Chemical Engineering Science, 1963, Vol. 18, pp. 471-483. Pergamon Press Ltd., Oxford. Printed in Great Britain.

Adipic acid formation by oxidation of cyclohexanol and

cyclohexanone with nitric acid
Measurements in a continuous stirred tank reactor
reactor stabilityt

W.J. VAN ASSELT and D. W. VAN -EVELEN

Central Laboratory Staatsmijnen, Geleen and
Laboratory for Chemical Technology, Technical University, Delft

(Received 18 February 1963)

Abstract-The reaction kinetics of the oxidation previously measured in batch experiments are com-
pletely confirmed by experiments carried out in a continuous stirred tank reactor, both during steady
and unsteady operation (starting-up).
The measurements have furnished some supplementary data about the rate of by-product formation
and about the influence of the NH4VOs and Gu(NOs)a catalysts.
The stability of the reactor is highly dependent on the concentration of the nitrous acid, which is
initially formed during the conversion of cyclohexanol and is partially consumed in the course of
the reaction. The production and consumption of HNOa can be controlled separately, and as HNOa
is absolutely necessary for effecting the oxidation, conditions can be created under which the reaction
in a continuous reactor dies out. After the analogy of the term “autothermic reactor”, the reactor
we are concerned with here may be called an “autoconcentrative” reactor in which, in general, two
stable steady states are possible: (1) HNOa concentration = 0, conversion = 0, and (2) both the
conversion and the HNOa concentration have a fixed value.
In between these two states there is mostly an unsteady state, characterized by an HNOa concentra-
tion which may be called the “ignition concentration”.

A. INTRODUCTION
As DEMONSTRATED before [2], the oxidation of
cyclohexanol and cyclohexanone with nitric acid
may be represented in the following reaction
diagram :
(a) Reaction A:B
The conversion of cyclohexanol to cyclohexanone
is initiated by HNOz and proceeds very rapidly
since, owing to the formation of an equimolecular
amount of HN02, the reaction is autocatalytic.
The reaction constant cannot be measured, but
is very large anyhow.

/
(b) Reaction B
r’2
_ principal reactions - side reactions \
D
The meaning of the symbols is given in Table 1. The rate of oxidation of cyclohexanone (B)
The investigation has yielded the data given below. has been determined [2] and can be represented by
the empiric over-all formula:
t The more chemical part of the investigation-the
determination of the reaction mechanism and the reaction
kinetics-has been nubhshed Il. 2.31 and will be summarized 431
- - = k,,[B]
briefly here. The present publication deals with the aspects dt
that are the most interesting to the chemical engineer, i.e.
the application of the reaction kinetics to a continuous (CHNOn- 2*9))[Bl
reaction.

471
 W. J. VANASSELTand D. W. VANKRE~ELEN

Tuble 1 where CHNOl= nitrous acid concentration, in

gmol/l. and
Symbol Name Formula pHNoS= partial pressure of HN03 in mm
Hg.
Consequently, the rates of the separate reactions
A Cyclohexanol
0 H -OH
are

(c) Reaction B + C
B Cyclohexanone
1
k,SBI
r2 = I + @69(C,,o,/pnNo,)2’3
In this reaction an equimolecular amount of
nitrous acid is consumed.
C “Nitrolic acid’
(6 hydroxyimino&nitro-
hexanoic acid) (d) Reaction B ‘f D
Hz @69(cmo~/Pmo3)2’3
OH
r’ =1 + o’69(c,o,/pHNo3)2’3 k,SBI

D “Diane” 1 0
hemihydrate form of Unlike in the former, no nitrous acid is consumed
(I, 2cyclohexanedione) in this reaction.

OH r”2
(e) Reaction B --, E
NOH
E Di-isonitroso This reaction proceeds at a measurable rate
cyclohexanone ,&O only at higher temperatures, above 70°C.
‘\ANOH r3

(f) Reaction C -+ F
HZ. Under the influence of H+ ions nitrolic acid
C
decomposes to adipic acid with simultaneous
F Adipic acid H C’ ‘COOH release of N20.
7
HaC COOH As r, $ r,, hardly any adipic acid forms under the
conditions under which k,,, has been measured.
‘C’
H2 The rate of this reaction (r3) has also been
G Lower decomposition measured (in batch reactions) [3] and may be
products HOOC (CH3)3 COOH
represented by
(glutark acid, succinic HOOC (CHz)a COOH
acid and other acids) etc.
- F =kNA[C]
= 35.1013 exp(- ~)(~)“‘,cCl
In this relation CHNos denotes the nitric acid 1
concentration in gmol/l.
where pHzO = partial water vapour pressure in
Nitrolic acid (C) and Dione (D) are formed
simultaneously in a ratio which was found to mm Hg.
depend on the HNO, and HNO, concentrations,
(g) Reaction D ‘2 F
Dione This reaction proceeds only under the catalytic
nitro ic acid influence of vanadate ions.

472
 Adipic acid formation by oxidation of cyclohexanol and cyclohexanone with nitric acid

In the discontinuous experiments carried out reaction rate constant (kH), could be determined
thus far, all attempts at determining accurate only in continuous experiments.
values of kv- the reaction rate constant of this
conversion-have failed. Success was achieved
only in the continuous experiments described in (j) Reaction E 2 G
the present publication. The experimental results Just like rz, this reaction becomes significant only
will show that k, is virtually proportional to the at higher temperatures; it has not been studied in
vanadate concentration and to the activity (vapour detail.
pressure) of nitric acid. In Fig. 1 the values of k,,

(h) Reaction D If, G reaction BfC

In the non-catalytic conversion Dione is further LD
oxidized to glutaric acid and succinic acid (about
70 per cent in all), and lower decomposition kNA (reaction C+F), k, (reaction D + F), and
products. kH (reaction D + G) measured in the batch ex-
The rate constant of this reaction is of the same periments are shown as functrons of temperature
order as kNA. Also here, accurate values of the and nitric acid concentration.

10-c
a .

6 -

/40% /‘/
/ / / /SO% /

/ / // /
/ 20 ‘I.
/
’ 6’ ,’ /
/

/ /’ ,‘) / //

/
Y /‘..//’ ,’ /
/
/
/ ,’ +/‘/ / ,’

/.. / /
/ / /’
.. / /
/
/ ,*,’ / / ,
w
/
.. /
?
/
A’/ ,/ /
-4
6 10 - ,/.A’,/ ,’ ,’
/“ .,’ /. ,’ - kox

/ / --- k NI
-...A...- k,(400/,)
/ ’ ,’ 0 ky(40%)20mmol NH,VO,/I
/ / II k,(4O%) IOmmol NH,VO,/I.
i/ / f
-Temp. (“Cl

40 45 50 55 6.5
lo-= 53.58
. 10 350 15 20
342 25 334 30 35
326 318 310 30269 294
b I!T.105

FIG. 1. Reaction kinetics measured in batch experiments.

473
 W.J. VANASELT
The object of the present investigation was, on
the one hand, to prove that continuous reactors can
be calculated on the basis of the above-mentioned
kinetic data, and, on the other hand, to investigate
and interpret the dynamic behaviour of these
reactors, in particular the stability.
B. EXPERIMENTAL
1. Apparatus
The reactor used in the continuous experiments
is shown in the diagram of Fig. 2. The reactor
consists of a glass, cylindrical vessel with a cooling
jacket; in the reactor a cooled draft tube is fitted.
Both the draft tube and the cooling jacket are
connected to a thermostat; the liquid flows and
the temperatures can be controlled separately.
Thermometer
Reactor I B\ffle (3 x)
iNO,
FIG. 2. Reactor used in the continuous experiments.
The stirrer speed can be varied between 1500
and 2500 rev/min. To reduce the rotary velocity
of the liquid, the reactor is equipped with some
batYes.
The nitric acid is introduced into the reactor base
via a rotameter, the cyclohexanol and the cyclo-
474
andD.W. VANKRE~ELEN
hexanone being fed to the middle part of the
reactor via a feed pump.
The reaction liquid leaves the reactor through
an overflow; the liquid volume is about 330 ml.
In some experiments the reactor is cascade-con-
nected with a second reactor having neither jacket-
nor draft-tube cooling, but being provided with a
cooling spiral fitted between the draft tube and the
wall. The capacity of the second reactor is about
600 ml. The degree of mixing has been measured
in both reactors with the aid of the response curve
of a step function in a dilute hydroxide solution.
It appeared to be ideal within the observation
errors.
2. Procedure
The feed rate of the nitric acid is about 2 l/hr,
that of the cyclohexanol and cyclohexanone being
90 to 180 g/hr. So, the residence time in the reactor
is approximately 10 min. The NHhVOJ and
Cu (NO,), catalysts, which are used in some of
the experiments, are dissolved in the nitric acid.
The thermostat for the cooling liquid is set
approximately 15°C below the desired reaction
temperature. By separately controlling the liquid
flow to the cooling jacket and the draft tube, the
reaction temperature can be set and kept constant
within O*l”C.
The reactor can now be started up by first filling
in nitric acid and, after adjustment of the temper-
ature and the stationary nitric acid feed current,
starting the anol supply. As a rule, a small amount
of HNOz is added as initiator. The steady state
is automatically reached after rather a long period
of time. The experiments 1 and 19 A, B (Table 2)
have been carried out in this way.
In the other experiments a special starting
procedure has been followed which brings on the
steady state more quickly. First, a batch reaction
is performed until the degree of conversion in the
reaction medium becomes equal to that of the
steady state in the subsequent continuous reaction.
This method is described under the heading “Cal-
culations”.
The steady state being reached, liquid samples
from the reactor overflow are collected in a mixture
of ice and hydrazine sulphate to stop the reaction
after which another test is started. The amount of
 Table 2. Some examples of oxidations in a continuous stirred tank reactor
- - -
-T
Feed Yum oj Nitro- 4dipi Gh SUC- e?l oj
-r -- I
Final Mean Yonver the Vent HNO: lie taric cinic the
Cyclo- 7yclo. Vitric HNO: cont. resi- siont pro- tw CORC. acid acia acid pro-
EXP remp hexa- hexa- acid cont. Catalyst* Of dence km7 ducts iucts #
No. no1 none HNO time + km
mmOl/ IlUll (ml/ 7 jmol (ml/ :mmo1
PC) mm) min) (mmol/l.) wt % (min) min) min) knin) min)
-
1 19.8 16.08 - 29.8 42.0 - 38.7 10.80 0600 9.65 375 2.75 0.39 0.12 10.04
2 15.0 9.93 497 29.3 42.0 - 39.8 10.70 0.502 750 240 2.15 0.28 7.46
3 25.0 9.93 4.97 29.4 420 - 39.5 10.85 0.718 10.70 190 484 0.61 10.80
4 15.0 8.33 6.81 28.9 42.0 2ov 40.0 11.00 0.507 7.68 220 2.31 1.18 0.07 0.13 7.75 3.4
5 25.0 13.21 6.62 28.6 42.0 3ov 38.7 11.10 0.713 14.16 90 345 4.75 5.32 0.20 0.35 13.50 20
6 15.0 7.32 11.71 29.8 42.0 - 40.0 10.50 0.494 9.41 45 150 3.26 0.42 9.28
7 19.8 7.32 11.71 29.9 42.0 - 39.8 IO.45 0606 11.43 50 100 5.33 0.72 11.38
8 25.0 7.32 11.71 30.0 42.0 - rcacti rdicsc 0
2 11.00 7.32 31.2 52.0 10 v 48.5 lo*00 0.679 1244 50 140 7.85 2.98 0.09 0.21 12.75 30
9 19.8
10 25.0 11.00 7.32 31.2 52.0 10 v 48.2 10~00 0.771 14.12 30 11.18 2.44 0.20 0.18
11 22.8 940 9.40 32.1 32.6 - 30.5 9.80 0.520 9.76 30 25 346 0.74 0.21 0.11 6.11
12 20.0 18.58 - 32.3 32.6 - 30.5 9.63 0.450 8.36 10 135 1.52 0.19 0.06 0.02 5.50
13 30.0 18.58 - 32.3 32.6 - 29.6 9.63 0.653 12.13 100 180 4.04 1.06 0.30 0.15 11.75
14 350 18.58 - 32.4 32.6 - 29.1 9.63 0.734 13.63 150 175 5.69 1.72 0.54 0.31 13.70
15 35.0 18.58 - 31.9 32.6 30 v 29.1 960 0.733 13.61 160 215 5.22 3.78 0.71 0.35 1350
16 35.0 1858 - 32.3 32.6 20 Cu 29.1 9.50 0.730 13.57 130 190 5.39 090 023 0.27 13.36
17 35.0 18.58 - 32.0 32.6 ecu + 201 29.1 9.60 0.733 13.61 145 235 4.67 3.68 0.23 0.31 12.70
18 10.0 18.58 - 32.5 60.6 - 58.1 940 0.510 946 45 270 564 0.46 0.03 0.11 9.58
19P 19.8 1640 - 30.0 42.0 - 38.6 10.60 0.595 9.75 340 2.88 0.37 0.06 0.15 10.07
I 34.0 38.6 - 38.0 18.65 0.900 15.73 190 5.11 1.68 0.27 1.29 15.87 econc

* v =
mm01 NH4voa/l.
cu =
mm01 Cu(NOs)a/l.
t Conversion calculated by means of k,, measured in batch experiments.
$ Calculated from the mcasurcd nitrolic acid concentration by means of the Dione/NA ratio.

I._ -WA-.. ,___._ __ _ .“: d _ - .- _ _. _ _ _. __

__ L? m. -1_-_ ,I _
 W.J.VAN~SELT and D.W. VANKREVELEN

vent gas has been measured by means of a rota- C. CALCULATIONS

meter; the gas has not been analysed, however.
Owing to the entrainment of gas bubbles, the
effective reactor volume depends on the stirrer
speed and the amount of cyclohexanol. For this
reason, the reactor contents are drained off and
measured after each series of experiments.
1. Unsteady states
An irreversible first-order reaction X J Y
taking place in an ideally mixed reactor can be
diagrammatically repzesented by

3. Analyses
The adipic acid, nitrolic-acid, glutaric acid, and
succinic acid present in the liquid samples are
determined by liquid-liquid partition chromato-
graphy, as described in one of the preceding
publications [l]. The HNO, concentration is where x,, = feed concentration of X,
determined in an amount of liquid pipetted directly Yo = feed concentration of Y = 0,
from the reactor. x, y = concentrations of X and Y in the
The HNO, concentration during the steady reactor, and
state has not been measured, but can be calculated z = residence time.
with sufficient accuracy from the initial concentra-
With t = 0 : x = X0
tion and the stoichiometric consumption of HNO,
at the degree of conversion measured. Y = Y,

4. Results According to PIRET [5], the concentration of the

substances can in this case be represented by
In Table 2 some examples are given of the
reaction conditions and the amounts of product
measured during the steady state. For complete
experimental data see Ref. [4]. Experiment 19
x=&+
(
x0- &).exp-[(krzl)J

(la)
is an example of the case where two reactors were
cascade connected; 19 A refers to the first reactor, if k = 0, so if no reaction takes place this equation
19 B to the second reactor. changes into the purgation equation
Figs. 3 and 4 show the results of measurements
made during the unsteady states. x = x0 + (X, - x0). exp( - t/z) (1’3

(x6-

(calculated from NA

o NA (measured)

0 05 1.0 1.5 2.0 2.5 x, 3.5 4.0 4.5 5.0

A tlr

FK+. 3. Change in concentration during starting-upof the reactor fled with nitric acid. Experiment 1)

476
 Adipic acid formation by oxidation of cyclohexanol and cyclohexauone with nitric acid

Anal- supply stopped

HNOi supply stopped
After reaction

; I
I
-An01/-anon&/‘)- supply HNOa- supply stopped ! I
i t-w Feed to

3QO-

280-

260-

240- 0 cl

220- O- measured CHNO__

2OQ-

1180-

o= measured CNA

I I I, , I , , , , ,
12 16 20 24 28 32 36 40 44 48 52
____F t in min
1

FIG. 4. change in concentration during starting-up according to a time schedule. (Experiment 2)

and are adjusted to the correct value. At t = 0, the

x,kt cyclohexanol feed is started. The measured change
y=m+(XO+YO-xa).exp- f - in the nitrolic acid concentration is shown as a
0 function of time in Fig. 3.
-
(x0 -&).exp-[(lctzl)‘] (2) In the above formulae k = k,,, x = concentra-
tion of the cyclohexanone (which is rapidly formed
from the anol), y = concentration of the oxidation
Consequently, in the steady state the following
equations hold : products, and so of nitrolic acid + Dione.
The change in the concentration of y has been
x0
W calculated by means of equation (2) and is re-
X=kz
presented by the upper line in Fig. 3. The sum of
and
the oxidation products can also be calculated from
k
Y=xo’kz+l the nitrolic acid concentration, in the following
way: 1 mole of HNOa is formed from 1 mole of
(a) Experiments performed without a special cyclohexanol, while 1 mole of HNOz is consumed
starting procedure. By way of example we take during formation of 1 mole of nitrolic acid. So
Experiment 1. This experiment (data about the the sum of NA and HNOz satisfies equation (lb);
reaction conditions and the steady state are given hence the HNOz concentration can also be cal-
in Table 2) was started as follows below. culated from the nitrolic acid concentration meas-
The reactor is Wed with nitric acid and the ured. As a result, the Dione/NA ratio at any
stationary HNO, feed current and the temperature moment is known, and the amount of Dione can

477
 W.J.VANASSELT
be calculated stepwise by trial and error. These
calculated values of the sum of the oxidation pro-
ducts are also stated in Fig. 3. They are in good
agreement with theory.
(b) Experiments performed with a special starting
procedure. By way of example we choose Experiment
2. This experiment was started in accordance with
a special time schedule; data about the steady
state can be found in Table 2.
After the reactor has been filled with nitric
acid, first cyclohexanol is supplied to it at the
stationary feed rate for a time equal to the required
residence time; nitric acid is not supplied in the
meanwhile.
At t = z, the anol supply is stopped and the
reaction is allowed to continue until the required
degree of conversion has been reached. At that
moment the supply of anol and HN03 is resumed.
If we assume that the reactor content does not
change during the anol supply, then, during the
first part of the reaction:
dCB1
-
Ao
= - - k,,[B]
dt V
or
LB]=++. Cl - exp(- k,N
* ox
where A, = mmoles of anone + an01 present in
the feed per set
= reactor volume (= 0.330 1.)
[yg] = concentration of the cyclohexanone
(mmol/l)
If the residence time is 10.7 min, it then follows
that at the moment when the anol/anone supply is
stopped
B = 307 mmoles/l.
During the subsequent period of after-reaction
(batch) :
CBII
- = ewC--k& - tJ1
CBlz
[B12 is calculated from the required degree of
conversion (50.2 per cent), and the period of the
after-reaction is then equal to tz - t, = 152 sec.
The total time needed for reaching stationary
conversion is then 10.7 + 2.5 = 13.2 min. The
concentration of HNOz + nitrolic acid follows
from the amount of cyclohexanol present in the
andD.W. VAN KREVELEN
feed. The Dione/NA-ratio, the nitrolic acid con-
centration and the HNO, concentration can be
calculated again by trial and error. This calculation
is continued also after 13.2 min, because, although
the degree of conversion remains constant, the
distribution of the products still changes. All these
lines are shown in Fig. 4. In this case, too, the
points found by analysis are in good agreement
with theory.
2. Steady states
(a) Principal reactions (A + B + C + F). The
degree of conversion during the steady state can
be calculated with the aid of equation [(3b). In
that case
Y = sum of the oxidation products
x0 = feed concentration of (anol + anone)
k = k,,,, to be read from Fig. 1.
The theoretical values of the sum of the oxidation
products are included in Table 2. If no vanadate
is present as a catalyst, the degree of conversion
can also be calculated from the sum of nitrolic
acid and adipic acid (known from the analysis).
The sum of the oxidation products is then equal to
(nitrolic acid + adipic acid) (1 + Dione/NA)
If vanadate is added, also adipic acid is formed from
Dione. Then first the amount of adipic acid formed
from nitrolic acid is calculated with the aid of km
after which the degree of conversion is found from
the sum of this amount of adipic acid and the
amount of nitrolic acid. These values, calculated
from the analyses, are also included in Table 2.
The amounts of adipic acid normally formed
being too small for verifying the value of kNA
measured in the batch reactions, some measure-
ments were performed in the second reactor (e.g.
experiment 19 B). The measured increase of the
amount of adipic acid in this reactor can also be
calculated with the formula
A adipic acid = (nitrolic acid). kNA.z
(b) Side-reactions
F
kvf
/
B-+D
\
kHL
G
478
 Adipic acid formation by oxidation of cyclohexanol and cyclohexanone with nitric acid
Vanadate accelerates the conversion of Dione to
adipic acid. The amount of adipic acid originating
from the Dione is equal to the amount found by
analysis less the amount formed from nitrolic acid.
The original amount of Dione can be calculated
from the measured nitrolic acid concentration
with the aid of the known Dione /NA ratio. By
the side of adipic acid, also glutaric acid and suc-
cinic acid are formed from Dione.
If the reaction is assumed to be first order, k, can
be calculated by using formula
1 formed. If vanadate is present the HNOl concen-
kv = F’
D, - (F’ + G)‘;
where F’ = total amount of adipic acid minus
(adipic acid from NA)
DO original amount of Dione (expressed
= In oxidations with 30% nitric acid considerable
as a monomer)
and
G = sum of glutaric acid and succinic
acid
In a similar way, kH (reaction velocity constant
of the decomposition of Dione to by-products)
can in many cases be calculated from the sum of
the amounts of glutaric acid and succinic acid. In
this calculation use must be made of the data given
in Ref. [l], from which it appears that if no van-
adate is added, 70 per cent of the amount of Dione
is converted (via an intermediate product) to
glutaric acid + succinic acid and 30 per cent to
lower decomposition products, whereas, if vana-
date is added, the intermediate product is com-
pletely converted to glutaric acid + succinic acid.
he calculation is as follows:
G x l/O.7 1 from the nitrolic acid decomposition. Probably,
without vanadate kH =
Do - G x l/0.7’;
G 1
with vanadate k, =
Do -(F’ + G)‘;
The data concerning kH and kV obtained from
the continuous experiments are given in Fig. 5.
D. DISCUWON OF THERESULTS
From a large number of experiments (partly
included in Table 2) it appears that, both during
the steady state and during the unsteady state,
479
there is good agreement between the theoretical
and measured degrees of conversion. This clearly
proves that the reaction diagram previously derived
is correct. From Table 2, experiment 10, it further-
more appears that when the HNO, concentration
approaches 0, no Dione but almost exclusively
nitrolic acid is formed.
In oxidations in which no catalyst is used the
amount of HNOz measured is approximately equal
to the difference between the amount of cyclo-
hexanol supplied and the amount of nitrolic acid
tration is higher, i.e. about as much as corres-
ponds to the amount of converted Dione. So,
during the reaction of Dione under the influence of
vanadate also nitrous acid is released.
deviations from the theoretical degree of conver-
sion are found below 30°C (e.g. Experiments 11
and 12). In these cases the sum of HNOz and nitro-
lit acid is also much smaller than the amount of
anol supplied. Here, some influence of the rate of
the conversion of anol to anone + HNOz (rI) is
observed for the fist time, since the above pheno-
menon can only be explained by the fact that not
all of the anol has been converted. At temperatures
over 30°C this effect is not noted. Neither has it
been observed in experiments using nitric acid
concentrations exceeding 35 per cent by weight,
not even at low temperatures ; hence it may safely be
taken that (rl) is highly dependant on the nitric
acid concentration.
Here, as in the batch experiments [2], the amount
of adipic acid found at a nitric acid concentration
of 30 per cent is much larger than would follow
this will also be due to the influence of disturbing
by-products. In calculating the degree of conver-
sion we started again from the calculated amount of
adipic acid.
The spread of the values of kv and kH, calculated
from the results of the continuous experiments,
is rather large, as is to be expected in view of the
analytical errors. As a rule, the amounts of glutaric
acid and succinic acid are small, so that the
relative error is large.
The few data known from the batch experiments
approximately agree with the values found from
 W. J.VANASSELT and-D. W. VANKRE~ELEN

10’ 20 30 40 io
I I I, /
352 344 336 32% 320 312 352 344 336 320 3x) 312
$- lo=,- &.) -batch experiments

FIG. 5. kv and kH values calculated from continuous experiments.

the continuous experiments. From Fig. 5, the follow-
ing conclusions can be drawn:
1. k, is proportional to the vanadate concentration.
2. kv is highly dependent on the nitric acid con-
centration, i.e. approximately proportional to
the HNOJ vapour pressure.
3. At a nitric acid concentration of 40 per cent the
ratio between k, and kH does not depend on the
temperature.
As in the batch experiments, copper does not
affect the reaction at low temperatures. The
influence of copper becomes noticeable only above
40°C; at these temperatures the amounts of glutaric
acid and succinic acid formed are larger than
corresponds to the decomposition of Dione,
owing, for instance, to side-reactions via non-
identified intermediary products. Cu partly sup-
presses these reactions . At a nitric acid concentra-
tion of 40 per cent, for instance, the increase in
yield upon addition of Cu is approximately O-5
per cent at 45°C and approximately 2.5 per cent
at 60°C. Vanadate improves the yield as long as
Dione is formed.
E. REACTOR STABILITY
As demonstrated, the conversion of anol to
anone is accompanied with the formation of an
equimolecular amount of HN02. Part of this
amount is consumed again in the formation of
nitrolic acid. So, during oxidation of pure hexanol
the amount of HNOz present is automatically
kept large enough to permit formation of nitrolic
acid.
However, it may be conceived that during
oxidation of a mixture of anol and anone the
amount of nitrolic acid formed under certain
conditions will exceed the amount of cyclohexanol
supplied. In that case all of the HNOz is consumed,
and, as nitrous acid is absolutely necessary for
making the oxidation proceed and also for initiat-
ing the conversion of anol, the reaction dies out.
This becomes evident when comparing experiment
7 with experiment 8, (Table 2).
The production (or supply) of HNOz can be
controlled by varying the anol/anone ratio in the
feed, or by supplying an additional amount of
HNO*. The consumption of HNOz can be inde-
pendently controlled by varying the reaction condi-
tions, such as temperature, residence time, and
nitric acid concentration. The amount of HNO,
produced under steady state conditions (oxidation
of cyclohexanol) must be equal to the amount
discharged (nitrolic acid + free HNO*).
During the steady state the following equation
holds for the continuous reactor :
WA1
-= - 1 ADI
z 1 + (Dione/NA)‘z
1
.k,,.{A, - NA(l + z))
= 1 + (Dione/NA)
Aok,,r 1
of DA] = -. (6)
I + k,,,z 1 + o*69(cmo2/Pmo3)2’3

480
 Adipic acid formation oxidation of cyclohexanol and cyclohexanone with nitric acid

.I nitrolic mid (20 OC)

/
0.1 . /
/
/
/
0 0.1 0.2 0.3 0.4
- HNO? cow. ~gmolll 1

FIG. 6. Graphical representation of equation (6) and (7) (40% HN03, T = 600 set and Ao = 0,545 gmol/l.)

where NA = nitrolic acid concentration 1. Lines III and IV intersect in one point, which
A, = feed concentration of anone (possi- at 15°C for instance, is represented by point C.
bly, quickly formed from anal) This is a stable reaction point; after a disturbance
The nitrous acid balance in that case is of the HNO, concentration, the reaction returns to
this point. This always happens when the degree
1 of conversion is lower than a.
+
1.1 + 069(CnNoJ~uNo~)~‘~ 2. If the degree of conversion only slightly
< J
HNOa consumed in the reaction exceeds a, there may be two points of intersection,
as are represented by the points A and B in Fig. 6.
+ CHNOl
= C&l (7)
Point A is not stable however. A slight disturbance
in the HNOa produced in in the HNOz concentration will either extinguish
discharged the primary
liquid oxidation the reaction (to the left of point A the consumption
of HNO, exceeds a A,) or cause it to move to
where CI = anol fraction in the feed which is point B, which is a stable reaction point.
converted to anone (normally equal 3. If the degree of conversion is much higher than
to the whole anol fraction) ; a, there is no point of intersection and, conse-
If HNOz = 0, also k,, = 0 and a = 0, because quently, no reaction takes place (In Fig. 6, at
HNOz initiates both the conversion of anol and temperatures above 25°C with a = 0.50). Under
that of anone. these conditions the oxidation cannot be realized
These formulae have been worked out in detail in a continuous reactor.
for As the temperature is raised from 20 to 25°C
40% HN03, r = 600 set and A, = 0.545 gmol/l. (Fig. 6), the points A and B approach each other
and, finally, coincide. Such a steady state has been
In Fig. 6 equation (6) is represented as a function observed in experiment 10 (Table 2), where an
of the HNOz concentration by line I, the left-hand 0.2”C rise in temperature sufficed to extinguish
member of equation (7) by the lines III (at various the reaction. The HNOz concentration could not
temperatures) and the right-hand member of be measured in this experiment, as at the very
equation (7) for instance by line IV, with IX= 050. moment of sampling the reaction died out owing to
Three cases are distinguished here: a slight disturbance.

481
 W.J. VAN~SELT and D. W. VAN KREVELEN

After the analogy of an autothermic reaction, In Fig. 8 the values of z from equation (7) are
in which, during the steady state, the heat produc- represented as a function of the nitrous acid
tion (reaction heat) equals the heat consumption concentration. From this figure it appears that the
(sensible heat of the reaction mixture and heat maximum residence time at which reaction is still
emission), we might speak here of an “auto- possible now amounts to about 720 sec.
concentrative” reaction. In similarity to auto-
thermic reactions, which usually do not start below 17 (set 1
a given ignition temperature, autoconcentrative
reactions require a given ignition concentration
600- 1
below which the reaction dies away.
Besides u, the temperature and the acid con- 600.
centration, some other factors such as the feed
concentration of anol + anone (A,) and the resi- 400.
dence time (z) also affect the stability.

Infuence of A, 200.

We shall consider again the reaction conditions

described above, so: 40 % HN03, r = 600 set 0.1 a2
and a temperature of 20°C. According to equation - HNOP ConC.(gmOl/~)
(7), A, may be represented as a function of the FIG. 8. Influence of residence time on stability.
HNOz concentration. At various values of o! 40% I-IN03 2O”C, co = o-545, 01= O-50
lines (III) may result which, if
If the stability limits found here are compared
to the experiments-some of which are included
in Table 2-it appears that reaction is still possible
may not intersect, so that a steady state cannot as a rule at a temperature slightly above the
establish. In Fig. 7 this required minimum A0 value theoretical temperature. Thus far, however, it has
is represented as a function of 01. been assumed in the calculation that HNO,
originates exclusively from the reaction of cyclo-
-I \ hexanol. However, HNOz may also form in the
$2
formation of by-products, while the conversion of
E
07 I \ Dione under the influence of vanadate also yields

-I \
2
Tz
HNO,. It is obvious that these effects add to the
stability of the reactor. An opposite effect is
produced if HNO, escapes from the solution.
The influence on the stability is small, however,
because the HNOz concentration in the critical
region is small, as a result of which little HNO,-gas
will disappear. Then, the total amount of escaping
gas approximately equals the amount of NzO
originating from the nitrolic acid conversion.
FIG. 7. Required minimum AIJ value represented as a In view of the above considerations on the
function of the anol fraction. 40 % HNOs, 2O”C, 7 = 600 sec. stability of the reactor it is obvious that, at tem-
peratures of, say, over 6O”C, the reaction can only
Inflitence of the residence time (7) be carried out with cyclohexanol.
This influence has been worked out further for In the industrial production of adipic acid,
the above-mentioned reaction conditions with however, the temperature of the primary reactor
CL= 050 and A, = 0.545 gmol/l. varies between 60 and 100°C and a mixture of anol

482
 Adipic acid formation oxidation of cyclohexanol and cyclohexanone with nitric acid

and anone, and even anone alone, instead of anol, acid. LINDSAY’S report of a batch oxidation of
may be used [6]. Theoretically, reaction would not anol/anone, in which at a temperature of 70-80X!
be possible in the latter two cases, were it not for the conversion reaches completion only after
the fact that owing to the high temperature, 40 minutes, can only be understood in the light of
nitrous gases are formed from the nitric acid and, this assumption.
in addition, HNOz is released in side reactions.
This brings LINDSAY [6] to the statement that the
NOTATION
reaction has to be carried out above 70°C and that
the frequently occurring retardations can be r
Reaction rate
k
first-order reaction rate constant I/=
partly avoided by addition of metallic copper as a
t Time
catalyst (this results in the continuous formation of 2’ Temoerature “K
a small amount of initiator). Consequently, the R Gas constant
continuous reactor is not stable in these cases, p Partial Pressure mmHg
C Concentration gmolll.
and the oxidation should be considered as a NA Nitrolic acid
reaction which repeatedly dies out and locally 7 Mean residence time
ignites again. The decomposition rate will then not V volume
be determined by k,,, but by the rate at which Fi Cont. of A, B
HNOz or nitrous gases can form from the nitric OLMol fraction cyclohexanol

[l] VAN ASSELT, W. J. and VAN KREVELEN,D. W., Rec. Trau. Chim. 1963 82 51.
121 VAN kWLT. W. J. and VAN KRIXELIN. D. W.. Rec. Trav. Chim. 1963 82 438.
[3j VAN ASSELT; W. .I. and VAN KRJWELE~, D. W, Rec. Trav. Chim. 1963 82 429.
[4] VAN ASSELT, W. J., Thesis, Delft, 1960.
[5] PIRET,E. L., Industr. Engng. Chem. 1950 42 817.
[6] LINDSAY, A. F., Chem. Engng. Sci. 1951 1 Suppl. 79.

R&n&--La cinetique de l’oxydation, determinee preablement en discontinu, a et& confirmed par des
experiences faites a l’aide d’un reacteur continu a, melange parfait.
Les mesures ont foumi des informations supplementaims concernant la vi&se de formation des
sous - produits et l’influence des catalyseurs NH4VOs et Cu(NOs)z.
La stabilim du reacteur depend de la concentration de l’acide nitreux, forme initialement lors de la
conversion du cyclohexanol et consomme en partie pendant la reaction. On peut controler separement
la production et la consommation de HNOa. Comme cet HNOa est indispensable ii l’oxydation on
peut c&r des conditions telles que la reaction s’eteint. Par analogie avec l’appellation “reacteur auto-
therme” on pourrait intituler le reacteur en question de “autoconcentratif “. Dans un tel n5acteur
deux &tats stationnaires stables peuvent se presenter:
1) concentration HNOZ = 0, conversion = 0 et 2) la conversion et la concentration en HNOa ont
une valeur fixe. Entre ces deux &tats on a generalement a faire a un &at instable, caracterid par une
concentration en HNOa qu’on pourrait intituler de “concentration d’ignition”.

Zusammenfasstmg-Die zuvor in Chargenversuchen bestimmte Reaktionskinetik der Oxydation

wurde in kontinuierlich durchgeftihrten Versuchen in einem Rtihrkessel besmtigt. Die Messungen
eraaben einige zuslitzliche Resultate iiber die Bildungsgeschwindigkeit der Nebenprodukte und den
Emfluss der -&mnoniumvanadat- und Kupfemitrat-Katalysatoren.
Die Stabilitat des Reaktors hiingt stark von der Konzentration des NOa ab, das wihrend der
Umsetzung des Cyclohexanols gebildet und teilweise im Iaufe der Reaktion verbraucht wird. Bildung
und Verbrauch von I-IN02 kiinnen unabhanaia davon kontrolliert werden und es konnen, da HNOz
fur die Oxydation unbedingt notwendig is~,Bedingungen geschaffen werden, unter welchen die
Reaktion im kontinuierlichen Reaktor zum Stillstand kommt. In Analogie zum “autothermen”
Reaktor kann der verwendete Reaktor “autokonzentrativ” genannt werden, wobei zwei stationare
Zust;inde moglich sind:
1) HNOa-Konzentration = 0; Umsatz = 0.
2) HNOa-Konzentration und Umsatz weisen einen festen Wert auf.
Zwischen diesen beiden Betriebsbedingungen liegt em nicht-stationares Arbeitsgebiet, charak-
terisiert durch die sogenannte “Ztindungskonzentration” der HNOz.

483