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541.461.6.01:541.593.21 1 :541.594.3
PREPARATION OF ADIPIC ACID BY OXIDATION OF CYCLO-
HEXANOL AND CYCLOHEXANONE WITH NITRIC ACID
Part 111. Reaction kinetics of the oxidation
BY
W. J. van ASSELT and D. W. van KREVELEN
Central Laboratory Staatsmijnen, Geleen and
Laboratory for Chemical Technology, Technological University, Delft
A. Introduction
As described in a previous publication 1, the oxidation of cyclohexanol
can be represented as follows:
ghtaric acid
succinic acid
1 W. J. van Asselr and D . W. van Krevelen, Part I, Rec. trav. chim. 82, 51 (1963).
Table I
Some results of oxidation experiments
~~ -
Products (2)
Adipic
ment acid (1)
Reaction conditions Time (1) Adipic Glutaric Succinic from N
Nitrolic acid acid acid nitrolic
acid acid
(min) (mmoles) (mmoles) (mmoles) (mmoles) (mmoles) (m
(roducts (2)
me,
Reaction conditions
I Ij
Time (1) Adipic Glutaric Succinic
Adipic
acid
from
Nitrolic acid acid acid nitrolic
i acid acid
(min) (mmoles) (mmoles) (mmoles) (mmoles) I (mmoles)
1
I
1
Cyclohexanol = 9.81 mmol 30 2.02 3.36 0.07
NH4V03 = 1 mmol 2.02 7.25 0.16
WN0z)o = 20mmol 90 2.00 7.40 0.30
(HNOz)tinal = 18 mmol 60
I
I
30.4%HNOs 2 I .64 0.15 0.06 0.07 ~ 0.01
Volume = 50ml 7 3.37 0.57 0.28 0.12 I 0.06
Temp. = 30.0" 15 3.90 0.91 0.57 0.15 0.18 4
Cyclohexanone = 10.61 mmol 35 3.42 1.46 1.10
(HN0z)o = ~IXUIIOI 60 3.07 1.77 1.41
Preparation of adipic acid by oxidation of cyclohexanol, efc. 82 (1963) RECUEIL 441
- __
with kox. For the calculation we depend on the chromatographic deter-
mination of nitrolic acid and adipic acid, because Dione and cyclohexanone
cannot be quickly determined in a simple way.
By the side of nitrolic acid, Dione is formed as a by-product, the ratio
in which Dione and nitrolic acid are produced (Dione/NA ratio) changing
with the reaction conditions 1.
If vanadate is used as catalyst, the Dione is converted to adipic acid.
Under the reaction conditions chosen this reaction appears to proceed at
a moderate rate, and in some cases both kox and kv can be calculated.
B. Methods
General procedures
The oxidation experiments were carried out in the reactor described in
the previous publications 1, 2, at temperatures varying between 10 and 40",
and at nitric acid concentrations of 67-20 per cent by weight of N H 0 3 .
1 g of cyclohexanol or cyclohexanone was added to 50 ml of nitric acid and
the temperature was kept constant within f 0.1". The nitrous acid concen-
tration is measured before and after the reaction.
Via a siphon, liquid samples of the reaction medium are collected i n an
amount of ice to which some hydrazine sulphate has been added, the
removal of the NH02 and the cooling effect causing the reaction to stop
immediately. These samples are analyzed chromatographically 1.
To study the side reactions, some oxidation experiments, in which pure
Dione was added to the nitric acid, were carried out in the same way; the
Dione dissolved rather slowly.
W. J. vat1 Asselt and D. W. van Krevelerr, Part TI, Rec. trav. chim. 82, 429 (1963).
W. J . van Asseli Thesis, Delft (1960).
442 W. J. van Assel! and D. W. van Kreveleti
!I
.- Nitrolic acid 0-
Adipic acid
I
0-
-o--o-o
.
z o
0 4 6 8 10 12 14 16 18 20 22
t Fig. 1.
_c Time (rnin)
so that the reaction-velocity can be directly found from the change in the
nitrolic acid concentration. To this end we introduce the concept potential
nitrolic acid concentration (NApot.). This is the difference between the
concentration at t = m, and the concentration of nitrolic acid (+ adipic
acid from NA) at time t. The NApot.is consequently proportional to the
Preparation of adipic acid by oxidatioii of cyclokexaiiol, e/c. 82 (1963) RECUEIL 443
As can be seen i.a. from Table 2 the oxidation rates of cyclohexanol and
cyclohexanone are equal. The conversion of -an01 into -anone consequently
proceeds much quicker than the further oxidation. It has also appeared
that extra addition of HNOz (which, as a matter of fact, is necessary i n the
case of cyclohexanone) does not affect kox. Neither does copper have any
influence on the reaction in this temperature range, as is to be expected1,
while the use of vanadate increases only the amount of adipic acid, without
affecting the conversion of cyclohexanone to nitrolic acid and Dione.
With vanadate being used as a catalyst, kox can be calculated from the
sum of NA and adipic acid formed from nitrolic acid (calculated with the
aid Of kNA).
b. So far, it has been assumed that the Dione/NA ratio remains constant.
Tn reality, however, the HNOs-concentration will decrease owing to forma-
444 W. J. van Asselt and D. W.van Krevelen
____ -. __ _ _ _ ~ _- -
T a b l e I1
Comparison of the reaction velocities (with and without a catalyst)
anol 10.0 2. I
anol 14.1 2.5
anol 20.0 4.3
tion of nitrolic acid, with the consequence that the Dione/NA ratio will
also decrease during the oxidation. The difference is greater as more nitrolic
acid is produced, in other words as the nitric acid concentration is higher
and/or the temperature is lower. The HNO2-concentration at any moment
can be calculated from the initial concentration minus the amount of
nitrolic acid formed. How much Dione has formed beside the nitrolic acid
can now be calculated stepwise over small intervals at the actual HN02-
concentrations; the cyclohexanone concentration as a function of time can
then be found by summation. An example of this procedure is given in
Table 3.
Even in cases as unfavourable as that of the example, the value of kox
calculated from the change in the -anone concentration proves to be only
slightly higher than that found previously (4.6 as compared with 4.3).
Various calculations have shown that the reaction-velocity constants
obtained by these two methods differ by no more than O-lO%. The values
found by the first method have therefore been maintained for the further
calculations.
e
NA + adipic A NA HNOz Dione/NA A Dione +
N A Dione Unconverted
acid cyclohexanone
) (mmoles) (mmoles/l) ratio * (mmoles) (mmoles)
(mmoles) (mmoles)
fig. 8 .
Preparation of adbic acid by oxidation of cyclohexunol, etc. 82 (1963) RECUEIL 447
Table IV
Oxidation of pure Dione with nitiic acid without a catalyst
In Figure 4 the values of kox at 20" read from Fig. 3 are plotted versus the
HN03-concentration. It can be seen here that above 30% HNO3 there
exists a simple empirical relation between koxxand the HNO3-concen-
tration.
The equation for the oxidation velocity can then be written as:
dC
dt
- kos .C = 2.8 . 108 C . ( C ~ h . 0-~ 2.9) . e-15850/11T
where: C = concentration of cyclohexanol, or cyclohexanone;
C H N O=~ concentration of H N 0 3 (gmol/I).
In a following publication * it will be shown that the reaction kinetics,
measured in batch experiments, are completely confirmed by experiments
in a continuous reactor.
Besides the values calculated from the standard experiments after com-
pletion of the oxidation proper, some additional data have been obtained
from the oxidation experiments with pure Dione.
1 kox 40%HN03
2kv ,, ,, 2OvI
3kv ,. ,. 1OV/
4kv 35%.. ,,
T1 1054-
The number of data is too small and, moreover, not accurate enough to
permit formulae to be drawn up also for kv and k H .
From the position of the lines 2 and 3 in Figure 5 (both running parallel
to line 4) the impression is gained, however, that the conversion of Dione
under the influence of vanadate is proportional to the vanadate concen-
tration.
(Received December 14th. 1962).