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1!)5 ~.
MARS
and D. W.
VAN KREVELEN
CONFERENCE
ON
OXIDATION
PROCESSES
Unter Umstanden lasst sich dicse Formcl in eine G1ciclmng umwnndcln, in der auch die
Litcraturunterlagen tiber die Oxydatlon von SehweCeldioxyd mittels Vllnlldiumo),,-yd-Klltlllysa.
toren, gut zum Ausdruck gelangen.
An Hand der Kinetik ist es mogllch die optimale Temperaturvertcilung in eincm FestbcttRcnktor, der zur Oxydation von Schwefcldioxyd angcwandt wird, zu ermittcln und das VcrhaItnis
zwischen den in eincm mehrstullgcn Reaktor angewandten Katlllysatormengen zu bercchren,
Die Ergebnisse dieser Bcrechnungen sind mit den Erfahrungen nus der Praxis vcrglichcn norden.
INTRODUCTION
In various manufacturing processes vanadium
catalysts play an important part. In particular,
the oxidation of sulphur dioxide with air (the
.. contact process "), the oxidation of naphthalene
to phthalic anhydride and, to a less degree, the
oxidation of benzene to maleic anhydride over
this type of catalyst arc widely applied in technical processes. In an analogous manner toluene
can be oxidised to benzaldehyde and benzoic acid,
anthracene to anthraquinone, methyl alcohol to
formaldehyde, whereas from aliphatic hydrocarbons a large number of oxidation products
(aldehydes, ketones and acids) can be derived.
Precisely those reactions which arc of great
importance in chemical industry arc strongly
exothermic. This has been a difficulty both for
the technical realization and for the studying of
the kinetics of these reactions.
Because of the fact that oxidation by means
of vanadium oxide catalysts finds much application in the authors' organisation, it was considered
important to investigate the technological bases
of these processes. For this investigation the
catalytic oxidation of aromatic hydrocarbons was
chosen as the starting point, as this oxidation
proceeds as an irreversible reaction, so that there
is no need to take into account the influence of
the equilibrium position. The conclusions, however, have a much wider scope and in principle
apply also to reversible reactions. By way of
example we shall consider the contact process for
the production of sulphuric acid. With the aid
of the reaction kinetics further information on the
design and performance of the apparatus will be
derived.
P.
MARS
and D. W.
VAN KREVELEN :
Apparatus
A diagram of the apparatus used is given in
Fig. 1. In a .. Pyrex" tube with an internal
diameter of 43 mm, the catalyst powder (par-
Voporizer
Converter
Condenser
Absorption trcm
gas meter
C ON F E n ENe EON
figure 2
O'x I D A T ION
4.01r---------;--r--.-----,---,~___,
IO:S 'llcl/rnlft 0 col
t
301+---,----r::+-1~-1--+-_+-___Ir--
14
12
16
120
10' "",'/m,n
0 col
100
l-
noplltholon. 33~
eo
60
vet -: .
/
4a
2a
/ /1
\ bonnno 317
I I
I
I
anthracene Z70 C
I,
1--'
Pe2
200
400
600
~I"nITIHg
eoo
P no C E SSE S
P.
MARS
and D. 'V.
VAN KREVELEN :
In the bed
I , In em
14
12
a ir
bed
to
lattice two kinds of oxygen ions may be distinguished. The greater part of the oxygen is
present ill about the same plane as the vanadium
ions. Two-fifths of the ions, h-owever, are arranged
in planes parallel to and alternating with the
first [9] (sec Fig. 5). We suppose the latter
"
~\
\
0025
aor
\ -,
0,
,'\
'.
0030
-,
bed
\
<, r-...,
0035
P naphthalene mm Hg
0040
0025
0030
0035
0040
CONFERENCE
O.N
OXIDATION
fJ k l
t
4
.>
Pn- 0 = k2 po~' (1 - 0)
(4)
/.
.:
/
I
(8)
109 Po
p
(2)
1 .
V.
Pon . (1 - 0)
nH=~nOI
k'2
noI =
PROCESSES
V/
./
/.;::
,
log
POz
POz-P(Po-P)
109
01
02
03
~
P
04
05
rate of the oxidation of the aromatic compound .For the degree of occupation by the oxygen it
may be expressed in the following formula:
follows that:
(1)
0=
k 2 .Po~
fJ .kl Pn + k 2 Po"
(5)
tt n
=- - - - - - -
_1_+
k l Pn
fJ
k2
Po~
(6)
P.
l\lARS
and D. W.
VAN KREVELEN:
-!. = .!:.. . In
V6
+.!.. In
(Pn)o
(Pn) final
k2
(Po,)o
(PO.)final
(7)
12
f3 (PR.
(Po)o -
II
1*-
1.3
- PRllnal)
paz
Paz B [Pbo-Pb!
Pb0
109_
Pb
10
09
377 C
Paz
,g PO z ' ,8 [PAo'PAl
PAo
-:
/.
"",*
II
V-
/"
1/
-:
-:
0.6
05
o. 4
O.3
Vtemp 270-C
~/
10
IZ
&
o.I~-
PA o
Vs log llA
14
p .*
nO
O.2
*;-
V< -
/-/ *
0.7
./
/337 C
08
109PA"
ZO
100
Vs
400
300
200
lo,/ho
Pb
500
~
k2
--l
r-,
"-
e.
...0 <,
<,
..... +.,0 3
1.6
47
1.7
<,
1.8
1.9
CONFERENCE
ON
OXIDATION
PROCESSER
2.
30
10
(P0 2 )O'
lo~ ~
02 e
.10
101o~ PRo
25 f-
I;!'
PRe
20
on porter catalyst
15
~
~oq
10
5
0
'l
'@
./
10
Thus it may be understood why the most different substances arc oxidized on V20 S in the same
temperature range (MAXTED [4]) and further, how
CALDERDANK [5] could find the initial rate of
oxidation of naphthalene to be proportional to
(Po )0'96. For, at constant k 1 and PR' formula (6)
can: for a wide range of Po ,, very well be approximated with the following formula:
<
Il
S
15
PRo
10Iog _ _
PRe
25
20
30
where m
q;if
',!>r:J
'j
Pso,
101
og
1.
48.
2
pressures in atm)
Pso, . Po,
'D880
i' -
D'34
(8)
P.
l\IARS
and D. W.
VAN KREVELEN :
630r--
--,
600
-r>.
570
E
~
540
510
480
450
420
("51 converl~r
----
->
secondconverter
He'Qhl in the bed
-----.i
k1
+ Cat -
O~
SOa
+ Cat
and
Figure 12 Oxidat ion of S02 on pure V2 Os
Kriehevskaycl (Iii. II)
300
PSO
T l f e.veat.
t
200
0
100
g'
o
/
0-
0/
02
PS0
- - a2i m
Vz
vPOa
0.4
0.6
I I
--
CONFERENCE
Cat
k2
+02~
ON
OXIDATION
PROCESSES
where
Cat-O
Teq
or:
( )
SOs
+ Cat
!. . {po.)n =
V. (Pso.)o
Pso.
(10)
K* Pso +Pso
Since for the gross reaction process the ratedetermining reaction is the re-oxidation of the
catalyst:
(11)
oteq
ot'
ot
(I8a)
C1
eq
{In _1__
1 - a.'
ot'}
(14)
Table 1.
Sulphur diOJ:ick oxidation (F. W. KilsTER [12]).
* Po, Pso,
nso = 2 k 2 K . K*
(12)
Pso, + Pso.
Now K* is small (as appears from the strong
retardation effected by SOs) so that the following
equation will approximately apply if the degrees
of conversion arc not too low:
Po. Pso.
Pso
Po, (
pso.)
nso = k Pso -
Pso,
Teq
ot CXeq
n
kl1
rOt I
=----,-
o =-=
ot
oteq
'liso = k
C1eq
we find:
. PO.
Pso (1 -0)
K* = -....:.:...---Pso .0
k2 .p~ . (1 - 0)
PSo.
where oteq is the degree of conversion at equilibrium, and ot' = degree of conversion as compared
no, =
nso. =
pso. ) equilibrium
= ( --
Time
sec.
Conversion
ll'O
21'4
265
377
38'0
52'1
576
72'{)
771
83'7
841
ar-e
k'(1)
2'82
341
335
330
325
312
n. NEUMANN and his collaborators [13] investigated the contact sulphuric acid process, especially
with the purpose to identify the intermediate
products formed on the catalyst. For a check of a
kinetic formula NEUMANN'S investigation into the
(18)
50
P. MARS and D. W. VAN KREVELEN : Oxidations carried out by means of vanadium oxide catalysts
k'
average
825
73'0
590
0095
0-120
0'107
0107
150
800
500
750
920
845
73'5
57'0
0172
0220
0'212
0'147
0188
150
300
500
750
96-5
905
820
720
0'291
0324
0-880
0'800
0315
450
150
800
500
750
970
92'0
840
760
0333
0370
0392
0'370
0'366
465
150
300
500
750
97'0
925
850
785
0400
0398
0'363
0'392
0889
475
150
300
0412
0'417
0412
0430
0'419
750
965
925
855
790
150
300
500
750
95'0
910
855
810
0418
0'410
0'428
0495
043(1
300
90'0
850
805
0483
0500
0-517
0'500
500
750
550
300
500
750
870
840
795
(0'444)
0-527
0-545
0535
See remark
In
Temp.
C.
Gas
velocity
Conversion
825
150
300
500
875
425
500
500
525
(1)
Pso.
dt
=k.
Po (Pso.)
08
.PSO
Table 1.
51
CONFERENCE
ON
OXIDATION
PROCESSES
10
,-
In-!-" ...In
-I
on pure V20S
Je. L Knchevskoyo (ht. II)
:
....
80
60
100
20
,-0<
In-'-
\6
I,
/
/
/
410'~~00~
14
/
/
JO
./ /
/i
/
1
.
I
/ '/ /
V
VI
o1/
4
390~/
. .
./
/
-
PO,' 1
( PS02)0
-CI(+ln-L-
,-"
10
V
J
15
(Paz)l
,-
_.
-cw.+ln~
40
20
20
25
/'/
18
Figure /3
1-
30
35
40
52
120
140
(Pso.)o
-O(+ln ..L
1-
160
180
200
reaction rate
P.
MARS
and D. W.
VAN KREVELEN :
THE 1IIANU}'ACTURE OF
paz
II
---
l---.
Pso 3
PSO z
1!2rp
am
SOa
X'" JD.rIe
(pso.)o
(Po.)'"
IX IXeq
Ju;
C~~')
k*
_
2
J__'_.- = J-;:_ t
(Po )"
(Pso.)o
with monlle-eooling
Clteq
IXeq
JIi"
tanh?
(I5)
(I6)
iXeq
op',ml,lm~
I\.
artua,)
<,
l><~
i\
"\
I~
1
01
I\'
1.
2.
3.
4.
/0
az
-'"
0.3
04
0-5
06
0 .7
08
09
10
58
The
The
The
The
CONFERENCE
ON
OXIDATION
PROCESSES
Table 3.
Ad 1.
where
k**
=_ . Po.
rJ. rJ.eq
570
2000
9140
Effectivity of
catalyst %
k*y(po.)n. (Pso.)o
45
164
400
20
atm. hr-l
P.
MARS
and D. W.
VAN KREVELEN :
A.d 2.
Under Ad 1 we estimated the optimum temperature distribution. Even, if for technical reasons or
for reason s of heat economy, the optimum temperature curve is not followed in most of the practical
applications, it remains a useful guide for the
temperature level to be applied in the second
converter, while, moreover, it may be used for
checking the performance of the two converters.
For, from the optimum temperature distribution
we can calculate the proportion between the
contact times to be applied for attaining a given
degree of conversion. Then we know the ratio
between the amounts of catalyst to be used and
we are able to check if the reaction conditions in
.the two converters are well adapted to each other.
A calculation showed that under optimum
conditions the ratio of the amounts of catalyst
necessary to obtain a conversion of from 0 to
81 % [converter 1) and a conversion of from 81 %
to 97% (converter 2) should be 23: 77. The
actual ratio between the amounts of catalyst in
the two converters is 27: 73. Of course, the
significance of this agreement should not be
overestimated. It may be concluded, howcver,that t he distribution of the catalyst is rather
impervious to the temperature distribution.
Ad.8.
Ad. 4.
VP8, (Pso)o
which reaches its maximum value at certain O2
and 502 percentages. Table 4 shows the corresponding values of these percentages, besides the
corresponding values of
1t
=1
and
1t
= i.
Table 4.
Influence of the 02 and 802 concentrations on the Teaction
rate.
%2
5'2
12
6 6
7'8
0'0
10'6
11
10
IH)
8
7
13'0
70
85
8'8
e-o
o-s
{j'1
8'8
5 2
5'3
5'3
5'2
5 1
49
47
CONFERENCE
ON
OXIDATION
1.
2.
3.
PROC ESSES
Tube converters;
Tray converters;
Combinations of 1 and 2.
-~
, , ,,
50 2
Figure 19a
(1938)
. .2 -
cold gases
air
air
50 3
heal exchanger
i:=1 -
Figure 19b
...,
50 3
Bachelard converter
(1939)
9, Fiv 48')
50 2
oir - -
50 3 - 1 - - - - - '
Agure 18 C Tentelew-converter
co 1900
56
P. MAns and D. W. VAN KnEIELEN : Oxidations carried out by means of vanadium oxide catalysts
57
= reaction rate
= partial pressure
rp = pore radius
.
. I I prevai'1'mg Po
r eq = Pso,
- - a t equiilib
I rium
Wit
11
Pso,
t = time of reaction
Xm
K
K*
R
Vent =
Va
IX
catalyst volume
= space velocity
a.' =~
IXeq
"eq
"0
".
REFERENCES
CONFEnENCE
ON
OXIDATION
PROCESSES
DISCUSSION
Prof. Joe M. Smith: (Purdue University, Lafayette,
lndiana)
The authors arc to be commended for attempting to
bring some unification into kinetic phenomena." Their
scheme of choosing a particular class of reaction and
specific catalyst appears to be a fruitful way to approach
this problem.
In connection with the paper proper, would the authors
care to comment on the following three points :
1 . It was interesting to note that the measured partial
pressure profiles in the fluidized bed were not flat. In
contrast the temperature is generally considered to he
uniform in such an apparatus and the authors utilized this
simplification in interpreting their kinetic data. This
situation would suggest that the transport mechanisms
for heat and mass are not the same, or at least individual
me chanisms do not h ave thesame importance "inheat and
mass transfer. 1<; this due presumably, to the ability of
the solid particles to carry energy but not significant
quantities of mass from the surrounding fluid?
2. On the basis of the measured partial pressure profiles, the authors con sidered that the Iluidized bed did not
behave as a stirred tank reactor, but instead integrated the
proposed rate equation. 'fhis procedure assumes that
there is no mixing in tile direction of flow, which is somewhat in contradiction to experimental results of GILLILAND
and DANCKWERTS. 'Vould it be possible that some longitudinal mixing did occur in the fluidized bed and that a
precise description of the reactor would be som ewhere in
between the stirred tank type, where mixing is complete,
and the narrow tubular form where mixing is negligible?
Perllaps tile shnpc of the partial pre ssure profiles led the
authors to conclude that the no-mixing assumption wus
the closest to the actual process.
3. One of the discouraging features of heterogeneous
catalysis is that frequently several different mechanisms
can be found which describe kinetic data equally well. A
knowledge of the intermediate products is helpful in such
circumstances, although their identlflcution is not always
possible. In this connection a mechanism based upon the
three steps, adsorption of oxygen on reduced catalyst
surface, reaction between oxidized catalyst and hydrocarbon in the gas phase, and desorption of the oxidiation
product, leads to a kinetic equation similar to the one
proposed . By assuming different individual steps to be
controlling and the others to be close to equilibrium conditions, it is possible for the resultant rate equation to
indicate, or not indicate, a maximum rate at certain
partial pressures of hydrocarbon and oxygen. 'Vould the
authors like to comment on other mechanisms they may
have considered?
The Author:
In contrast with the oxidation in the liquid phase
mentioned by you, catalytic oxidation reactions in the gas
phase do not provide certainty that the reaction proceeds
via radicals.
The Author:
For our investigations wc used three catalysts :
(a) The" I.G. Farben catalyst" for thc preparation
of phthalic anhydride, which was prepared by impregnation oC potassium aulphatc-i-contnlnlng silica gel with
a vanadyl sulphate solution. (Fiat Final Report No. 649).
(b) The .. Porter catalyst," prepared by drenching
corundum in a solution of vanadium, molybdenum and
phosphorus oxides in hydrochloric acid. (Am. pat. spec.
no. 2,204,130).
(c) A trade-mark catalyst for the oxidation of sulphur
dioxide containing 77% V20jl and 10'0% K20 (carrier:
kieselguhr).
The Author:
1. Indeed I In our opinion the transport mechanisms
of heat and mnss arc not the same in the fluidized bed,
'Vhen dealing with ma ss transfer to the catalyst surface
in a fluidized bed no viewpoints differing from those held
in connection with fixed bed transfer present themselves.
In a fluidized b ed, however, the catalyst particles serve
us heat accumulators in the removal of heat; these
particles nrc cooled as they circulate along the reactor wall.
58
P.
MARS
and D. 'V.
VAN KREVLEN :
The Author :
From measurements made by means of a thermocouple
enclosed in a glass tube, wnich was inserted in the bed at
different heights, it appeared that the temperature is
practically the same in all parts of the bed.
The temperature of the particles themselves is very
dilflcult to measure. Calculation of the temperature
dirrerenee between the catalyst particles and the surrounding gas by the generally known heat transfer relations
showed this difference to be always less than 1C.
The Author:
From our measurements we concluded that the situation
on the surface of a .. reduced catalyst" is not parttcularly
favourable for obtaining high yields of phthalic nnhydrlde :
the highest yields were obtained under conditions promoting strong oxidation of the catalyst. 'Vllether radical
reactions play a part in this connection is not known to
us.
50