Pergamon Chemical Engineering Science, Vol. 52, No. 24, pp.

4593-4605, 1997
~" 1997 Elsevier Science Ltd. All rights reserved
Printed in Great Britain
PII: bUUOg-IZ~Ug{~7}UU3UI-1 0009 2509/97 $17.00 + 0.00

Uncatalysed oxidation of cyclohexane

in a continuous reactor
Y. Wen*, O. E. Potter* and T. Sridhar **
* ICI Explosives, Kurri Kurri, Australia; * Department of Chemical Engineering, Monash
University, Clayton, Australia

Abstract--This paper examines the kinetics of the oxidation of cyclohexane. Recognising that
catalytic effects of the reactor wall may impact on the kinetics of organic oxidations, especially
in laboratory scale reactors, these experiments are conducted in an aluminium reactor. In
addition, a novel technique is introduced which permits these oxidation reactions to be studied
without the intervention of gas-liquid mass transfer and thus yields homogeneous kinetics data.
A kinetic model for the reaction is proposed. © 1997 Elsevier Science Ltd

Keywords: Uncatalysed oxidation; cyclohexane; continuous reactor

INTRODUCTION The reaction was represented by a three-component

Liquid-phase-hydrocarbon oxidation processes play
a significant role in the modern petrochemical indus-
try. For the last 25-30 years these processes have
become a widespread subject of theoretical and ex-
perimental studies. Liquid-phase oxidation of cyc-
lohexane is a typical example of this kind of reaction,
and is of considerable industrial importance. It sup-
plies raw materials, such as cyclohexanol, cyclohex-
anone, adipic acid, etc., for the production of nylon-6
and nylon-66.
The oxidation of cyclohexane is carried out indus-
trially at a pressure of about 1.0-1.6 MPa to maintain
liquid condition in the reactor, and a temperature of
423-453 K. The conversion is limited to below 10%.
This is because the cyclohexanol and cyclohexanone
are more readily oxidisable than cyclohexane, and
even with the limited conversion a whole range of
further oxidation products are formed such as adipic,
glutaric, succinic and oxalic acids and their cyclohexyl
esters. Moesdijk (1979) gives a historical review of
the industrial routes to caprolactam and its inter-
mediates.
The reaction mechanisms of cyclohexane oxidation
have been well documented in the research, especially
by Russian scientists (Berezin et al., 1966; Emanuel
et al., 1967). Much of the voluminous patent literature
focusses on the effect of operating variables such as
temperature, pressure, catalyst and contacting condi-
tions on product distribution. Studies of the kinetics
of this reaction are rare and a comprehensive rate
equation is not available.
Spielman (1964) investigated the influence of reac-
tor type on the selectivity and yield of the intermediate.
: Corresponding author.
4593
consecutive reaction sequence and a five-component
sequence of simultaneous and consecutive reactions.
He found that, at any conversion level, selectivity and
yield of intermediate were higher in a batch or plug
flow reactor than in a continuous flow stirred reactor.
This result did not take into account any mass trans-
fer limitations and a uniform concentration of dis-
solved oxygen was postulated.
Based on a comprehensive set of experimental data
from a laboratory scale batch and continuous reac-
tors, Steeman et al. (1961) found that the optimum
conditions for cyclohexane oxidation were 428-438 K
and 8-10 atm. As the efficiency of the oxidation to
useful products decreased with an increasing degree of
conversion, and the cost increased with the number of
reactors, it was shown that three well-stirred auto-
claves arranged in series would be optimal. Saunby
and Kiff (1976) also studied the non-catalytic oxida-
tion of cyclohexane and found that three CSTRs in
series with equal conversion employed in each reactor
was the optimum economic process in terms of num-
ber of reactors, conversion per reactor and overall
conversion. This study also failed to identify the rate-
limiting steps because it ignored the possible interven-
tion of mass transfer.
Alagy et al. (1974) carried out cyclohexane oxida-
tion studies in a 1501 cylindrical reactor in which
stirring was by gas injection and by tangential injec-
tion of a liquid flow. The work examined the influence
of mass-transfer phenomena on reaction selectivity,
the use of boric acid as a coreagent, and determina-
tion of the optimum reactor configuration. The pro-
cess described in this work showed that the reaction
between alcohol with boric acid protected the alcohol
from further reaction. Industrial use of such a tech-
nique has been confounded by the problems of boric
4594 Y. Wen et al.
acid recovery which adds, substantially, to the
costs.
Because one of the advantages of homogeneous
catalysis is the control of reaction selectivity, it is not
surprising that liquid-phase oxidation is an area in
which homogeneous catalysis has contributed greatly
to industrial processing. The catalysts normally used
are organic acid salts of cobalt, manganese, iron, cop-
per, chromium, lead and nickel. The catalysts enable
the reactions to be carried out at lower temperatures,
and the milder conditions prevent the development of
processes of extensive oxidative degradation. The
papers published in this area have been reviewed by
Sheldon and Kochi (1973) and Lyons (1980). The
primary effect of dissolved metal salts and complexes
on the homogeneous oxidation of alkanes is to in-
crease the rate of reaction by catalysing the homolytic
decomposition of hydroperoxides.
Tolman et al. (1989) describe the studies carried out
at Du Pont's Central Research Laboratory. It was
observed that the Co catalyst was rapidly deactivated
by the products of the decomposition reaction. In
order to prolong catalyst activity, many transition
metal complexes with chelating ligands were tested.
Cyclohexyl hydroperoxide is the first primary inter-
mediate formed during oxidation of cyclohexane. It
is present at a higher concentration (4.3% of the
oxidate) in molybdenum glass reactors than in steel
vessels (1-2%) (Berezin et al., 1966). When cyclohexyl
hydroperoxide is free from traces of metals, it is reas-
onably stable (Hawkins, 1961). Using a combination
of pulse calorimetry and chemical luminescence tech-
niques, Tolman et al. (1988) discovered a new
family of long-lived catalysts for converting cyclohexyl
hydroperoxide (HP) to cyclohexanol and cyclo-
hexanone. Based on the (bis(2-pyridylimino)isoin-
dolinato) ligand, these catalysts are very active and
long-lived, allowing cyclohexyl hydroperoxide to be
converted in a selective, low temperature process.
Studies on the oxidation of cyclohexane have been
carried out at Monash University since the late 1960s.
Several experimental programs have been undertaken
which were concerned with the determination and
correlation of many of the quantities required for
calculation of mass transfer rate under reacting condi-
tions. Homogeneous kinetics as well as gas-liquid
reaction studies in both stirred tank reactor and a flat
interface vessel, have been reported. Solubility data on
oxygen (from 312 to 373 K) and nitrogen (308 to
443K) in cyclohexane under pressures up to
1.62 MPa were measured (Wild et al., 1978; Suresh
et al., 1988a). The diffusivity of gases dissolved in
liquids was studied and two methods for determining
diffusion coefficients were proposed (Sridhar and
Potter, 1977). Using the equipment designed and
constructed for conducting experimental studies
on organic oxidations, measurements of gas-liquid
interfacial areas in agitated vessels (Sridhar and Potter,
1980b) and gas holdup and bubble diameters in agi-
tated vessels under conditions ranging from ambient
to the reaction temperature (Sridhar and Potter, 1978,
1980a) were reported. Mass transfer studies were also
carried out (Suresh et al., 1988a) in two types of
agitated gas-liquid reactors, i.e. a flat interface reactor
and a gas sparged stirred-tank reactor. The mass
transfer coefficient for the solution of oxygen in cyclo-
hexane without reaction over a wide range of temper-
atures and pressure was measured.
Suresh et al., (1988a-c) have examined the un-
catalysed oxidation in a stainless steel batch reactor.
Uncatalysed and catalysed oxidation of cyclohexane
was examined in a batch reactor under homogeneous
as well as heterogeneous condition, and under differ-
ent contacting conditions by Suresh (1986). According
to the general free radical mechanism of hydrocarbon
oxidation, a kinetic model for the oxidation of cyclo-
hexane was derived and the parameters of the model
were determined from the experimental data (Suresh
et al., 1988b). This model is able to account for the
transition in the kinetics from a zero-order depend-
ence on oxygen at high concentrations to a first-order
dependence at low concentrations, and is able to pre-
dict with reasonable accuracy the development of the
concentration of total products as well as of total
intermediates. A reactor model accounting for the
relative rates of mass transfer and chemical kinetics
was proposed (Suresh et al., 1988c).
The papers of Suresh et al. (1988a-c; 1990) repres-
ent one of the few attempts where the reaction regime
was unambiguously established by direct measure-
ment of dissolved oxygen concentration. These stud-
ies also led to the first experimental determination of
the enhancement factor in a bubbling reactor for any
gas liquid reaction. This was made possible by the
use of light transmission technique to measure inter-
facial area and dynamic response following a step
change in gas composition for determining mass
transfer coefficients. The nature of the interactions
between bubbles was also clarified.
The general features of the batch oxidation, under
the conditions of high mass transfer rates that typi-
cally obtain in bubbling agitated contactors, shows
that as the free radicals accumulate, the reaction velo-
city begins to increase. This is indicated by decreasing
dissolved oxygen concentration and increasing ab-
sorption rates. In this slow-reaction regime, the reac-
tion is not fast enough to take place appreciably in the
diffusion film, and absorbed oxygen gets through the
bulk of the liquid. Due to the autocatalysis, the ab-
sorption rate increases with time and the dissolved
oxygen concentration decreases. The autocatalytic
nature of the reaction led to oscillatory behaviour
when the system approached the diffusional sub-
regime (Suresh et al., 1991).
Due to autocatalytic behaviour and the influence of
mass transfer on the reaction, the batch reactor be-
comes a rather inconvenient device for the intrinsic
kinetic study since the reaction rates are dependent on
the entire past history of the reactor. A new reactor
system is needed for the study of chemical kinetics
which is the aim of the present project. In addition the
possibility of decomposition of the hydroperoxide
 Uncatalysed oxidation of cyclohexane
with high selectivity has motivated the search for
operating conditions which will maximise the concen-
tration of hydroperoxide. Cyclohexyl hydroperoxide
can then be decomposed to the desired product under
mild operating conditions to obtain a higher overall
selectivity.
Compared with the kinetics of cyclohexane oxida-
tion in steel autoclaves, Berezin et al. (1966) found that
in a glass reactor the reaction proceeds with greater
difficulty than in a metal reactor and therefore it must
be run at a slightly higher temperature. In a glass
reactor, the concentration of cyclohexyl hydroperox-
ide is much higher than the concentrations of cyclo-
hexanol and cyclohexanone and the maximum value
is 3-3.5 times higher than that reached in a steel
reactor.
Consequently, a new reactor system is needed to
study chemical kinetics and is the subject of this
paper. In this study the oxidation of cyclohexane was
carried out in a continuous reactor system. A novel
feature of the reactor allows gas-to-liquid mass trans-
fer and chemical reaction to be decoupled. This is
accomplished by predissolving oxygen into the cold
liquid and pumping this saturated liquid as a feed to
a well mixed reactor. The operating pressure of the
reactor is high enough to prevent any desorption of
gas. In fact the reactor contains no gas phase. Such
a reactor allows the determination of reaction rates in
a direct and accurate manner. An additional com-
plication is the catalytic action of the material of the
reactor wall, especially in laboratory reactors with
large metal surface to liquid volume ratios. In order to
oxygen
©
cyc,ohex
i. Autoclave
2. Syringe pump
3. Fluidized bed sand bath
4. Preheater
5. Reactor
6. Metal ball
Fig. 1. Schematic diagram of the reactor system.
4595
simulate the behaviour of commercial reactors where-
in the surface to volume ratios are much smaller, it is
desirable to avoid the catalytic action of the wall
material. Therefore, reactors made of aluminium have
been used in this study.
EXPERIMENTAL PROCEDURES
The oxidation of cyclohexane was carried out at
temperatures of 418-443 K and under pressures of
2.5-4.5 MPa. Although Berezin et al. (1966) stated
that the dangers in the cyclohexane process had been
exaggerated, the question of safety in organic oxida-
tion was brought into sharp focus by the Fiixborough
explosion of June 1974.
The continuous stirred tank reactor (CSTR) system
is shown in Fig. 1. The system mainly consists of an
autoclave, an ISCO syringe pump (Model LC-5000)
and a reactor. The autoclave was used to saturate
cyclohexane by bubbling oxygen gas for at least
40 min under ambient conditions and required oxy-
gen saturation pressure. The saturated liquid was
loaded into the syringe pump and pumped into the
reactor at the required liquid flowrate. The pressure in
the reactor, which was controlled by a back-pressure
regulator, was higher than the saturation pressure
used in the autoclave so as to prevent oxygen gas
being desorbed from the liquid. As a result the reactor
contains no gas phase and the reaction is between
predissolved oxygen and the liquid cyclohexane. The
reactor is 30 c m 3 in volume and the reactor and lines
were made of aluminium alloy. The reactor contained
a small ball which was moved magnetically to ensure
8
SOAP BUBBLE
GAS METER
11 LIQUID SAMPLE
7. Magnetic plate
8. Heating elements
9. Electric motor
10. Back-pressure regulator
11. Gas-liquid separator
4596 Y. Wen et al.
good liquid mixing. A tracer test confirmed that the
reactor was well-mixed. The reactor was placed in
a heated fluidised sand bath, in which the heating
elements were controlled via Eurotherm temperature
controllers. The pressure of the reactor was controlled
at approximately 1.0 M P a higher than the saturation
pressure. The unreacted gas passed through the
reactor and was measured after pressure let down by
a soap film meter. At the same time, the liquid flow
rate at the sampling point is also recorded. These two
measurements allow the calculation of dissolved oxy-
gen concentration within the reactor. The estimation
of dissolved oxygen concentration from the separate
measurements of desorbed gas and liquid flow
rates involves an error of around 15%. The procedure
was verified by measuring the solubility of oxygen
in cyclohexane for which independent measurements
are available in Wild et al. (1978) and Suresh et al.
(1988a).
MATERIALSAND ANALYTICALMETHODS
Analytical grade cyclohexane, cyclohexanol and
cyclohexanone and high purity oxygen gas were used
throughout the experiments. A gas chromatographic
method (Katnik and Johnson, 1970), was used to
analyse cyclohexanol, cyclohexyl hydroperoxide and
cyclohexanone. Firstly, sufficient triphenylphosphine
(TPP) was added to quantitatively convert any
cyclohexyl hydroperoxide to cyclohexanol. Then
using ethyl acetate as an internal standard, total
cyclohexanol (including converted cyclohexyl hy-
droperoxide), cyclohexanone and unreacted cyc-
lohexane were determined by GC. The cyclohexanol
concentration itself was calculated by subtracting
hydroperoxide from the sum of hydroperoxide and
cyclohexanol. If any solids were found in the samples,
tetrahydrofuran (THF) was added to dissolve them.
A Hewlett-Packard gas chromatograph fitted with
a thermal conductivity detector was used. The
chromatograph column was a 3 m × 0.003 m stainless
steel tube packed with 12.5% QF-1 followed by
a 3 m × 0.003 m column with 3.0% QF-1, both sub-
strates coated onto Chromosorb GAW, DMCS,
60-80 mesh.
Due to the low conversion obtained in this study,
the gas chromatographic method is not sufficiently
accurate for the determination of cyclohexane conver-
sion. Here an alternative method is introduced. Cyclo-
hexane conversion was determined by converting all
the sample quantitatively to CO2, which was ab-
sorbed in a mixture of 4% ethanolamine in pyridine
and titrated with tetrabutyl ammonium hydroxide.
The method was checked by injecting samples of
cyclohexane with known amounts of cyclohexanol
and cyclohexanone.
The concentration of cyclohexyl hydroperoxide
was separately determined by iodometry. The total
amount of acids was determined by titration with
potassium hydroxide. Details of the analytical tech-
niques are available in Wen (1992).
RESULTS AND DISCUSSION
Experiments on the oxidation of cyclohexane were
carried out in the aluminium CSTR system at three
different temperatures, 423, 433 and 443 K, and at
various residence times. Due to equipment limitation,
the highest oxygen saturation pressure which could be
set was 4.5 MPa. Therefore three different pressures of
2.5, 3.5 and 4.5 MPa were investigated.
A typical concentration profile during reactor start
up are shown in Fig. 2. The data shown in the figures
were obtained under the conditions of 433K,
2.5 MPa and for a residence time of 48.6 rain. The
figures illustrate that cyclohexane conversion in-
creases and dissolved oxygen decreases with reaction
time. Hydroperoxide is the first product formed, cyclo-
hexanol is the second, followed by cyclohexanone.
The concentration of hydroperoxide is much higher
than obtained in a stainless steel reactor. The max-
imum conversion and the concentration of each prod-
uct at steady state depend on the availability of dis-
solved oxygen. The figures show a sudden increase in
cyclohexane conversion and product concentrations,
which indicates the autocatalytic nature. Note that
the reactor reaches steady state in about four resi-
dence times.
The steady-state results of chemical analysis and
dissolved oxygen measurement at temperature of
443 K with an oxygen saturation pressure of 3.5 M P a
are shown in Fig. 3. These figures show that at low
residence times, the conversion of cyclohexane is
small and as a consequence the conversion of oxygen
is also low. The concentration of oxygen in the liquid
leaving the reactor is high and intrinsic kinetics will
control the reaction. The dissolved oxygen concentra-
tion at zero residence time corresponds to the solubil-
ity of oxygen in cyclohexane under the conditions
prevailing in the saturator. At intermediate residence
times, the conversion rises dramatically and the
oxygen concentration falls steeply. This region, called
the ignition regime, is characterised by large increases
in the concentration of cyclohexanol and cyc-
lohexanone [Fig. 3(b)]. It appears that the decompo-
sition of hydroperoxide which leads to the formation
of these compounds accelerates the rate of cyc-
lohexane reaction and the appearance of an ignition
regime is characteristic of autocatalytic reactions. At
large residence times, the reaction goes to complete
conversion based on the available oxygen. Under
such conditions, the concentration of oxygen within
the reactor is very small.
Three main intermediates, namely, cyclohexyl hy-
droperoxide, cyclohexanol and cyclohexanone are
formed in a certain sequence. Apparently, hydro-
peroxide is first solely produced while the dissolved
oxygen is high, and then it decomposes once the
oxygen concentration in the liquid drops below a
certain level.
The isothermal cyclohexane conversion results
were investigated with different pressures (Fig. 4). It
is apparent that the low residence time region and
the autocatalytic ignition region are unaffected by
 Uncatalysed oxidation of cyclohexane 4597

(s)

% O

• %
0
0
o%
I I f i I ~ I

50 100 150 200 250 300 350

Time (rain)

1.5
(b)

A &
A & &
A A A

'~1.0
E

~0.5
o
r- [] 0 0 0 []

17

• 0
I I i I
0.0 i ~t ~'I i I ,

50 100 150 200 250 300 50

Time (min)

Fig. 2. Concentration profiles during start-up of reactor (433 K; 2.5 MPa; 0 = 48.6 min).

pressure. In these regions, the reaction is zero order in
oxygen since the oxygen concentration is high
enough. However, the high residence time region is
oxygen limited and hence shows a dependency on
pressure since this affects inlet oxygen concentration
and total oxygen availability.
The effects of oxygen saturation pressure on cyc-
lohexyl hydroperoxide and its selectivity are shown in
Fig. 5. It is observed that oxygen saturation pressure
does not significantly affect the formation of hydro-
peroxide. Higher oxygen saturation pressure means
higher initial dissolved oxygen concentration.
It is useful to examine the effect of oxygen concen-
tration on the formation of secondary products. Since
cyclohexane conversion minus hydroperoxide forma-
tion is equal to the sum of N O L + O N E + Acid +
etc. formed, the term X - H P is used in the following
discussions and refers to all the products produced in
the cyclohexane oxidation except hydroperoxide.
Figure 6 shows X - H P against the O z / H P ratio under
all operating conditions studied. The figure shows
that as long as the dissolved oxygen is kept high and
the O 2 / H P ratio is greater than 2, the total products
will be dominated by hydroperoxide. The data
around O 2 / H P ratio of zero in Fig. 6 were obtained
from complete conversion. The data clearly show that
conditions of oxygen starvation lead to increased hy-
droperoxide decomposition.
Cyclohexyl hydroperoxide, cyclohexanol and cyclo-
hexanone are the main intermediate products. When
the oxygen concentration is high, hydroperoxide con-
centration is more than 80 mole% of the total inter-
mediates; cyclohexanol is less than 20 mole%; and
cyclohexanone is only a trace. However, when oxygen
concentration is small, the percentages of cyc-
lohexanol and cyclohexanone increase. The data
show that the concentration of cyclohexanol is always
higher than that of cyclohexanone.
Now let us examine the relationship between inter-
mediates and cyclohexane conversion. Figures 7(a)-
7(c) plot cyclohexyl hydroperoxide, cyclohexanol and
cyclohexanone concentration against the cyclohexane
4598 Y. Wen et al.

(a)

0
_o 0
li0

O
O
I n I J
0q
0 10 20
Residence Time (rain)

1.5

O
E 1,0

.=
"O
&
E
L. A El
C$ 0.5
e-

0°01
0 10 20
Residence Time (rain)

Fig. 3. Concentration of various components at steady state (443 K; 3.5 MPa).

conversion under all reaction conditions of temper- quired in the kinetic model. The differences in reactors
atures and pressures concerned. They show that the made of stainless steel and aluminium are that the
concentration of hydroperoxide depends only on the autocatalytic process starts earlier in the stainless steel
cyclohexane conversion despite varying temperatures reactor than in the aluminium reactor because
and oxygen pressures. Cyclohexanol and cyclo- hydroperoxide decomposes faster. It appears that the
hexanone exhibit the same characteristics. This is typ- stainless steel reactor wall acts as a catalyst for
ical of a kinetic scheme operating under the kinetic peroxide decomposition.
regime with similar activation energies for the differ- The scheme for cyclohexane oxidation can be repre-
ent reactions. Deviations are expected and seen at sented as follows.
high conversion corresponding to oxygen limitations. Initiation:
Note that the hydroperoxide concentration exhibits
a maximum while cyclohexanone and cyclohexanol r, =f,(c~). (i)
show a monotonic increase. This does indicate that
the main products of peroxide decomposition are Propagation:
alcohol and ketone.
R* + 0 2 ~ RO2* (2)

THEORETICAL MODELLING
RO~ + RH ~ Products + R* (3)
Suresh e t al. (1988c) have presented a kinetic model RO* + PH ~ Products + R*. (4)
based on their stainless steel batch reactor data. Since
the kinetics in an aluminium reactor are demon- Termination:
strably different from that in a stainless steel reactor, it
is interesting to examine what modifications are re- r, =~(ER*] + ERO*]). (51
 Uncatalysed oxidation of cyclohexane 4599

i i v i

(a)
0

0
>

_Q A

1<
.c
0

0 i I I I I I I I I I
0 10 20 30 40 50 60
Residence Time (min)

i i i w

• {b)
r- • A
O

QJ
=b
r.
O
O
c~
o 2
X
Q)
J=
O
o
>,
O A
A

O~ I i I i I i I i I

0 10 20 30 40 50

Residence Time (mln)

Fig. 4. Effect of oxygen conversion at steady state (a) 433 K and (b) 443 K.

The production of radicals is from cyclohexane at the and total intermediate formation (rt) are given
start of the reaction. As the reaction products begin to below:
build up, degenerate branching becomes important
and the products increasingly become the main source kolk3CL(Ce + fl)
rc = (7)
of radicals. kol + ko2Ce + k3CL
It is assumed that the rate of initiation depends
k3CL(Cp + fl)(kol + ko2Ce)
linearly on the total product concentration. For a re- ro = (8)
actor fed with pure cyclohexane, such a model does k01 + ko2Ce + k3CL
not permit the reaction to commence. In actual prac- k3CL(Ct,, -t- fi)(kol -- ko2CL)
tice, the cyclohexane used always contains some prod- rx = (9
k01 + ko2Ce -t- kaCL
ucts as impurities. Furthermore, it is possible that
alternative sources of free radicals exist in the reactor. Note that the rate of reaction is finite even when the
For these reasons, we modify the expression used product concentration is zero. fl is a constant and
previously for the rate of initiation to the following equals (o~/k). At a high oxygen concentration, the
form: expressions for Ce, CL and Cr at steady state for
a CSTR can be obtained:
ri = k Ce + ~ (6)
Ceo + Okolfl
Cv ( 1O)
where k and a are constants and only depend on the I - Okol
reaction temperature, c~ is the rate of reaction at the
start of reaction when no products are present.
As a result of this modification, the new rate
expressions of cyclohexane (re), oxygen conversion (ro) (11)
4600 Y. Wen et al.

(.)
A

CD
0
E

m0 A

l-

0
U
&

i I i I t I i t i I i
0
0 10 20 30 40 50 60
Residence Time (min)

2.0
(b)

w
0 1.5
g Q

• 0

e.
1.0

t-
O
0 0
0
Q. 0.5

0.0 I I I
0 10 20 30
Residence Time (min)

Fig. 5. Effect of oxygen saturation pressure on hydroperoxide concentration at steady state (a) 433 K and
(b) 443 K.

(1 -- Okol)Cjo + Okox(Ceo + fl)

Ct = (12)
O
O [ X 423K,2.5blPa (1 - Okol) + Okoz(Ceo + ~)

OO
• 433K,2.51VlPa
¢ The intermediate products include hydroperoxide, al-
x • 433K.3.SMPa cohol and ketone. Since the major focus of this study
o

o~ A
l O 443K,3.5MPa is the hydroperoxide, it would be useful to derive
a separate expression for its rate. The products from
reaction (3) include mainly cyclohexyl hydroperoxide,
cyclohexanol and cyclohexanone. The cyclohexyl
hydroperoxide formed from reaction (3) is assumed
0~
>
g 1 to undergo two steps as follows:

RO~' + R H ~ R O O H + R* (13)

RO* + ROOH ~ Products + R*. (14)

Firstly, hydroperoxide is produced from cyclohexane

2 4 6 8 10 12 14
in reaction (13) and decomposes to form cyclohexanol
Oxygen/hydroperoxide (moletmole)
and cyclohexanone in reaction (14). Hydroperoxide
will react further along with other products in reac-
F i g . 6. E f f e c t o f o x y g e n c o n c e n t r a t i o n o n p r o d u c t s other tion (4) to form the secondary products. Since
than hydroperoxide at steady state. the cyclohexyl hydroperoxide is formed from
 Uncatalysed oxidation of cyclohexane 4601
2.0 cyclohexane, the rate of formation is assumed to be
equal to the rate of cyclohexane conversion. The rate
1.5
of its decomposition is determined by the reactions
• • O A •
(14) and (4) to produce the first products which
1.0
• [] • include cyclohexanol and cyclohexanone, and the
0o secondary products which are acids, water, etc. The
0.5
x rate constant of the decomposition of hydroperoxide in
x
0.0
(14) is denoted by kill,. Based on this simplified model
1 2 3 the net rate of cyclohexyl hydroperoxide production i~
Cyclohexane Conversion (mole%)

2.0 k3CL(Cl, + fl)(kol -- km, Cill, - ko2Cile)

(b) rill, - (15)
k01 + k02Cl, + k3CL
~ 1,5
T h e c o n c e n t r a t i o n of h y d r o p e r o x i d e in an a l u m i n i u m
o
c 1.0 C S T R at steady state is
m
x
.¢
A •
Ok3CL(Cp + fl)(kol -- (kill" 4- ko2lCHp )
_o 0.5 C ill, = C ill,o
u
kol ÷ ko2Cp 4- k3CL
0.0= i i (16)
1 2 3 4
Cyclohexene Conversion (mole%) When oxygen concentration is high, the above equa-
~ 2.11
(e) tion simplifies to that given below:
o
E 1.5 (1 -- OkoOCnp o 4- Okol(Cpo 4- fl)
C,e = (I 7 )
(I -- Okol) + O(klte 4- ko2)(Cl,o 4- fl)
~ 1,0
There are four kinetic constants ko~, ko2, k~ and
• O A QD
~ 0.5 knl, and a constant 13which have to be determined. An
a•
estimate of ko~ and [3 can be obtained by fitting the
O.G _- ~ C-C¢ 'A =.
0 1 2 3 steady-state experimental data at high oxygen con-
Cyclohexane Conversion (mole%)
centrations ( Q ) to eq. (7). At high oxygen concentra-
Fig. 7. Relationship between product concentration and tions eq. (7) predicts a linear relationship between
conversion under various conditions as steady state• the rate of consumption of cyclohexane and the

1.4 • n • i • u • n • i • n • , • t • n ,

1.2 433K []

~4
1.0

0.8
i []

(a)
0.6

0,4

0.2

• i , | . | . i . , . i • t , i . t
0.0
0 2 4 6 8 10 12 14 16 18 20

3 $
Cp (mole / cm ) x 10

Fig. 8. Effect of total product concentration on rate of cyclohexane reaction at steady state.
4602 Y. Wen et al.

Table 1. Constants for the kinetic model in an aluminium CSTR

Temperature (K) ko~ ko2 k3 kne fl

423 3.3 x 10 -4 -- -- -- 0.65x 10-s

433 6.5 x 10 -4 0.7 3xl04 2.6 1.29 x 10 -5
443 12.0x 10 -4 1.5 7x104 4.2 2.58 x 10 -5

Note: kot is in s-X; ko2, k3 and kup in cm a (moles); fl in mole/cm 3.

(,)
.... O2-1mKI. - - Conv-lxed.

",,. / A
_o
0
I

/,- ....,,

. . . . . . . . . .

0 50 100 150 200 250 300 350

Time (min)

i i i i i i

.... ;,~-m-~d. I m ~.~,,~ I

"'''--. ...................
_o
0
:s /,

/ ~ ~ O ~ O0 0 0 0 0 0
/" 0
"°00

! J !
0
0 50 100 150 200 250 300 350
Time (rain)

Fig. 9. Comparison of theoretical predictions with experimental data (during reactor start-up) (433 K;
2.5 MPa; 0 = 48.6 min).

concentration of products. Figure 8 shows such a rela-
tionship and allows kol and 13 to be determined from
the slope and intercept, respectively. The plot shows
that 13is the rate of reaction in the absence of products
and represents a possible 'non-radicar route for the
oxidation of cyclohexane. Using non-linear regression
ko2 and kup could be determined by using eqs (12) and
(17). In fact, the values of ko2 and kHp reflect the
differences between the cyclohexane conversion and
CI, and between the conversion and Cup. k3 was
estimated using the start up data. Only a rough value
for ka is needed because the results are not very
sensitive to its value (Suresh et al., 1988b). Table 1
shows the constants obtained by these methods.
The predicted concentrations of total products, in-
termediates (including hydroperoxide, cyclohexanol
and cyclohexanone), hydroperoxide itself and dis-
solved oxygen are compared with the experimental
concentration-reaction time curves. The conditions
of these experiments are over the temperatures of
423-443 K, inlet oxygen saturation pressures
of 2.5-4.5 M P a and different reaction times. The
 Uncatalysed oxidation of cyclohexane 4603
, , i

6.0

5.0 ~%%%
.... O'2-pr~
1 -- Cony-pred.
.... 1
4.0 '~N.AA

3.0

2.0

1.0

S , , , X, , A A , , ,
0.0
50 100 150 200 250 300
Time (mln)

6.0 (b)

5.0
.... lnterm-p~l.
1 I 0 l-IP-expt 1

4.0

_¢
O
3.0 •
s. ~-~---
tL A
h__..JK____. O .........
• -
qlt ....

Is•
2.0

° ~ 0 0 0 0 0 0
1.0

0.0 iI~ i , I , I I , I i

0 50 100 150 200 250 00

Time (min)

Fig. 10. Comparison of theoretical predictions with experimental data during reactor start-up (443 K:
4.5 MPa; 0 = 15.8 min).

reaction times shown in the figures were recorded at the Arrhenius equations for the various rate constants
the sampling point. There is a time delay because of can be set up. The acitvation energies were deter-
the tubing between the reactor exit and the sampling mined by employing the non-linear regression using
point. Residence time distribution studies have shown the rate constants at different temperatures. These
that this could be modelled as a pure time delay. This equations are shown below:
time delay is calculated from the volume of the tubing
between the reactor and the sampling point and the kol = 8.06(108)EXP( - 100.3 × 103/RT) (18)
flow rate. This time delay is incorporated into the
model and its magnitude can be read from the figures. ko2 = 3.5(1014)EXP( - 121.8 x I03/RT) (19)
Figures 9 and 10 show typical comparisons of the
experiments with model predictions. The comparisons
kne = 4.6(109)EXP( - 76.7 x I03/RT). (20)
between experimental data and predicted results are The activation energies for kol, ko2 and knp are
quite good, considering the number of independent 100.30, 121.8 and 76.7 kJ/mole, respectively. The ac-
measurements and the complexity of the experiments. tivation energy for k3 is not estimated because k3 is
Also, note that small errors in the estimation of the not known very accurately. The Arrhenius equations
time delay are possible and explain why in some cases for kol and ko2 obtained from the stainless steel batch
the simulation is offset from the experimental data. reactor (Suresh et al., 1988b) are given here:
The effect of temperature on the rate constants can
be seen in Table 1. With the kinetic constants for the kol =8.6(101°)EXP( - 115.2xI03/RT) (21)
oxidation of cyclohexane at different reaction temper-
atures of 423, 433 and 443 K in an aluminium CSTR, ko2 = 3.5(1014)EXP( - 130.4 x 103/RT). (22)
4604 Y. Wen et al.
Table 2. Comparison of kol (s-1) with previous study
Temperature (K) Stainlesss t e e l Aluminium
(Suresh et al., 1988b) (this work)
423 5 . 0 x 10 - 4 3.3 x 10-4
433 13.0 x 10-4 6.5 x 10-4
443 37.6x 10-4 12.0x 10-4
A reasonable agreement is shown m activation ener-
gies obtained in different types and material of reac-
tors. Comparing the rate constant kol at different
temperatures obtained from a stainless steel reactor
(Suresh et al., 1988b) and k01 from an aluminium
CSTR of this work (see Table 2), stainless steel acts as
a catalyst for the oxidation of cyclohexane. The differ-
ences in the rate constant varies from 50% at low
temperatures to 300% at higher temperatures and
suggest that the oxidation of cyclohexane is enhanced
by the stainless steel reactor wall. In addition, the
product distribution suggests that the decomposition
of the hydroperoxide is also facilitated by stainless
steel. The rate of oxidation in a stainless steel reactor
is equivalent to a rise in temperature of 9-10 K com-
pared to that in the aluminium reactor used in this
study.
CONCLUSIONS
A continuous reactor system was introduced to
enable more accurate kinetic analysis. A novel feature
of the reactor allows mass transfer and chemical reac-
tion to be decoupled. This is ensured by predissolving
oxygen into the cold liquid and pumping this
saturated liquid as a feed to a well-mixed reactor. The
operating pressure of the reactor is high enough to
prevent any desorption of gas. In fact the reactor
contains no gas phase, and as a result there are obvi-
ous safety advantages,
The oxidation of cyclohexane was carried out in
a continuous stirred tank reactor made of aluminium,
The need for aluminium reactors arose from the rec-
ognition of the possibility of stainless steel acting as
a catalyst for the decomposition of cyclohexyl hydro-
peroxide. The reaction was found to proceed more
slowly in an aluminium reactor than in a stainless
steel reactor. However, the concentration of cyc-
lohexyl hydroperoxide is much higher in an alumi-
nium reactor, since stainless steel acts as a catalyst
and cyclohexyl hydroperoxide decomposes easily to
cyclohexanol and cyclohexanone,
The experimental results show that cyclohexyl hy-
droperoxide is a dominant product at high oxygen
concentration in an aluminium CSTR. Its selectivity
decreases with an increase in residence time. The
product distribution shows that the concentration of
cyclohexanol is always higher than the concentration
of cyclohexanone within the residence times studied in
this work.
The kinetic model derived previously from a stain-
less steel batch reactor has been modified and a
kinetic expression for cyclohexyl hydroperoxide has
been developed. The rate of the reaction is first order
in total products when oxygen concentration is high.
The kinetic model captures the essential trends ob-
served in the experiments.
Acknowledgements
The authors are pleased to contribute to this issue honour-
ing the contributions of Professor M. M. Sharma to Chem-
ical Engineering. We have benefitted from numerous dis-
cussions with him on his visits to Monash University.One of
us (TS) was the Kane visiting professor at UDCT in 1995
and acknowledges useful discussions on intricacies of or-
ganic oxidations. The authors appreciate the continuing
interest shown by Dr. A. K. Suresh.
NOMENCLATURE
C concentration, mol/cm 3
CHp concentration of hydroperoxide, mol/cm 3
CHPO initial concentration of hydroperoxide,
mol/cm 3
CL concentration of the dissolved oxygen,
mol/cm 3
CLo initial concentration of the dissolved oxy-
gen, mol/cm 3
C. concentration of total products, mol/cm 3
Cpo initial concentration of total products,
mol/cm 3
CR concentration of cyclohexane, mol/cm 3
functional relationship between the rate of
initiation and the concentration of total
products
f, functional relationship between the rate of
termination and the total concentration of
free radicals
HP cyclohexyl hydroperoxide
k rate constant in the expression for radical
initiation rate, sec-1
kol rate constant in the expression for cyclo-
hexane conversion rate, sec-1
ko2 overall rate constant, cma/(mole s)
k3 overall rate constant, cm3/(mole s)
kne rate constant of the decomposition of hydro-
peroxide in reaction (14), cm3/(moles)
PH Reaction product, hydrocarbon
rc rate of reaction of cyclohexane, mole/(cm 3 s)
rHp rate of formation of cyclohexyl hydroperox-
ide, mole/(cm 3 s)
ri rate of initiation of free radicals,mole/(cm3 s)
rt rate of accumulation of intermediates,
mole/(cm a s)
ro rate of reaction of oxygen, mole/(cm a s)
rt rate of termination of free radicals,
mole/(cm 3 s)
RH cyclohexane
ROOH hydroperoxide formed as the primary oxida-
tion product of the hydrocarbon RH
T absolute temperature, K
X cyclohexane conversion in molar fraction
 Uncatalysed oxidation of cyclohexane
Greek letters
:~ constant in eq. (6)
fl constant
0 residence time
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