KINETICS OF LIQUID PHASE OXIDATION OF CUMENE

IN BUBBLE COLUMN"
KAZUO HATTORI**, YUJI TANAKA, HIROYUKI SUZUKI,
TSUNEO IKAWA AND HIROSHI KUBOTA
Tokyo Institute of Technology, Tokyo
Liquid phase oxidation of cumene in the absence of solvent was carried out in a bubble column in
temperature range from IOO° to I3O°C. The reaction scheme in the batch-wise operation was
classified in terms of three periods: the induction, the steady chain-propagation and the termination
periods. The kinetics in the steady chain-propagation period, which is industrially important, was
studied and the rate expressions of chemical steps were derived.

I. Introduction the result of a kinetic study carried out in a bubble

column is reported.
Liquid phase oxidation of cumene (isopropyl benzene)
is one of the important reactions which are applied on 2. Experimental
a large commercial scale. It is well known that the
reaction proceeds with a complex radical mechanism. The schematic diagram of the experimental apparatus
Although much work has been directed to studying the is shown in Fig. 1.
reaction mechanism, there are few kinetic studies which The bubble column reactor, 50mm in diameter and
give quantitave knowledge of the reactor operation. Only 400mm in length, was made of Pyrex glass. At the
Fortuin et al.3>4) reported some results obtained from bottom of the reactor a perforated plate of Pyrex glass
the engineering point of view. In the present paper, with 19 holes, 0.8mm in diameter, was placed as a gas
distributor. One or two reflux condensers were placed
at the top of the reactor.
Gases containing oxygen were supplied after being
dehumidified by silica-gel. Cumene, supplied by Mitsui
Petrochemical Industries Ltd., was washed by con-
centrated sulphuric acid and an aqueous solution of 2N
sodium hydroxide. Being dried by calcium chloride,
it was distilled under nitrogen atmosphere. The distil-
late obtained at the boiling point of 152.5~153.5°C
was supplied to the reactor without solvent. Benzoyl
peroxide of the market reagent grade was used as an
initiator.
After the cumene in the reactor was heated to a
desired reaction temperature under the bubbling of
nitrogen, the initiator was added and at the same time
the bubbling gas was switched from nitrogen to the gas
containing oxygen. The reaction was thus started.
The temperature of the reactant mixture in the reactor
was controlled within ±1°C at a constant temperature
in the range of 100 to 130°C. At suitable time inter-
vals, parts of the reactant mixture were sampled and
analyzed. Concentration of cumene was determined by
gas chromatography. The column packed with silicon
SE-30 was used at 110°C. Cumene-hydroperoxide was

Fig.
detected quantitatively by iodometry.
The experimental apparatus
3. Mechanism for Chemical Steps of the Reaction
Received on July 24, 1969
The liquid phase oxidation of cumene will be ex-
Kazuo Hattori is with Mitsubishi Heavy Ind. Co., Mihara,
Hiroshima plained in terms of a radical mechanism. Referring to

72 JOURNAL OF CHEMICAL ENGINEERING OF JAPAW

previous works2>10), the following mechanism for chemi- acids, may accelerate the decomposition rate of ROOH
cal steps of the reaction will be assumed. Below, R-, and also act inhibitively on the radical oxidation of
RH and ROOHdesignate cumyl radical, cumene and RH. In this period, at more than about 50% in con-
cumene-hydroperoxide, respectively. version of cumene, therefore, the ROOHconcentration
(Initiation Steps) has the maximum value and then declines marked-
From initiator (I112) '. ly. The selectivity for ROOH produced from RH
In, -> 2In- I ( } decreases sharply, as shown in Fig. 2. The maximum
In-+RH >R-+InH1 u; value of ROOHconcentration experimentally obtained
By decomposition or dehydrogenation of cumene : was not reproducible. It will be understood that a slight
RH->R-+H- ] () change in purity of the reactant cumene must have a
RH+O2 >R-+HO2-I K}
sensitive effect on this maximumvalue.
By decomposition of cumene-hydroperoxide :
ROOH > RO- + -OH ki 5. Chemical Rate Expression in the Steady Cham-
RO+RH >R-+ROH k2 (3)
à"OH+RH > R- +H2O h
Propagation Period.
(Propagation Steps) The industrial operation of this reaction is usually
R-+O2 >RO2- k, 1 ,v
continuous. The conversion of cumene in the reactor
RO2-+RH >R-+ROOHh I W
effluent is usually less than 40%, to obtain high selec-
(Termination Steps) tivity of ROOH.The reaction scheme in the continuous
2R- > R-R h operations, therefore, corresponds to the steady chain-
R- + RO2- > ROOR &7 (5) propagation period in the batch operation. The authors'
2RO2- > ROOR + O2 ks interest in the present kinetic study was directed to
ki represents the reaction rate constant of each corre- this steady chain-propagation period. Assuming the
sponding elementary step. Besides the above reactions quasi-steady state of radical concentrations, the following
there may exist the following chain branching reactions, rate expressions follow from the reaction mechanism
which produce some byproducts for shown in Eqs. (l) to (6). The assumption of the
O y
quasi-steady state will be satisfied in the steady chain-
f \-c-ch3 propagation period. For the derivation of Eqs. (7) and
RO- åº f I +CH3-
(8), refer to Appendix 1.
CH3-+O2 -åº CH3O2- f (6) kt[Ot]
~rRH ~ *,[O,]
,+fa[RH]
rrTTi MKHJV
/ fa[ROOH]
h
CH3O2- +RH åº HCHO+H2O+R- + 2/fa'[ROOH] (7)
_ &[O2] ,- -, /_fc[RQQHl

CH3 J
I
0-C
+H2O+R-
-CH2 rB00H~ MO2]+fe[RH]MKHJV
- fe'[ROOH]
h
(8)
Decomposition of cumene-hydroeproxide without produc-
ing radical also has to be taken into account.

i\. The Reaction Periods in the Batch Operation

A typical example of experimental data obtained in
the batch operation is shown in Fig. 2. The reaction
scheme in the batch operation was characterized by
being classified in the following three periods.
(The induction period) In this period, the reactions
of Eqs. (l) and (2) proceed mainly as the initiation
steps. The amount of chain
cumene-hydroperoxide
carrier R- produced from
ROOH, in the scheme of Eq.
(3), is too small to initiate the reaction.
(The steady chain-propagation period) In this period,
the initiation steps of the reaction are expressed by Eq.
(3). The increase of concentration of ROOHaccelerates
the reaction rate first, but the decrease of RHconcentra-
tion then reduces the reaction rate. The maximum
reaction rate is obtained at a certain conversion of RH,
which is about 30%.
(The termination period) As the reaction proceeds,
there accumulate byproducts, such as ketones, aldehydes,
carbinols andviaacids, which are produced fromcarbinols
consecutive Fig. 2 An example of experimental results and
reactions ROOH. These, especially and reaction periods in batch operation

VOL.3 NO.1 1970 73

 ki is the specific rate of the total decomposition of where poj is the partial pressure of oxygen, which is
ROOH, and/is the ratio of decomposed ROOH-produced assumed to be in equilibrium with the concentration of
radicals (refer to Eq. (3)) to the total decomposed oxygen in liquid phase, [O2]. hi is £4JF//[RH]a«, if
ROOH, that is. ki=ki'f.
[O2]-HpoJ, where H is Henry's constant. At low
In most cases of liquid phase oxidation of hydrocarbons, values of poj, the approximation of Eq. (9) is not
it is said that the effect of the partial pressure of oxyygen correct. The experimental results showed that, under
in the feed gas is negligible because the rate of reaction a specific bubbling condition with a constant oxygen
between free alkyl radicals and oxygen molecules is
very fast, i. e. felX^l^&iCRH]. However, in the case
partial pressure, ofK was
the conversion RH.almost
The constant
adaptability independent of
of Eq. (8)
will be discussed later.
of oxidation of cumene, which is a tertiary hydrocarbon, Substitution of Eq. (9) reduces Eq.s (7) and (8) to
it was reported7>8) that the effect of oxygen pressure
on the reaction rate is minor, but not negligible. There- - rRH = X[RH][ROOH]0-5 + 2/fc'[ROOH] (10)
fore, taking an average value of [RH], that is, [RH]a«, rROoH = X[RH][ROOH]0 5 - £/[ROOH] (ll)
the following replacement will be approximately placed
in Eqs. (7) and(8).
__V__ , fkT^ MQ2] JkT 6. On the Induction Period
K -~~~kl T Vjfc8 ^£4[O2]+*B[RH]k5V h
1 + -£-/*,
The experimental data obtained with different amounts
(9) of the initiator are shown in Fig. 3. The larger amount
of the initiator gave the shorter induction time of the
reaction. Although a slight decrease in selectivity of
ROOHconverted from RHwas observed with increase
of initiator concentration, the rate of reaction during
the steady chain-propagation period was almost the same,
as seen in Fig. 3.

7. Rate of Decompositoin of Hydroperoxide

It was assumed that the rate of decomposition of
ROOHwas independent of oxygen existing in the
system. Therefore, the following experimental procedure
was used to observe the decomposition of ROOH.
When a certain time elapsed after the start of the
reaction, the bubbling gas containing oxygen was replaced
Fig. 3 The effect of initiator concentration on reaction by pure nitrogen. Then the change with time in the
concentrations of RH and ROOHin the reactant mixture
was followed. The experimental data obtained are shown
in Fig. 4. Decomposition rate of ROOHwas found to
be proportional to the concentration of ROOH alone.
As seen in Fig. 5, the plot of In[ROOH]/[ROOH]
against time shows that the experimental results fit
this first-order kinetics, where [ROOHL is the initial
concentration of ROOHat the time of switching the
bubbling gas from oxygen-containing gas to nitrogen.
It was also observed that the specific rate of reaction
k! was independent of [ROOH]o in the steady chain-
propagation period at a constant temperature. In the
termination period, on the other hand, the rate of
decomposition of ROOHwas markedly accelerated. From
the Arrhenius plot of the observed value of ki in the
steady chain-propagation period, shown in Fig. 6, it
was obtained that :
ki1 = 1.57 x 1014exp(- 24,800/i?T) (12)
The value of /, which is the ratio of decomposed
ROOHreacting with RH(refer to Eq. (3)) to the total
decomposed ROOH,will be obtained from the comparison
between consumed ROOHand RHin the experimental
result shown in Fig. 4. Since the consumed amount
Fig. 4 Decomposition of cumene-hydroperoxide under of RHand ROOH,however, was so small, an accurate
nitrogen atmosphere value of f was not obtained. It was estimated as about
74 JOURNAL OF CHEMICAL ENGINEERING OF JAPAN
 Fig. 5 First-order kinetic plot
of decomposition of cumene-hydro-
perox i de

0.4 independently of temperature.

8. Interpretation of Experimental Results

Assuming isothermal conditions and constant density
of liquid reactant mixture (these assumptions will be
reasonable), the design equations of the batch-wise
operation were given by
df[RH]
dd
J [ROOH]
= Trooh (14)
The numerical dd rates,
values of reaction Trh and trooh
were evaluated by differentiating
of concentration of RH and
the experimental curves
ROOH vs. reaction time
(refer to Fig. 2). Substituting the evaluated values of
Trooh and Trh in Eqs. (10) and (ll), the rate constant
K is determined, since the values of ki and/are given
as mentionedabove. Fig. 6 Arrhenius plots of rate constants
The value of the rate constant K determined were
ascertained by the integral method. Substitution of
Eqs. (10) and (ll) into Eqs. (13) and (14) yields the
following differential equations.
- -^=|p- = X[RH][ROOH]0 5 + 2/^'[ROOH] (15)

dlR^?lii = X[RH][ROOH]0 5 - *.'[ROOH] (16)

atf
Since these equations are difficult to integrate analytically,
an analog computer was used to solve them. The
concentrations of RHand ROOHobtained experimentally
at about 5% in conversion of cumene were used as
the initial conditions of the integration. The integrated
curves fit in well with the experimental data as shown
in Fig. 7. It should be noticed that the value of
K obtained above depends on the bubbling conditions,
such as the gas flow rate and the partial pressure of
oxygen.

Fig. 7 Comparison between calculated curves and

experimental data

VOL.3 NO.1 1970 75

 The arrow mark shows the correction from pOt to
po'2> where poj is easily
use of Eq. (17),
obtained graphically by
as shown in the figure
Fig. 8 Plot of reaction rate vs. oxygen pressure

Fig.9 PlotofKvs.po2'

-ro2, is equated to the mass transfer rate of oxygen

9. Effect of Oxygen Transfer on Reaction Rate
through the gas-liquid interface.
It is assumed that the consumption of oxygen except -ro2== -i ~(^02-P02) =trooh4"£1[ROOH] (17)
in producing ROOHis negligible and, therefore, the rate
of consumption of oxygen, rch, is the same as the rate where po2 is the partial pressure of oxygen in gas phase
of production of ROOH, trooh+^i/;[ROQH]. Neglecting and poj is that in equilibrium with the dissolved oxygen
also the accumulation of oxygen in the liquid phase, in liquid phase. To derive Eq. (17) another important
76 JOURNAL OF CHEMICAL ENGINEERING OF JAPAN
assumption is made, That is, the reaction of interest
is in "the slow reaction regime". It means that the
amount of reaction in the liquid film near the gas-liquid
interface is negligible in comparison with that in liquid
bulk. This assumption is reasonably satisfied for the
present system, as noted in Appendix 2.
Numerical values of constants in Eq. (17) were deter-
mined in the following manner. The value of Henry's
constant, if, for pure cumene was given by Low6),
who also remarked that the effect of temperature on
the values of H is negligible. This value was used for
the reactant mixture, because no information about H
in cumene-hydroperoxide was found. Mass transfer
coefficients, ki, were estimated from the following
correlation proposed by Calderbank et al. X).
à"l\pDiJ U"**V p2
The properties, p and '[i, of the reactant mixture, 30
%conversion of cumene, were measured at room temper-
ature and wereextrapolated to the reaction temperature.
The diffusion coefficient in liquid was deduced from
the experimental data of Low6). The calculated value
of ki for instance at 120°C is 0.108cm/sec. It coincides
well with the value deduced from experimental results
obtained in the authors' laboratory5), 0.095cm/sec. The
latter were obtained for the CO2-H2O system in a
Fig. IO Plot of l/K vs. l/p,
bubble column, 50mm0. The inter facial area, as, was 'O*
evaluated from photographic observation by assuming
that bubbles were ellipsoids. The gas holdup, <p, was
directly measured from bed expansion. Appendix I : Derivation of Eqs. (7) and (8)
Since values of the reaction rate trooh are obtained
In the steady chain-propagation period the pseudo steady state
as mentioned above, poj can be determined from Eq. for concentrations of free radicals, R-, -OH, RO and RO2- is
(17) at a specified condition of bubbling. As the partial assumed. Taking mass balance for radical RO2-,
pressure of oxygen in gas phase, pos, the arithmetic h{Ahh ~ h1)[RO2-]4 + fe(4y8 - h2) [RH][RO2-]3
mean between the value in feed gas and that in effluent + (^[RH]2 + ^5*7[RH][O2] + W&8[O2]2.
gas, was used. Some experimental values of reaction - WLROOH]) X [R02/]2 + 2^iW7[ROOH][O2][RO2-]
rates at 30% conversion of cumene and differences - W[ROOH][O2]2 = 0
Assuming 2\lhk% =h 2) and solving for [RO2-],
between po2 and poj are shown in Fig. 8. f 1= _ ^4[O2]V^i[ROOH]

IO. Rate Constants in Chemical Steps hyjks [RH] + kJh [O2] + WkCROOH]
(A-l)
The third term in the denominator will be omitted compared
Once values of poj are determined for specified condi- with the firsthandIthe second terms2) and k& will be equated
tions, rate constantsThis Kare
values of poj.
plotted against corresponding
is shown in Fig.9. If K is to h2\ thus
expressed by Eq. (9) as a function of poj, plots of 1/K LR°2 J ~ ^4[o2] +^5[rh] y h [A 2)
vs.because
1/POJ will give a straight line at constant temperature,
Eq. (9) is rearranged as Meanwhile, rates of reactions for RHand ROOHare given by
- rRH = £5[RH][RO2-] + 2/MROOH] (A-3)
trooh = &5[RH][RO2-] - ^[ROOH] (A-4)
k~kNh/h kUh/hvpo,'I uy;
As seen in Fig. 10, this relation is well satisfied and
Substitution of Eq. (A-2) into Eqs. (A-3) and (A-4) leads to
Eqs. (7) and (8).
the effect of poj on values of K is small but not to
be neglected, especially at high temperature.
Arrhenius plots of the rate constants obtained from Appendix 2 : On the Assumption of "the Slow Reaction
Regime"
Fig. 10 are shown in Fig. 6. Finally, K is expressed
by To testify that the reaction of interest is in the slow reaction
1.00 x 107exp(- ll,800/RT)POJ , . regime, the following assumptions are made.
K ~~ 1 + 7.41 x 10-5exp(9J900/i^T)>s/ ^"J 1) Mass transfer resistance of oxygen in gas phase is neg-
lected.
The solid curves in Fig. 9 are calculated from Eq. (20).
2) The equilibrium between gas phase and liquid phase at
the interface is attained, and

VOLv3 NOi.l 1970 77

 (A-5)
[O2]i = HPo2 / = fraction of ROOHreacting with RHto total
where subscript i shows the value at the interface. [In2] decomposed
= initial concentrationROOH
of initiator [[g-mol/Z]
- ]
3) The rate of chemical reaction in liquid phase is approxi-
mated to be proportional only to the concentration of dissolved
H - Henry's constant [g-mol/Z-atm]
kt - reaction rate constant, subscript i (=1, 2, à"à"à")corresponds
oxygen at any instant of the batch operation. to stoichiometric equation
ro2 = - Jfcr[O2] (A-6) K = overall rate constant defined by Eq. (9)
According to the film theory and the above assumptions, the ki - liquid phase mass transfer coefficient [m/hr]
mass transfer rate of oxygen from gas phase to gas-liquid kr = apparent reaction rate constant [1/hr]
interface, N\, and that from liquid film near the interface to JVi = mass transfer rate of oxygen through gas-liquid
liquid bulk, N2, are given by9) interface [g-mol/m2 - hr]
2V2 = mass transfer rate of oxygen from liquid film to liquid
(
H A bulk [g-mol/m2 - hr]
Ni = hpH Po2 ~ coshrp0* J
(A-7) [O2] = concentration of oxygen [g-mol/Z]
(
N2 = kiBH
Po> (A-8) po2 = partial pressure of oxygen in gas phase [atm]
pol - partial pressure of oxygen which is in equilibrium
cosh r with dissolved oxygen in liquid phase [atm]
where r = JkrDi /ki, j8 = r/tanhy (A-9) Qg = volume flow rate of oxygen-containing gas
[/(at 0°C, latm)/hr]
The pseudo first-order assumption in Eq. (A-6) for the chemical
reaction rate is not proper in the present system, but is used for R = gas constant [cal/g-mol-°K]
the sake of convenience. Here, the value of the rate constant, [O2], [RH] and [ROOH] = concentration of oxygen,
cumene and cumene hydroperoxide, respectively
kr, is assumed to be [g-mol/Z]
kr" d[o2] (A10} fo2, trh and trooh - reaction rate for O2, RH and ROOH,
respectively [ g-mol/Z - hr]
At the present reaction conditions, i. e. £^130°C and ^o2^0.1 T = absolute temperature [°K]
atm, the maximumvalue of kr is about 300 1/hr. t - temperature [°C]
Values of other constants for the reactant mixture at 120°C 0 = reaction time [hr]
are
y- = viscosity of liquid reactant mixture [kg/m-hr]
Di^4.5 10"5m2/hr, £^3.9m/hr p<P = density
=gasholdup of liquid reactant mixture [kg/m3]
[-]
Substituting these values in Eq. (A*9),
r^0.03
and thus Literature cited
coshr= 1.00, j8= 1.0
1) Calderbank, P. H. and Moo-Young, M. B.: Chem. Eng.
Therefore, from Eqs. (A-7) and (A-8) one can obtain Set., 16, 39 (1962)
Ni = N2 (A-ll) 2) Emanuel, N. M., Denison. E. T. and Maizus, Z. K.:
"Liquid Phase Oxidation of Hydrocarbons", Plenum
This means that the consumed amount of oxygen in liquid film Press, 1967
near the gas-liquid interface will be neglected, and the assump-
tion of "the slow reaction regime" will be reasonably 3) Fortuin,
182 (1953)
J.P. and Waterman, H.I.: Chem. Eng. Set., 2,
accompl ished. 4)5) Fortuin, J.P.T. : and Waterman, H.I.: ibid., 3, 608of (1954)
Hirahara, Master thesis. Tokyo Institute Tech-
Acknowledgement nology, 1966
The authors thank to Mitsui Petrochemical Industries Ltd. 6) Low, D.I.R.: Canadian J. Chem. Eng., 45, 166 (1967)
for supplying cumeneused in the present work. 7) Kucher, R.V., Kovbuz, M.A., Bugrova, E. M. and Vasil'-
Kevich, I. M. : Zhurnal Prikladnoi Khimii, 35, 170 (1962)
8) Nemtsov, M.S., Radchenko, 1. 1. and Fisher, S.A. : Khim.
Nomenclature Nauka Prom., 2, 306 (1957)
9) Sherwood, T.K. and Pig ford, R.L.: "Absorption and
as - interfacial area [1/m] Extraction," McGraw-Hill, 1952
Di - diffusivity of oxygen in liquid reactant mixture 10) Twigg, G.H. : Chemistry and Industry, 12, 476 (1966)
[mVhr]

78 JOURNAL OF CHEMICAL ENGINEERING OF JAPAN