THE PREDICTION OF THE PERFORMANCE OF

PACKED-BED CATALYTIC REACTORS IN THE

AIR-OXIDATION OF o-XYLENE

P H CALDERBANK, K CHANDRASEKHARAN and C FUMAGALLIt

Unlverslty of Edmburgh, Kmgs Bulldmgs, Mayfield Road, Edinburgh EH9 3JL, Scotland

(Recewed 2 December 196)

Absfract-The kmetlcs of the catalytic au-oxldatlon of o-xylene to phthahc anhydrIde over various commercial
V,O, and T10rV205 catalysts are extended and a model derived which correctly predicts the temperature and
yield profiles m a quasi-Isothermal fixed-bed reactor of commercial dlmenslons The model predicts the relative
freedom from thermal run-away of commercial fixed-bed reactors and IS used to demonstrate the possrtuhtles of
operation at elevated Xylene concentrations
In what follows, XH, TA, PI and PA refer to o-xylene o-toluakdehyde, phthahde and phthabc anhydrlde
respechvely, sometimes abbreviated to A, B, C and D

INTRODUCTION measuring the disappearance rates of xylene and m-

In a previous paper [l], one of us has reported the
kmetlcs of the arr-oxldatlon of o-xylene to phthahc an-
hydride over a catalyst compnsmg a layer of pure V,Os
on a Carborundum support A spmmng catalyst-basket
reactor (S C B R) was used In a subsequent paper[2]
Perelra and Calderbank measured the mass-transfer h-
mltatlons of this type of reactor and as a consequence
the measurement procedure was altered The new data
lead to some modlficatlon of the earlier high temperature
rate equations
The reaction scheme at low reactant concentrations
consists of the followmg first-order reactlons
and has previously been described over the temperature
range (370-55O)C [ 11
The energy of activation for xylene disappearance falls
from 26 kcal/mol at (3704lO)C to a lower value (now
found to be 13 kcal/mol) above 440C and m which the
first order behavlour obtains only at low hydrocarbon
concentrations movmg to fractlonal order as the latter LS
increased
These results have now been found to apply to a
vmety of other commercml catalysts and to some pre-
pared m this laboratory from T102 and V20, as shown in
Table 1 below, which should be read m relationship to Fig
1 which gives the first-order rate constants for hydro-
carbon disappearance and includes for comparison pu-
blished data on naphthalene oxldatlon from a source
recently referred to [l I]
ExPERmmNTAL
The SC B R was previously found suitable
tMontedlson, hillan
termedlates but not of phthahc anhydride which 1s ca-
talytically oxldlsed by air over most metallic surfaces In
order to determine C, selectrvltles without influence of
metals, a catalytic-tube-wall reactor (C T W R ) was
used this comprised a tltanmm tube of 3/8 m dla and 2 ft
m length inserted mto a brass block thermostat The
tube was internally coated with catalyst (TIOrV,Os) by
pouring an aqueous slurry of it into the tube followed by
a fairly loose-fitting rod to remove the surplus, whereaf-
ter the deposit was dried and then smtered for 12 hr at
(420-450) to give a layer about 1OOpm thick This reac-
tor was also used to measure the disappearance rates of
xylene when allowance was made for the mass transfer
rate using the methods descrtbed by Vlllermeaux[3]
The S C B R was again used to determine precise
kinetics at high temperatures about only s1x catalyst
pellets were used to secure a high mass transfer rate In
add&on, some measurements were made with T10TV205
catalyst deposited, as described for the C T W R , on the
periphery of a rotatmg ceramtc disc m the S C 3 R
Product analysis was by on-line G L C with IR analy-
sis of CO and CO* A programmer was used to alter the
reactant flow rate or reactor temperature once every
hour over a preset range for a 24 hr period, three samples
were also taken by a motorlsed gas sample-valve at five
minute intervals 314 hr after a change Temperatures and
analytical results were stored on a data-logger for sub-
sequent computer processing
Figure 1 shows that rates of xylene removal per umt
surface area of catalyst are remarkably independent of
the catalyst composltlon, even though the V205 content
varies conslderably
CATALYm PROPER=
There IS a conslderable recent patent literature relatmg
to catalysts for xylene oxidation important examples are
hsted under [4] These generally relate to TIO,V,O, The
mixed-oxides are applied as an aqueous slurry to inert
substrates and after drying smtered to a thm layer (50-
for 100)~ for several hours at temperatures Just below
450C Blanchard[5] has shown that the C, selectivity
with T102-V20T oxides shows a maxlmum at about 5%

1435
1436 P H CALDERBANKet a[

12 14 16

103/T, OK-1
Rg 1 Fust order rate constants for xylene oxrdation with air over various catalysts (Table 1)

Table 1

Symbols Experlmental
Hydrocarbon to Fig 1 reactor Catalyst Preparation

CTWR and
A This laboratory
Spmnmg Disc

T102
o-Xylene D SCBR (SO, m feed)
i V&5
\ GLO,
B SCBR Slmdar to above Commercial
Fixed bed Slmdar to above Ref [lo]
Commercial
c SCBR V,O, on Carborundum
Ref [I]
Naphthalene Flxed bed V,O, Ref [It]

VZOscatalysts (composition and preparation) referred to m Fig 1

V205 by weight It has been found m this work that it 1s
important m achieving a high selectlvlty, to finely grind
the mlxed-oxide slurry before apphcatlon to the sub-
strate m order to reduce the accesslblltty to gas of the
latter and for the same reason to apply a sufficient
thickness of the catalyst, even though the substrate by
itself may be mert catalytically Several patents[4] claim
advantage m applying a glaze to ceramic substrates, m
this it 1s important to reduce the alkali metal Ion content
of the glaze as far as possible by use of borex since alkali
metals largely inhibit the further oxidation of TA A
small P205 content significantly assists m mamtaming a
high C, selectivity at high conversion by rnhlbltlon of PA
over-oxldatlon
T10rVz05 catalysts deactivate almost comptetely and
lrreverslbly when heated above about 500C
KINETICS
The present measurements confirm those previously
reported for a V,O, catalyst supported on
Carborundum [ 11 except for the revised activation energy
for xylene disappearance at high temperature (>440C)
previously referred to The results are seen to be
generally applicable to commercial catalysts despite varl-
atlons m the ratio of total to superficial surface area for
the various catalysts, the rate constants being reported
for the superficial areas only In summary the principal
features are as follows
(1) Xylene disappears at low concentrations by first-
order reaction with respect to xylene with an energy of
activation falling from 26 kcal/mol between 370 and
440C to about 13 kcal/mol between 440 and 550C pro-
vided thermal deactlvatlon does not take place m the
latter range Rates of reaction at temperatures between
370 and 440C are almost completely mdependent of
oxygen partial pressure becoming mcreasmgly dependent
on the latter as the temperature IS raised
Slmdar behavlour has been observed m benzene oxlda-
tlon over V*O,-MOO, [6]
At high temperatures and high xylene concentration,
the reactlon tends toward a zero order with respect to
xylene and first order with respect to oxygen At low
temperatures and lugh xylene concentrations, reversible
deactlvatlon takes place Slmrlar behavlour has been
 The prediction of the performance of packed-bed catalytic reactors m the ar-oxldatlon of o-xylene 1437

observed m naphthalene oxldatlon over VZ0,-Sn02 [7]
(2) Tolualdehyde and phthahde drsappear with the
same first-order rate constants as does xylene above
440C
(3) The reactlon selectlvlty to C,, (PA and precursors)
at low converslons IS constant and mdependent of tem-
peratures above 370C varying between 0 75 and 0 82 for
dflerent catalysts
(4) Phthahc anhydride undergoes combustion rela-
tlvely slowly on the catalysts exammed
(5) The reactlon rate decreases sharply at tem-
peratures below 370C and the hydrocarbon dls-
appearance rate becomes first-order with respect to
oxygen bemg independent of xylene partial pressure
REACTIONMECHANISM
From the foregomg It IS seen that an adequate reaction
model must explam the changes m order of reactlon and
actlvatlon energy referred to above In particular, the
change m reactlon order with mcreasmg hydrocarbon
concentration and the fact that the mltlal selectivity
remains independent of temperature must be m-
corporated A feasible reactlon scheme which deh-
berately does not detail every definable step m the
sequence but meets the above requirements IS shown
below It mcorporates the classlcal redox model of
Mars and Van Krevelm[8] extensively apphed m pre-
VIOUSstudies of hydrocarbon oxldatlon over V,O,[9] In
what follows, a! and 0 are the fractions of unoccupied
oxldised and reduced active sites (V+ and V+) m which
the valence IS arbltranly spectied
the observed uutlal overall selectlvlty to PA of about
75% smce reactlon (b) gtves PA exclusively but con-
sumes only half of the reactant 02 m the form of the
amon
At the steady state, from eqns (at(d), the rate of
xylene disappearance IS aven by,
where m IS the moles of O2 which react per mole of
xylene consumed
By ehmmatlon of a and /3
k (XH)
r= 1 - 2 (XH)] (1)
1 + mk(HX) c b
kc(02)
Smce CO and H,O are the principal combustion
products, the values of m for the various reaction steps
are calculated accord&y It ~111 be seen later that the
energy of activation for reoxldatlon (step c) 1s zero and
further that the energy of activation for reaction (step b)
1s higher than that for chemlsorptlon (step a) so that kJk,
wdl only be slgmficant at low temperatures when eqn (1)
~111 show a maxlmum rate as the xylene concentration 1s
raised, passmg mto strong through reversible catalyst
deachvatlon at 400C, the lowest of the three tem-
peratures studied At higher temperatures eqn (I) re-
duces to,

(a) X-H+V5++(V4+ X H) (2)

Ly l-(a+8)

Chemlsorptlon of xylene which shows the first-order exclusive dependence on

(Transfer of one electron) xylene concentration at low concentrations with decreas-
mg dependence as the xylene concentration 1s raised
(b) (V+ X H) + V + OZ- + 2V4 + X-O-H Further increase m the xylene concentration leads even-
1-(a+B) a P tually to zero order w r t xylene and first order w r t
oxygen As the temperature IS lowered, the reactlon wdl
Reaction virtually extmgulsh as the term [ ] m eqn (1) approaches
(Transfer of zero At very high temperatures, since k, S- kc, r+ k,(O,)
second electron) and the hot-spot temperature m the fixed-bed reactor
becomes very dependent on the oxygen content of the
X-O-H undergoes further sequential oxidation to PI feed while Its extent of rise 1s limited by the zero
and finally PA but as TA IS formed, about 25% of the actlvatlon energy of kc An exclusive first-order de-
xylene simultaneously combusts as shown below It has pendence on oxygen concentration IS also observed at
previously been reported[l] that TA subsequently ox- temperatures below 370C (Fig 1), but the low values of
ldlses m very lugh yield to PA and that some of the the rate and actlvatlon energy imply that this catalyst
xylene oxldlses directly to PA wlthout passmg through re-oxldatlon step should be rate controllmg at high
TA and PI temperatures also Smce this 1s not so, we must conclude
that the catalyst actlvlty has undergone a nearly step
(c) 2V4 + 02 + 2v5+ + 02- + 0 change at about 370C The catalyst re-oxidation rate
B above this temperature IS therefore not to be deduced
(d) X-O-H from low-temperature experiments The lower Cs selec-
0+X-H< tlvlty observed m the low temperature region also m-
Combustion dlcates a change m mechamsm probably consequent
upon a change m the nature of the oxldlsmg species
Reaction (d) presumably has an equal probability of From an elaboration of reactlon (d) above one may
leadmg to TA and thence PA or to combustion to mve attempt to predict the selechvlty to PA at all levels of
1438 P H CALDERBANKet at

conversion in the back-mLxed reactor where ex- 80

perimental data arc available for confirmation [I] Firstly,
7O
w e m a y recognlse that T A and PI are i m m u n e from nng
rupture by oxygen atoms in the reacting system because - GO

of xylcnc inhlbltlon (It has been observed[I] that T A

50 CSTR 0,o
along undergoes partaal combustion with au" over the
catalyst but not w h e n it is formed from xylene )
Secondly, w e can rccognlse that P A m a y undergo
combustion by oxygen atoms, competing with xylene In 3O
i
this role A slmphfied scheme is shown below for the 13-
0 ~'0
case of an extenmvcly oxldmed surface [(XH)--~O] which
Induces linear kinetics
> IO

O2 + 2V 4+ )O 2- + O + 2V s+ (Fast) ~'~ 0 ,'o 2b ~o 40 .40 ~o 40 8b do ,oo

Conversion of xylene, %
O2 - + X H k ) PA Fig 2 C S T R data below420C
kf
O+XH ) PA It will be appreciated that it IS not posslbte on the
foregoing assumptions to predict select~vltles from the
O+XH ki ) CO. Zero actavatmn energy rate of combusUon of P A alone, as is shown in Fig 2,
because there is an interaction b et w een X H removal and
O+PA ) CO~ P A combustion It may also be noted that any means to
p ro m o t e the last two reaction steps above will lead to
O + 2V 4+ ) 02- + 2V s+ } improved selectavlty
O+O ) 02 Slow At this point, tt is appropriate to ask the Important
question as to wh y the initial (low conversion) Ca selec-
Thus the selectivity to P A m a S C B R [(PA/XH)= tivity v a n e s somewhat (0 75-0 82) with catalyst com-
constant] is given by, position I m p r o v e d selectlvltles are obtained by fine
grmdmg of V205 with an excess of TIO2 Bond[13] has
O = - d(PA) k'(XH)(O 2-) + k ~ ( X H ) ( O ) - k~(PA)(O) shown that there is no reaction b et ween these oxides
d(XH) k'(XH)(O 2-) + 2k~(XH)(O) below 500C so it seems likely that the effect is one of
crystahte size, as found for sdver catalysts by
1 (k~
- k~ ~ PA Harrlott[12] It has previously been pointed out that a
5% by weight V205 catalyst ground with TIO2 has about
O=
( the same activity for xylene oxidation as does pure V20~
1 + \ k ; + k'(02-10)] deposited on carborundum so the reduction IS crystal
where sine on grinding and dilution seems apparent At tem-
PA peratures below 37&C, when the reaction mechanism
changes, the T1Oz-V205 catalyst shows a much greater
actlwty than does V205 (Fig 1)
If for X = O = P A , 0 = 0 75, from the a b o v e ( O 2 - / O ) = It seems likely that T14+ functions as a third body for
2k~/k' Thus oxygen atom recombination following their generation m
reaction (c) Th e surface mobility requirement accords
3 with Blanchard's finding [5] that the most selective V2Or-
0= (3) TiO2 compositions are those showing the least energy for
k~ X
oxygen exchange
The acUvatlon energy for xylene removal falls above
It may also be seen from Fig 2 that eqn (3) agrees 440C to half its value below this temperature suggesting
reasonably well with observations of the C8 selectivity in that pore dLffuslon has b e c o m e influential (The B E T
the S C B R if area of catalyst V is about 2000 cm2/g c o m p a r e d with its
superficial area of about 5 cm2/g )
k~ I It will be seen later that the change to a low activation
= i6 [# .f(T)] energy rate controlling step at high temperatures IS es-
sential to explain the thermal stability of fixed-bed reac-
and is an i m p r o v e m e n t on the equation derived from tors and to predict then- temperature profiles
independent measurements of P A combustion m Ref [1]
RATE EQUATIONS
which IS of the same f o r m as eqn (3), but In which the
equivalent of The red o x kinetic model (eqn 2) degenerates to linear
form at low h y d ro carb o n concentraUons, thus the first-
k__~= 1 order rate constants for hydrocarbon dmappearance at
k~ 44 low concentrations were determined, principally with the
 The predlctlon of the performance of packed-bed catalytic reactors m the an-oxldatlon of o-xylene 1439

S C B R for catalyst V (3/W pellets) and found to be as _A.

follows for the reaction scheme as shown below and
previously
k. = S. ew
( >R,Ts

and m 1s defined m eqn (1) values being grven in Table 2

A one dimensional plug-flow model of the fixed-bed
reactor was programmed using published correlations for
the heat-transfer coefficient from bed to wall[lO, 15,161
Heat and mass transfer rates from catalyst to fluid were
calculated from the Jo and I,+ factors of Thodos et
al [22,23]
where E IS taken to be carbon monoxide The dtierentlal equations given below were numerl-
tally integrated using a fourth-order Runge-Kutta
method[lX] Iteration subroutines were used to deter-
k $k tk (>37O)C = 0 75
L 4 3 mine the surface temperatures and concentrations at
each step m the integration In the parameter eshmatlon
k, k., k3 (>37O)C = 29 46 25 # f(T)
the cnterlon was that the function below should be a
k, + k4 + k3 (>370 6 44O)C mmimum

1
27,120 g mol
=1/3exp 197-- -
C R,T ghratm

k, + k,+ k, (>44O)C = l/3 exp 10 19-- g + c (ho - JD~~+~ (To- To,

c Z?,T I ghratm
k, = kz (>37O)C = k, + k4 f k3 (=44OPC
k, (>37O)C = exp
These umts may be converted on multlphcatlon by 3 to
cmlsec at 400C takmg the supeticlal area of catalyst V
as 5 cm/g
The data are given m more detail m Table 2
THE PLUG-FLOW MODEL
The redox kmetlc model (eqn 2) was used to predict
the observed temperature and yield profiles m a one mch
tubular reactor The kmetlc parameters were adjusted by
systematic trial m order to secure good agreement with
the observed profiles[14] To this end the first order
kmetlcs above were used to start the search routme
which mvolved finding fourteen parameters of the redox
format as detaded below
The redox model for each reaction step gves
(4)
gD g,
Summation was camed out for a set of thn-teen dls-
Crete points to compare the predlctlon with the smoothed
experimental yield and temperature profiles The weigh-
mg factors g,+ gg, gc, g, and gT were chosen by con-
sldermg the magnitude of the different terms involved in
the above equation
The lmtml estimates of the parameters were obtamed
as above and subsequently by visual matchmg of the
predicted response with the measured profiles The mml-
mlzatlon of the above function was carried out by
Powells method[20] The results strongly indicated that
the activation energy for the reoxldatlon of the catalyst
was very small Durmg the search of the parameter
space, the activation energy of the catalyst reoxldation
step was found to be zero and step 6 to be kmetlcally
neghmble Kinetics below 713K are not invoked by the
model because of the very rapid rise, over a few ems of
mlet reactor length, to above this temperature

-7% = r, + r, -I-r4 = k,a(P, - Pn s)

r, = k,aPas r4 = k4aPAs
r2 = k2aPB s rs = k5aPc s
r, = kJaPA s r, = ksaPDs yz=r,-r2=kga(PBs-P,)
where
kpo, s
Q = k,P 02S+PAS(mlklimpk,+m4k4)tP,sm2k2+ PcsmJcs+PDSm6k6

Table 2

Step -AH
(n) m (kcallg mol) Ts G 440C T.>WC T.bWC T,=-440C

1 1 109 9651 0715 27 12 13 56

3 65 550 8320 0 617 22 12 13 56
4 3 2% 15309 1 134 27 12 13 56
2 1 99 2466 13 56 13 56
5 1 88 zi 2466 13 56 13 56
6 35 254 1354 1354 30 50 30 50
1440 P H CALDERBANK eta!

y$$=rrr5=kgn(Pcs -PI21

dPD - PD)
yz=r5+r4-r6=Iga(PDs

where

Fig 4 Effect of doubhng mass velocity on the temperature

profile Go = 9492 kg/m hr, & = 644K. 4 = 691K, 1, PredIcted
profile, n, Experimental data pomts
where

02
(6)

n=6

g, r,(-AH). = ha(Ts - T) 0
IO

Results are shown for a one mch diameter reactor m

Figs 3-7, from which It IS seen possible to predict the
effects of variations m jacket temperature and flow-rate
on the yield and temperature profiles under the con-
&tlons grven m Table 3

pc = 2 28 g/cm3, E = 0 56, a = 4 18 cm/g, d, I

=254cm k-
C,, = 0 26 Cal/g C, PT = 1 atm, PA, = 0 01 atm
g, = 8 X lo- atm, g, = 5 X lo- atm, g,
= 1 X lo- atm,
gD = 8 x lo- atm*, g, = 130CZ
02
The parameter estunates are given m Table 4

Fig 5 Concentration profiles m fixed-bed reactor Go=

4746 kg/m hr, Ti = Tf = 693K. 1, PredIcted profile, R = PA/PA,,
I, Experimental data pomts, 2, Predtcted profile, R = PJP,,, 0,
ExperImental data pomts, 3, PredIcted profile, R = PC/PA,, 0,
ExperImental data pomts, 4, Predlcted profile, R = PdP,,. 0,
ExperImental data pomts

700 The experimental data at higher xylene concentrations

m the feed (1 5%) show partml deactlvatlon of the ca-
talyst, probably due to crystahte smtermg and loss of
I. cm
area at the hot-spot where the temperature IS predlcted
Fig 3 Effect of inlet feed temperature on the temperature profile
m fixed-bed reactor G, = 4746 kg/m2 hr. T, = T,, 1, Predicted
to rise uutlally to about 600C
profile for r = 753K, 8, Experimental data pomts, 2, Predicted A noteworthy feature of the reactor model above IS
profile for T, = 683K, 0, Expenmental data pomts the fact that the fimte rates of heat and mass transfer are

Table 3

k
(kd> hr) (kg mol/m2 hr atm) (kcal$ hr C) (kcalI$hr C)

4746 75 135 1 948

9492 117 210 8 1267
 The predlctlon of the performance of packed-bed catalytic reactors in the air-oxldatlon of o-xylene 1441

Table 4

s A

Step (&%J ei>

1 3828 14 67
3 0 358 12 23
4 1 295 13 02
2 0 556 11 10
5 3 190 13 84

Step 6 kmetlcally mslgmiicant

U, m = 0 722 x lo-, # f(T), g mol/g set

was found to be 0 722 x lo- g mol/g set #f(T)

pressure
Flock[21] has slm~larly found a low actlvatlon energy for
catalyst reoxldation
From the foregoing value of k,P,, m, where P = 0 2 atm
and the value m the same units of k1+3+4(20x lo-), as It
applies approximately over the temperature range of
interest (420_52O)C, It appears that the capture cross-
section of V for o-xylene is Just over twice that of a
O*- vacancy for oxygen It may also be rigorously com-

20 80
1
puted from the foregoing reactor design equations ap-
phed to a typical commercial operating case, that the
2. em
fraction of oxldlsed catalytic surface m the plug-flow
Fig 6 Concentration profiles m fixed-bed reactor G.=
4746 kg/m hr, T. = T, = 713K, 1, PredIcted profile, R = P,/P,<, reactor, vanes from about 50% at the inlet to 100% at the
I, Expenmental data points, 2, Predicted profile, R = PJP..,, , 0, outlet, consequent upon the rapidity of catalyst reduction
Expenmental data pomts, 3, PredIcted profile, R = PC/P,,,l, by xylene even at relatively low concentrations com-
Expertmental data pomts, 4, Predicted profile, R = PJP,., Cl, pared with the rate of re-oxldatlon by oxygen
Expenmental data points
The measured disappearance kinetics at low reactant
concentrations (Table 2) have all to be adjusted To
obtain correct model predIctIon, the rate of reaction 1
has to be increased while the rates of reactions 3 and 4
are reduced to give an mltlal selectlvlty of 80% instead of
75%
It 1s possible that there may be a significant mass
transfer resistance m the S C B R , such that, as ex-
plained later, the rates of the reactlons A-+B+C are
under-estunated, (see Table 5) even at very high rotor
speeds The high uutml selectivity at high temperatures
could not be observed m the S C B R , because of com-
bustion on the walls of this reactor
Further apphcatlon of this procedure to our system
reveals that It 1s not capable of discerning large errors m
the mltlal values of the actlvatlon energy used to start
the parameter search because mstabtltttes are found to
artse from excursion from the mltlal guess
any large
and these are avoided, thus the computation tends to
IO 80
I. cm retam the input actlvatlon energy and to find the op-
Fig 7 Effect of increasing o-Xylene concentration at the inlet of timum pre-exponential factor to suit Thus the actlvatlon
the temperature profile G, = 4746 kg/m+hr, T, = T, = 693K. 1, energies for the five reaction steps were refined by
PAi= 0 01 atm (Profile measured pnor to changmg P_&, 2, PAI= matchmg the model to experimental profiles with an
0 015 atm (Profile measured under unsteady state condltlons), 3, approximate confidence interval of 95% However, a 6
P,,= 0 015 atm (PredIcted profile), 4, P,,= 0 015 atm (ProMe
measured under steady state conditions), 5, PAI= 0 01 atm (Profile parameter model obtained by settmg all actlvatlon ener-
measured by reducing P,, from 0 015 to 0 01 atm) ges to zero gave virtually the same value of the muu-
mum objective function
almost exactly compensatmg as far as the reaction rate 1s
concerned so that their mcluslon m the model does not APPLICATIONS OF TEE P.F MODEL
affect the temperature profiles very much although the Since the cost of manufacture of PA LS strongly de-
yield profiles are more largely influenced pendent on the quantity of excess air pumped, it 1s
The value of kpo,,, with air at near atmospheric desirable to increase the hydrocarbon loading, d this can

CES Vol32 No 12-C

1442 P H CALDERBANK et al

be done wlthout thermal runaway and Ignition The lower m the measurement of the disappearance rates of A and
fiamablllty hmht of xylene m a~ IS not known with any B particularly the latter, which may partly explain the
preclslon but 1s beheved to be from 1 to l& by volume kmetic correction factors found necessary m reconcllmg
With a feed of lfi o-xylene, the model shows an the fixed-bed model to experunental observation (Table
unacceptably hsgh hot-spot of 568C at a flow rate of 2) The net rate of formation of TA 1s the drfference
4746 kdrn* hr m the 1 m dla reactor However, if the between two large rates and therefore very sensitive to
catalyst m the first 4 metre of the reactor 1s diluted with small uncertamtles m the latter
mert packmg to the extent of 66% by volume of active
catalyst only, the hot-spot temperature for the 14% xy- NOTATION
lene feed, as above falls to 500C bemg about that actlvatlon energy, k cal/mol
observed with undiluted catalyst and a 1% feed specfic area of the catalyst, cm/g
It 1s estimated that the saving on equipment and run- heat capacity, Cal/g C
mng costs for a 40,000 t/y plant using the rich-feed tube diameter, cm
dluted-catalyst strategy would be about 27% There 1s mass velocity, kg/m hr
therefore a strong incentive to determine with accuracy gas film heat transfer coefficient, k Cal/m* hr C
the flammability lumts for the xylene oxldatron system gas film mass transfer coefficient, k mol/m* hr atm
under condltlons such as obtam on the plant and to reoxldatlon rate constant of the catalyst,
design for rich-feed operation with safety g moljg set atm
The model correctly predicts that the hot-spot tem- rate constant, g mol/g set atm
perature 1s qmte sensitive to the oxygen partial pressure mean molecular weight of the feed, g/g mol
m the feed Thus, m practice, It 1s possible to reduce moles of O2 consumed per mole of hydrocarbon
temperatures or increase the hydrocarbon loading, d reacting
tzul-gas 1s recycled to the appropriate extent basket stlrrmg speed, rev/m
average pressure in the reactor, atm
TEECST.R MODEL partial pressure, atm
Slmdar calculations to the foregoing were camed out feed flow rate m S C B R , I /m
for the perfectly mixed reactor m order to evaluate the partial pressure ratio
limitations of the S C B R as it was used m the kinetic gas constant, Cal/g mol K
determinations, the kinetics comprised Table 2 and the rate of reaction evaluated at the surface con-
heat and mass transfer coefficients found by Perelra and ditions, g mol/g set
Calderbank[2] Some results are shown as effectiveness pre-exponential factor, g mol/g set atm
factors m Table 5 below, from which it 1s seen that temperature of the Jacket fluid, K or C
catalyst surface temperatures at normal experunental bulk temperature of the fluid m S C B R , K or C
condltlons of operation differ mslgmficantly from those inlet temperature of the feed, K or C
m the fluid but that slgmficant concentration differences overall heat transfer coefficient from bed to Jacket
can sometimes arise fluid, kcal/m hr C
In practice It 1s therefore easy to equate the measured weight of the catalyst m S C B R , g
rate of reaction to the mass transfer rate equation and fractional conversion of o-xylene
thus evaluate (PJ -P) provided the mass transfer co- mole fraction
efficient can be estimated In ths work, usmg few ca- distance measured along the axis of the reactor
talyst pellets on the periphery of the spmnmg basket, from the inlet, cm or m
mass transfer coefficients appear to be much higher than
m a packed-bed configuration, to Judge from the absence Greek symbols
of an effect of rotational speed on the observed reaction a fraction of unoccupied oxldlsed s&es
rates fi fraction of unoccupied reduced sites
y defined m eqn (5)
Q, = 0 25 1 /mm, PA, = 0 01 atm, T, = T,, A defined m eqn (4)
w=331g, a = 5 cm/g, E = 0 4, p density of catalyst, g/cm3
N=60OORPM, c bed voldage
k, = 3 27 X 10m4g mol/cm* set atm, B selectlvlty to C, products
h = 8 95 x lo- Cal/cm set C Q defined m eqn (6)
q effectiveness factor (see Table 5)
From the above, It IS seen that significant errors arise AH heat of reaction, k&g mol
For the fixed bed reactor modelhng, any set of con-
Table 5 sistent umts may be employed

T, (C) 450 500

Subscripts
T. - T, (C) 151 1 58 S surface condition
rl.4 0 91 0 84 p predicted value
118 044 0 19 0 observed value
?c 1 03 103
m mean value
11D 0 95 0 88
I inlet condltlon
 The predIctton of the performance of packed-bed catalytic reactors m the air-oxldatlon of o-xylene 1443

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