the kinetic runs, is repre-
sented in Figure 2. It had a capacity of about 1 L and
was filled with 300 cm3 of liquid.
Only pure oxygen has been employed in these runs. A
stirrer of particular shape, in Figure 2, was employed. This
stirrer operates in such a way that both phases can be
considered completely mixed and very high interfacial
areas, related to the rotating speed, can be obtained. The
effect of stirring on gas-liquid mass-transfer rates can be
determined with the sulfite method described by Char-
pentier (1981) and Linek and Vacek (1981). This can be
done by comparing the absorption rates of oxygen, in
aqueous solutions of sodium sulfite, of opportune con-
centration, containing cobalt ions, as catalyst, stirred at
different values of rpm, with the one obtained in a solution
of the same type, well stirred, but without producing
bubbles. This last condition has been considered by us,
as a fluid dynamic reference situation, in which interface
area is obviously known. In the same fluid dynamic con-
ditions, the mass-transfer coefficient of oxygen, in the
working organic solution, has been determined, with the
amperometric electrode. Increasing rotating speed, with
2ol J
10
0
0 500 1mo 1500 ZOW 2500 rpm
Figure 3. Effect of stirring, with the turbine represented in Figure
2, on the apparent interfacial area.
respect to the reference described conditions, increases the
mass-transfer rates of oxygen, in the sulfite solution. This
effect is due mainly to the increase in interface area, but
the mass-transfer coefficient also increases with stirring.
Since these two parameters appear to be always coupled
in the mass-transfer relationships, it is convenient to define
an "apparent interface area" in which both the stirring
effects on the true interface area and on the mass-transfer
coefficient are contained. The mass-transfer coefficient
is consequently considered constant, with stirring, and
equal to the one measured in the described fluid dynamic
reference conditions. The obtained values of apparent
interface area, at different stirring speeds, are reported in
Figure 3. It must be pointed out that the trend of Figure
3 probably is different in the case of solvents other than
water. On the other hand, in our case, viscosity and
density of the employed organic solvent were comparable
with respect to water, and the observed values of gas
holdup were also similar, despite the different surface
tensions. On the basis of these facts, we have assumed,
as a reasonable approximation, the apparent interface area
 Ind. Eng. Chem. Res. Vol. 26, No. 1, 1987 157
I InAl
equal, in the two mentioned systems, at the same rpm.
400 r
The possible error in this procedure would be, according
to us, of the same order of magnitude of the experimental
error in the kinetic measurements. The stirred reactor,
operating in batch conditions for both the liquid and gas 300 I
phases, is quite similar to the one just described. Since
the oxidation reaction is very fast at high levels of inter-
facial area, care must be taken, in batch runs to avoid the 200
dead time in mixing reagents. If this aspect is neglected,
erroneous conclusions could be reached about the presence
or not of autocatalytic effects in the reaction. 100
Kinetic runs in batch conditions have been performed
on fully hydrogenated THEAQ and EAQ, respectively,and
on partially hydrogenated mixtures.
Runs have been performed by introducing the liquid, 0 1000 2000 3000 4000
Time I S I
kept a t 50 "C and under nitrogen, a t constant feed rate
into the reactor, which has been previously fiied with pure Figure 4. Fitting of the evolution of current as a function of time
oxygen. In practice, oxygen mass transfer and reaction in an absorption run performed at 20 "C.
rates become significant only when the level of the liquid
reaches the impeller. Table I. Kinetic and Thermodynamic Parameters
Reaction rates were measured, in all types of reactors, Determined for the Oxidation of THEAQHz
by measuring the oxygen consumption by a gas volumetric Henry const, atm cm3/mol H,,oc = 112 100
buret. This buret measures and replaces reacted oxygen Hb, o c = 109 000
mass-transfer coeff, cm/s kL(20 "C) = 5.5 X
without requiring any manual intervention. All the kL(50 "C) = 6.6 X
reagents have been supplied by Montefluos S.p.A. kinetic const, cm3/(mol s) kc = 3830 f 300
Results and Discussion Table 11. Rates of Oxygen Consumption Obtained in the
Oxidation of THEAQHz by molecular oxygen occurs Levensoiel Reactor. in Different Ooerative Conditions"
through the following steps: (a) diffusion of oxygen from interface liq PO,' rates, 103kL,
the gas phase to the gas-liquid interphase and (b) diffusion area, cm2 flow rate atm mol/s x lo6 cm/s
of oxygen from the liquid interphase into the bulk of the 89.62 0.744 1 2.568 3.12
solution with chemical reaction. 89.62 0.372 1 2.713 3.30
By operation in the presence of pure oxygen, the first 89.62 0.372 1 3.230 3.93
step can be ignored. The other two steps can occur si- 89.62 0.372 1 2.903 3.53
multaneously. Therefore, in order to evaluate the extent 89.62 0.372 1 3.400 4.13
34.23 0.372 1 1.507 4.80
of the reaction occurring in the liquid film, the enhancing 34.23 0.744 1 1.395 4.44
factor or Hatta number must be determined. This has 34.23 0.372 1 1.395 4.44
been done by evaluating oxygen mass-transfer rates both 89.62 0.372 0.4 1.12 3.41
in the absence and in the presence of the reaction. De- 89.62 0.372 0.5 1.30 3.16
termination of the oxygen mass-transfer rates across the 89.62 0.372 0.6 1.69 3.43
gas-liquid interphase in the absence of the reaction has "Initial concentration of the organic reagent was 2.9 X lo4
been performed with the Clark electrode. These rates can mol/cm3. The rpm of the stirrer was 300 in all cases, and the
be expressed, in the case of oxygen adsorption, as temperature was 50 "C.

ygen concentrations. The results are summarized in Table

(4)
11, along with the operating conditions. In the adopted
conditions, very low conversions were obtained, that is,
Integrating relation 4 from 0 to any value of Co, until about 3% in a hour, although residence times were rather
saturation, after the introduction of the proportionality long. Moreover, a change in the interface area produces
factor between oxygen concentration and current intensity, a change in the reaction rate. Therefore, it is possible to
we obtain conclude that the reaction is sufficiently fast to lower the
1 1 1 1
concentration of oxygen close to zero in the bulk liquid,
according to the classification of the gas-liquid reactions
reported by Charpentier, consequently:

where F(i) is a function of the electrode current measured.

The proportionality factor b can be obtained by dividing
the oxygen concentration a t saturation by the corre-
sponding current intensity, and it resulted in b = 2.62 X
IO-* mol/(cm3 nA). As expected, the trend of F ( i ) as a
function of time was, in all cases, a straight line whose slope
gives the mass-transfer coefficient. In Figure 4 mean
In Table I1 are reported the values obtained for KL in the
different runs. The comparison of these values with the
value of kL obtained in the absorption-desorption runs
should give directly the enhancing factor if, effectively,Co,
E 0. Since the values obtained in the comparison are in

values of i obtained in absorption runs, performed at 20
"C, are reported. Data have been fitted by eq 4 with an
average value of kL = 5.5 X cm/s (ai= 0.16 cm-l).
Table I shows the mass-transfer coefficients and Henry's
law constants obtained, respectively, at 20 and 50 "C.
Kinetic runs have been performed in the Levenspiel
reactor with various feed rates, interfacial areas, and ox-
the range 0.5-0.75, it can be concluded that Co, cannot be
considered equal to zero, and consequently, the enhancing
factor would be near to the unity.
Other kinetics runs have been performed in the CSTR
reactor of Figure 2, which is characterized by a much
greater interphase area. Runs have been performed at 50
OC and at different feed rates and concentrations of the
158 Ind. Eng. Chem. Res. Vol. 26, No. 1, 1987

Table 111. Kinetic Results Obtained for the Oxidation of Oxygen retained
("1
THEAQH2 in the Continuous CSTR Reactor of Figure 2"
liq
flow rate
104coR,
mol/cm3 rpm 100(conversion)
kc,
cm3/(mol s)
800 1
1.561 3.38 1900 77.8 4360 700 ~

1.427 3.38 1900 81.0 4630

1.111 3.38 1900 86.4 4422 600 -
0.783 3.03 2000 90.7 3440
0.694 2.49 2000 92.4 3734 SO0 -
0.555 2.83 2000 94.6 4246
0.833 3.38 1900 89.0 3467
1.111 2.26 1900 85.0 3100
1.111 0.99 1900 88.0 3090
"The temperature was kept in all cases a t 50 "C and the liquid
volume a t 300 cm3.

organic reagent. The speed of the stirrer has been kept

a t 1900-2000 rpm, which corresponds to 41-43 cm2/cm3
of the apparent interface area, as it can be observed in
Figure 3. The results together with the operative condi-
tions are reported in Table 111. These runs have been
interpreted by assuming a second-order kinetic law and
employing the relation
that is, eliminating Co, the rate of oxygen consumption
becomes
Po,
kLai has been calculated as the product of kL, determined
with the electrode measurements, per the apparent in-
terface area reported in Figure 3. This product must be
equal to the product of the true parameters. This proce-
dure is convenient because it allows us to separate the
influence of fluid dynamic effects on mass transfer from
the influence of other factors.
The values obtained for kc, in the different runs, are
reported in Table 111, while the mean value is reported in
Table I. As it can be seen, the values obtained for kc in
the different runs are reasonably scattered in the range
of the experimental error for a foaming gas-liquid system
as the one considered. With the introduction of the mean
value of k c in the Hatta number
(Do,k&n)"2
Ha = (9)
kL
it is possible to evaluate that in the runs reported in Table
111, the Hatta number is about 0.2-0.4, that is, a range to
which corresponds an enhancement factor of 1 (Charpen-
tier, 1981). The conclusion is that oxidation of THEAQH,
is a moderately slow reaction occurring mainly in the bulk
liquid, whose rate is affected by the mass transfer across
the liquid film.Therefore, both interfacial area and liquid
holdup should be maximized in the industrial reactor. The
second-order kinetic relation has been chosen on the basis
of the following observations: (a) If a zero order is at-
tributed to oxygen, the low conversions obtained in the
Levenspiel reactor cannot be justified. (b) Changes in
THEAQHz concentrations in the runs of Table I11 are well
interpreted with the second-order law. (c) The oxidation
of phenol proceeds with the same kinetic law. (d) Also the
runs performed in batch conditions can be well interpreted
Time i s )
Figure 5. Kinetic runs performed in batch conditions a t 50 "C (rpm
= 1800). Curve 1 is related to a 212-cm3THEAQH, solution with
concentration of 7.5 g/L; curve 2 to 270 cm3 of solution with con-
centration of 15 g/L; curve 3 to 290 cm3 of solution with concen-
tration of 30 g/L. Curve 4 is related to 300 cm3 containing 30 g/L
of mixture of quinones hydrogenated for about 80%. Curve 5 is
related to a solution of 10 g/L of fully hydrogenated EAQ. Except
for curve 5, experimental points have been fitted by employing the
described kinetic model with the parameters of Table I. Continuous
lines in curves 1-4 are calculated, while the points are experimental.
with the second-order kinetic law. In fact, in Figure 5 is
reported the uptake of oxygen, as a function of time, for
three runs performed in batch conditions a t different
concentrations of fully hydrogenated THEAQ. The tem-
perature was always kept at 50 "C. The runs have been
fitted by introducing the parameters in the equations
-- -
02' ' rtransf - rreact
(12)
dr VMVL
d VL
- - - filling rate
= constant (13)
dr
and by integrating. Here r = t - tdelay, where tdelay is the
time necessary for filling the reactor with the solution a t
the level of the impeller. V0,' is the volume of the
transferred oxygen, while Vo,'* is the volume of reacted
oxygen.
By solving the above-mentioned equations, it appears
that reaction rates are only deceleratory, in accordance
with a second-order kinetic law.
No autocatalytic effect, therefore, is present in contrast
with the behavior of hydrogenated durohydroquinone,
reported by James and Weissberger (1938) and by James
et al. (1938). In Figure 5 are also reported, for comparison,
kinetic runs performed, respectively,on fully hydrogenated
EAQ and on partially hydrogenated mixture of EAQ and
THEAQ. As it can be seen, the kinetic behavior of the
mixture is equal to the behavior of pure hydrogenated
THEAQ, while the behavior of EAQ is completely dif-
ferent, because the reaction rate seems to be insensitive
to the organic reagent concentration and equal to the
mass-transfer rate of oxygen. That is, oxidation of EAQHz
 Ind. Eng. Chem. Res. 1987,26, 159-161
is faster than oxidation of THEAQH2.
The absence of autocatalytic effects could be explained
in a classical autoxidation by assuming that steady-state
conditions for the involved radicals are readily achieved.
On the contrary, it is difficult to explain, on the basis of
the corresponding radical mechanisms, the second-order
kinetic law. It is reasonable to suppose that the hydrogen
bond in this reaction can be transferred directly to the
oxygen molecule as already suggested by Etienne and
Fellion (1954), for explaining the mechanism of dihydro-
phenazine autoxidation. Similarly, it is possible that ox-
ygen forms a complex with the hydroquinone followed by
the formation of two radicals that rapidly react, giving a
molecule of hydroperoxide as in the scheme
OH
OH
HO OW
The formation of radicals would be the rate-determining
step, and consequently reaction rates can be expressed as
r = kcl[complex] = kclKe[CR][Oz]
= kc [CR][02] (15)
where k , is the equilibrium constant for the formation of
the complex and kc1 is the true kinetic constant. Runs
performed in batch conditions at different temperatures
showed an activation energy of about 15 kcal/mol for the
apparent kinetic constant kc. This fact confirms that the
mechanism 14 is more reliable than classic autoxidation
mechanism.
However, both of the mechanisms explain well the
greater reactivity of EAQHz due to the greater aromaticity
of this molecule with respect to THEAQHz.
Acknowledgment
Thanks are due to the Montefluos S.p.A. Company for
financial support.
Vapor-Liquid Equilibria by UNIFAC Group
Contribution. 4. Revision and Extension
Detlef Tiegs and Jiirgen Gmehling*
Lehrstuhl Technische Chemie B, University of Dortmund, 46 Dortmund 50, West Germany
Peter Rasmussen and Aage Fredenslund
Instituttet for Kemiteknik, T h e Technical University of Denmark, DK-2800 Lyngby, Denmark
Revised UNIFAC interaction parameters are presented for a number of groups, especially the aniline
group. Parameters are given for 52 pairs of groups where the parameters have not previously been
available. N-Methylpyrrolidone has been introduced as a new group, and interaction parameters
with five important groups are given.
The range of applicability of the UNIFAC group-con-
tribution method is dependent on the availability of group
volumes (Rk), group-surface areas (QJ, and group-inter-
action parameters (ann and ann). Extensive tables with
parameters for 41 commonly applicable groups have been
OS88-5SS5/8?/2626-0159$01.50/0
159
Nomenclature
ai = specific interfacial area referred to the liquid volume,
cm2/cm3
CO, = concentration of oxygen in the liquid, mol/cm3
CR = concentration of the organic reagent, mol/cm3
Do, = molecular diffusivity of oxygen in the liquid, cm2/s
E = enhancement factor
F = feed rate of liquid, cm3/h
H = Henry’s law constant, atm cm3/mol
Ha = Hatta number
kL = oxygen mass-transfer coefficient, cm/s
kc = second-orderkinetic constant, cm3/(mols)
i = current intensity, nA
P O , = partial pressure of oxygen, atm
Ro, = rate of oxygen consumption, molls
S = exposed interfacial area, cm2
t = time, s
V , = volume of liquid, cm3
V , = molar volume
Registry No. EAQ, 84-51-5; THEAQ, 15547-17-8; EAQH2,
839-73-6; THEAQH2, 68279-54-9; H202, 7722-84-1; 02,7782-44-7.
Literature Cited
Berglin, T.; Schoon, N. H. Ind. Eng. Chem. Process Des. Deu. 1983,
22, 150.
Charpentier, J. C. In Aduances in Chemical Engineering; Academic:
New York, 1981; Vol. 11.
Clark, L. C. US Patent 2913 386, 1959.
Denisov, E. T. In Comprehensive Chemical Kinetic; Banford, C. H.,
Tipper, C. F. G., Eds.; Elsevier: New York, 1980; Vol. 16, p 125.
Etienne, A.; Fellion, Y. C. R.Hebd. Seances. Acad. Sci., Ser. C 1954,
238, 1429.
James, T. H., Weissberger, A. J. Am. Chem. SOC.1938, 60, 88.
James, T. H.; Snell, J. M.; Weissberger, A. J . Am. Chem. SOC.1938,
60, 2984.
Levenspiel, 0.; Godfrey, J. H. Chem. Eng. Sci. 1974, 29, 1723.
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Nitta, T.; Akimoto, T.; Matsui, A.; Katoyama, T. J . Chem. Eng. Jpn.
1983, 16(5), 352.
Powell, R. Hydrogen Peroxide; Noyes Development Co.: New York,
1968.
Ulmann, T. Encyclopedie der Technischen Chemie; Wiley: New
York, 1969; Vol. 17.
Received for review October 22, 1985
Accepted June 16, 1986
presented by Gmehling et al. (1982) and supplemented by
Macedo et al. (1983).
UNIFAC parameters have been published for various
specific group interactions. Recent examples of such
publications are shown in Table I. The parameters
1987 American Chemical Society