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P.-L. FABRE
Laboratoire de Chimie Inorganique, EA 807 CNRS, Universite Paul Sabatier, IUT Chimie, Av. G. Pompidou,
81100 Castres, France
A pilot plant electrolyser was built, which, in design, was similar to an industrial reactor used for
metal recovery from waste waters. Increased mass transport rates were achieved by applying a pulse
to the reactor solution. The ®rst reaction tested on this new cell was the indirect oxidation of
cyclohexanol in aqueous solution by means of an iodinated intermediate species. Several electro-
chemical methods, such as cyclic and linear sweep voltammetry and chronoamperometry, were used
for the study of the reacting system. The results from these analyses have allowed optimization of the
reactor operating conditions. A mathematical model for the process has been established which
predicts the reactor yield and conversion as a function of the main operating parameters.
The reaction employed to test the reactor perfor- diameter reduction in the mixing zone makes it pos-
mance is the indirect oxidation of cyclohexanol to sible to have a wider amplitude range and a uniform
cyclohexanone, which is carried out in an aqueous, velocity pro®le entering the reaction zone.
homogenous phase by means of an inorganic cata- The electrodes are made of a series of rigid ex-
lytic electron carrier. panded platinized titanium grids of high surface area,
placed in the reaction zone, which consists of a glass
cylinder that allows for dierent electrode con®gu-
2. Pilot plant reactor rations. The characteristic dimensions of the grids
employed in this work are shown in Fig. 2. The re-
The process is depicted in Fig. 1. The electrolyte so- action zone arrangement (shown in Fig. 3) used for
lution is prepared in the tank; it is fed to the base of the cyclohexanol oxidation reaction has a working
the reactor, then passes through a mixing zone fol- electrode surface area of 0:4 m2 . The grids are inter-
lowed by the reaction zone. The solution is fully changeable and their number can be increased. A
recycled. In the present con®guration of the process, radial con®guration, used when a divided cell is
reactor and tank volumes are V1 2 dm3 and required, can easily be installed.
V2 10 dm3 , respectively.
A pulsating movement is applied to the electrolyte
in the mixing and reaction zones to maintain high
mass transfer coecients between the solution and 3. Cyclohexanol oxidation
the electrode. The pulsating device is a pneumatic
system operating at 7 bar over a Te¯on membrane 3.1. Reaction system
0:4 m in diameter. The pulsating movement follows a
signal of the type: y a cos
2pft, where a is the The direct electrochemical oxidation of alcohols is
amplitude, f the frequency and t the time. If v0 is the usually dicult to accomplish because it requires
steady ¯ow velocity, the instantaneous velocity of the electrode potentials greater than 2 V vs SCE [7]. In-
liquid phase is given by direct oxidation of primary and secondary alcohols
can be achieved by means of an electrocatalytic
v v0 2pfa sin
2pft
1 couple. Indirect electrochemical oxidation or reduc-
The hydrodynamics of a pulsed ¯ow system are tion has been studied during the last twenty years,
characterized by the Strouhal number, expressed as and the applications of organic and inorganic inter-
mediates such as iodide [8], bromide [9], nitrate [10],
Sr
2pfa=v0
2
manganese dioxide [11], NaCl±RuO2 [12], PVH [13],
In a pulsated device the mass transfer coecients are N -hydroxilamine [14], N -hydroxiphthalimide [15] and
a function of the Strouhal number. The piston fre- triarylamine [16] have been developed.
quency can be set between 0 and 1:5 sÿ1 and the Cyclohexanol oxidation is carried out by the an-
amplitude varies from 0.01 to 0:1 m. odic oxidation of iodide, to an intermediate product
The mixing zone is made of glass and ®lled with I which reacts with cyclohexanol to give cyclo-
glass beads as turbulence promoters for the solution. hexanone and to regenerate Iÿ . Tertiary alcohols
The ratio of the lower to upper diameter is 2 to 1. The cannot be oxidized this way.
3.2. Kinetics
4. Experimental details
presence of cyclohexanol or ter-butanol. For both dynamic conditions the system can be considered as a
couples, the peak current is a linear function of the continuous stirred tank reactor [24]. In this case all
sweep rate, showing that the whole process is diu- the electrolyte is recirculated after dilution in the
sion controlled [22]. reservoir (Fig. 7).
Chronoamperometry experiments allowed us to Mass balances for cyclohexanol over the reservoir
determine the correct current density values to be and the reaction zone, considering ®rst order kinetics,
used in pilot plant operation, and showed that the can be written as follows:
intermediate species has a very short life time. This
(i) Reaction zone (CSTR). Cf and Ce are the
result, however, does not agree with the cyclic vol-
cyclohexanol concentrations in the feed and in
tammetry plots, in which we ®nd a signi®cant ca-
the exit of the reactor, respectively; K is the ap-
thodic wave corresponding to I reduction. As the
parent reaction rate coecient; V1 and V2 are the
process appears to be diusion controlled, the pul-
reactor and reservoir volumes and Q is the vol-
sating parameter settings should have an important
umetric ¯ow rate.
eect on the pilot performance. The current±poten-
tial plots have allowed us to establish the optimal pH dCe
V1
Q KV1 Ce QCf
10
and potential (1:1 V vs SCE) at which the electrolysis dt
should be carried out. accumulation exit reaction feed
(ii) Reservoir. Here Cf is the concentration in the
4.2. Pilot plant operation exit of the tank, after dilution.
dCf
The electrolyses were controlled by means of a V2 QCf QCe
11
dt
Heinzinger PTN 32±40 power supply. The total liquid
accumulation exit feed
volume circulating in the whole installation was
0:035 m3 . Products were analysed by gas chroma- Analytic solution of these equations leads to
tography on a Chrompack 50 m polar column; split
C f t C0 Ks1 1 Ks1
injector 200 C; FID 240 C, oven 130 C, 16 psi.
C e t exp ÿ t
12
The usual concentrations employed on pilot plant 1 Ks1 1 Ks1 s1
electrolyses were: 0:05 M KI, 0:1 M NaCl, 5% volume C0 Ks21 1 Ks2
Cf t exp ÿ t
ter-butanol. Sodium chloride was used as supporting Ks21 ÿ
1 Ks1 2 s2 s1
electrolyte, and ter-butanol was added to increase the
C0
1 Ks1 2 s2 Ks2
cyclohexanol solubility in water. The initial cyclo- ÿ exp ÿ t
hexanol concentration was found to be an important Ks21 ÿ
1 Ks1 2 s2
1 Ks1 s2
operating variable and was set at values between 0.05
13
and 0:2 M. where C0 is the initial cyclohexanol concentration and
Empirical results from a preliminary factorial de- s1 and s2 are the residence times in the reactor and
sign study at laboratory scale have shown that the reservoir, respectively. I is continuously generated
volumetric ¯ow rate has no in¯uence on the conver- and its concentration is assumed to be constant
sion rate or overall selectivity [3]. This observation is during reactor operation, so that the chemical reac-
con®rmed by the experimental results obtained from tion rate based on cyclohexanol consumption can be
pilot plant electrolyses. Flow rate in all these experi- expressed by a ®rst order kinetic equation in which
ments was kept constant, providing a steady ¯ow the intermediate concentration is included in the rate
velocity of 3:3 10ÿ4 m sÿ1 . constant K.
In the ®rst seconds of electrolysis the solution This apparent rate constant
K is a function of the
takes on a brownish yellow colour. At the same time amplitude and frequency of the pulsation, current
hydrogen evolution begins and the pH slowly rises. density and initial concentration of cyclohexanol,
Iodine continues to be generated; within a few min-
utes the electrolyte becomes dark red and pH reaches
a stable value (iodine is reduced at the cathode).
Electrolyses were carried out at constant current. For
all the reported experiments cell voltage was constant
(between 4 and 4:5 V) as well as the anodic potential
which, in every case, had values of 1.0 to 1:2 V vs
SCE. The catalytic behaviour of the couple Iÿ =I
allows operation at constant current, cell voltage and
working electrode potential [23].
5. Process modelling
* In literature it is considered that, for hydrodynamic conditions yielding Sr £ 4, the problem is that of a plug ¯ow reactor, and not a CSTR
[23]. Our installation does not behave as a plug ¯ow reactor, since there is no concentration pro®le along the axial direction of the ¯ow in
the electrodes zone. The case without pulsation will be treated as a CSTR.
A PULSED FLOW REACTOR FOR ELECTROORGANIC SYNTHESIS ± II 481
[17] I. Koltho and J. Jordan, J. Amer. Chem. Soc. 75 (1953) 1571. [22] Southampton Electrochemistry Group. `Instrumental
[18] Z. Ogumi, S. Ohashi and Z. Takehara, Electrochim. Acta 30 Methods in Electrochemistry', Ellis-Horwood (1990).
(1985) 121. [23] P. Roquero, A. Ghanem, P. Cognet, G. Lacoste, J. Berlan,
[19] G. Dryhurst and P. Elving, J. Anal. Chem. 39 (1967) 606. P. Fabre and P. Duverneuil, Chem. Engng Science 51
[20] M. Pourbaix, `Atlas d'EÂquilibres Electrochimiques', Gaut- (1996) 1847.
hier-Villars (1963). [24] A. Ratel, P. Duverneuil and G. Lacoste, J. Appl. Electro-
[21] A. Bard and L. Faulkner, `Electrochimie: Principes, Meth- chem. 18 (1988) 394.
odes et Applications', Masson, Paris (1983).