Chemrcol Engrmenng SCWICC Vol 34 pp IKE-t331

Pergamon Press Ltd I?79 Pnnted m Great Bntam

PREDICTION OF PACKED-BED CATALYTIC REACTOR

PERFORMANCE FOR A COMPLEX REACTION
(OXIDATION OF o-XYLENE TO PHTHALIC ANHYDRIDE)

K CHANDRASEKHARAN and P H CALDERBANK

School of Engmeermg Science, Umverslty of Edmburgh. Kmg’s Buddmgs. Mayfield Road, Edmburgh EH9 3JL,
Scotland

(Recelued 15 December 1978)

Abstract-Statistical best-fit kinetic and transport parameters are denved from temperature and yield profiles
observed in a pdot-plant catalytic reactor in whtch o-xylene IS oxldlsed with au to phthahc anhydride and Its
precursors Published data are used to begn the search routine and the tuned parameters are seen to be plaublble
The overall model has good extrapolattve power to the point where catalyst deactlvatlon becomes apparent

INTRODUCTION msensrtlve over this range The reactor operates under

Models of varying complexity have been proposed to relative freedom from thermal runaway wrth a much
simulate the performance of packed-bed catalytic reac- more gradual nse m the temperature profile than that
tors and reviewed recently by FromentIl] Generally, predlcted by the reactor model incorporating the pub-
the agreement between the predlcted and the observed hshed kmetlc data for the same catalyst referred to
temperature and yield profiles IS not satisfactory, even below The catalyst was surface coated and estlmatlons
for a smgle reactlon[2-4, 281 Usually the a pnon design for a moderate thickness of catalyst (25-50 p) revealed
of a fixed-bed reactor wtthout a nummum number of that the combmed external and internal transport
prlot plant measurements cannot be consldered very gradients would increase xylene concentration at the
rehable, particularly for complex multi-step networks outlet of the spinning basket reactor used by Calderbank
mvolvmg large heat effects as m the case of the vapour et al in their kinetic study by about 20%[14] It was
phase oxidation of o-xylene over vanadmm pentoxide therefore concluded that this kmetlc data m the high
catalysts The present paper examines the experimental temperature region (>713K), having an actlvatlon energy
field profiles obtained m the latter reaction over a com- of 13 56 kcallgmole for the first order xylene dlsap-
merclal catalyst m a pdot plant fixed-bed reactor[S. 141. pearance rate, IS not adequate and cannot explam the
m order to evaluate the vahdlty of plausible kmetlc and much lower hot spot temperatures observed m the pilot
transport models plant reactor, wherein the same catalyst was used
The kmetlcs of o-xylene oxldatlon to phthahc anhy- However, the combmed selectlvlty levels pnor to gradual
tide has been studied m some detail [6-l l] although the deterioration in the laboratory spinning basket reactor
high exothermlclty makes It ddiicult to approach lso- agreed with those observed in the pdot plant The avall-
thermal condltlons Catalyst dtlutlon, rf used to reduce able kmetlc data were therefore used as an mltlal ap-
the reaction rates, causes the yteld of phthahc anhydrlde proxlmatlon m the estimation of more refined kmettc
to be reduced owmg to inescapable catalytic activity of parameters from the non-aothermal pilot plant data
the dduents. partlculary at high temperatures and the
long contact bmes typrcally used tn laboratory reactors Modelhg of jixed-bed reactor
Slmdar problems have been experienced m benzene The estlmatlon of the parameters tnvolves the mml-
oxidation [ 121 The presence of large areas of metal sur- nusation of the ObJectWe function
face m spmnmg basket or reclrculatlon type reactors also
results m the combustion of phthahc anhydnde and other 4 = wJ(PA"-PA)*+ wez(P*"-P~)2+wc~(P~o-Ppc)2
intermediates such as phthahde, o-tolualdehyde, etc ,
+ wDz(PD"-PD)*+ WTP(To_ Ty (1)
and the metal surface acquires an Increasing catalytic
actlvtty with the period of operation, resulttng m poor
selectlvlty to phthahc anhydrtde [ 131 wtth respect to the optlmlsatlon variables The welghtmg
Plot plant measurements with a packed-bed catalytic factors were chosen by consldenng the magmtudes of
reactor, however, reveal that phthahc anhydnde IS the various terms mvolved m eqn (1) and the observed
remarkably stable despite peak temperatures of about yield and temperature profiles were smoothed over a set
110°C above the feed inlet temperature which was vaned of thuteen dtscrete points The correspondmg predicted
m the range 410-48WC at short contact times (Cl set) values were obtamed by using a one-dlmenslonal plug
typlcalIy encountered m commercial practice with the flow model accountmg fot mterphase temperature and
so-called “Amencan type” catalyst Also. the combined concentration gradients The governing equattons are
selectwlty to CL hydrocarbons (phthahde, o-tolualde- summarrsed m Table 1 and the relevant data m Table 2
hyde and phthahc anhytide) IS found to be temperature The global rates of reactions were evaluated by solvmg

1323
1324 K CHANDILASEKHAFWN and P H CALLXERBANK

Table 1 Reactor model eauatlons

-yl g : R
-M

EM = k;, (p-f)

6
dT
- Y2 (T - Tc)
?iF= ,":I AP Rq.n

hfa (Ts - T) = (- AHq,

.9, Rbn

T
P = (P, P* PC PD: , p" = (PAS PBS PCS PDY

EM = (RMdI, RMB RMC, %DjT

9

z = 0 p=pl

T = T
I

PI= 0 0 o>*
(PA , I

Iteratively a set of nonhnear algebraic equations by don-Fletcher-Powell method as modtied by Stewart[l6]

Broyden’s method[U] and the set of ordmary dtierentml to accept fimte difference approximations to the gradlent
equations were mtegrated numencally by the Runge- of the objective function Also used were the Powell’s
Kutta-Merson method The muumlsatlon of the ObJec- denvatlve free search method [17] and a quasi-Newton
twe function m eqn (1) was accomphshed by the Davl- method capable of handhng constramts, using the

Table 2 Summary of the data used m packed-bed reactor modellmg[51

catalyst vanadium per&acids with uadisclosad pmmotars on
ailicon carbide
Pore vclluma IOO4cm3 Pore radius = 4444 OA,
Bm' 2
Surface area = 2000 c

d = 0 63 an. dt = 254cm. c = O26cal

P P
gm OC
P 2 28 =, Eb = 0 56. PT = 1 atm,
P = cm3
*
q 001atm, P = 018amn, TIf q TC* = 693°K,
'A,1
O2
kx* = -4 gpro1a
2 09 x 10 3 Go* = 0 1319 A ,
g cm2sec atm cm2 set
Cal Cal
hf" = 3 75 x 10-3 , u* = 2 63 x 10-3 I
cm2 set % cm2 set Oc
VA = 6 x 1o-7 atm2, we = 5 x 10-7 atm2, WC = 1 x 10-7 atm2,

= 9 x 1O-7 atm2, vT = 132 OC2

UD

a
109.000 1 0 715 13560

296,ooO 3 1 13rr 13560

XH * COX** 55o.ocxJ (1091,000) 6 5 (10 5) 0 617 13560

99.000 1 2 466 13560

B8.000 1 2 466 13560

254,000 (795.000) 3 5 (7 5) 1354 30500

** The quamities given z.nbrackets refer to COX bsmg taken a* carbon

dioxide
* Unless stated otheru=se
 PredIctIon of packed-bed catalytic reactor performance 132s

modified DavIdon-Fletcher-Powell relatlonshlp to up- R~,,=(s,+s~+sJ)P~&=R,M+R~M+R~M

date the direction mamx [ 181 RMB = (s&s - slpA)@R = R4 M - RI M
In view of the widely dtierent heats of combustion of R MC=(SJPC-SPB)@R=RSM-R~M
xylene to carbon monoxide and carbon dioxide, the R~~D=-(s~P~+s~PA)~~=-RR~M-R~M (2)
choice of combustion product E affects the kmettc
parameter and E was mltmlIy taken as carbon monoxide
to stabdlse the lmtlal search The reactlon scheme IS that
observed by one of us[lO] m spuming basket measure-
ments with the same catalyst, except that the combustion Smce oxygen was present m large excess, kaPm can be
of phthahc anhydrlde IS suppressed, as shown regarded as a constant dependent on temperature The
transport parameters (U, k, II,) were estimated from
published correlations m the lIterature[l2.201
Since an estimate of actlvatlon energy and pre-
exponential factor of k, was not avadable for the cata-
lyst used m the pdot plant, except an mdrcatlon that k,
must have a high value to make 19~ tend to umty and
yield first order kinetics, the actlvatlon energy of k, was
tentatively fixed at zero The final tuned estimates of the
11 kmetlc parameters are summarized m Table 3 The
search towards the muumum of the ObJectWe function
proceeded rapidly m the mitral stages but subsequently
DISCUSSION the search became very slow owing to the high degree of
Each step m the above network IS assumed to follow correlatton between the pre-exponential factors and
the “Redox format” which has been quite successful m actlvatlon energies Consequently, the search was mter-
correlatmg the rate data for a vmety of hydrocarbon rupted to examme the predlcted profiles when the
catalytic oxtdatlon reactlons[19,25,26] The rate gradlent matnx was sufficiently close to zero (Figs 1 and
expressions derived from either the steady state (non 2) The remarkably good agreement between the predlc-
equlllbnum) adsorption of oxygen model[25] or the ted and observed profiles at the final tuned estimates and
“Redox” model postulating the direct participation of a vu-tually flat nununum of the ObJectWe function sug-
lattice oxygen lons[19] become identical For the net- gests that any further improvement m the mmlmum
work shown above, the rate expresslons for xylene (A), value of the ObJectWe function wdl be largely illusory It
o-tolualdehyde (E). phthahde (C) and phthahc anhytide was therefore decided to test the extrapolative power of
(0) can be wntten as the tuned estimates at the extreme condltlon used m the

Table 3 11 Parameter modeC”Redox format” E = carbon monoxide

Final tuned
Initial guess*
estimates
-0 1 0 715 3 828
=1
-0 ;
1 13r, 1 295
s2 1
-0 ) 0 617 0 358
gUl0lC
=3 p 8ec atm
-0 ;
2 466 0 556
%
-0 :
2 466 3 190
s5 1

13560 14668

13560 lx)21

13560 12228

13550 11099

P5 j 13560 13838
1

-2 -6
2 Y 10 7 221r x 10

0’
0q

36 8 89
1326 K CHANDRASEKHARAN
and P H CALDERBANK

pdot plant The close agreement m the prediction of the objective function can be altered m a favourable dlrec-
magmtude and position of hot spot temperature at other tlon rf U 1s allowed to increase from Its earlier estimated
operatmg condltmns can be seen from Figs 3-6 Further value to accommodate the larger heat release when E IS
anaiysn of the estunated rate constants revealed that the taken as carbon dioxtde The resultmg nine parameters
parameter estimates were highly correlated and the
activation energes were not well estimated In the sub-
sequent analysts wth E taken as carbon dioxide, the 603

activation energes of all the rate constants were, there-

fore, fixed at thev reported values and that of k, at zero F7= 1
as before The transport parameters were now treated as
optlmisation vanables since the mmlmum value of the

613
t

Rg 3 Temperature profiles for TI = Tc = 683K and PA, =

0 01 atm - ExperImental profile, ---- Predicted profile
obtamed by usmg the tuned model parameters, COX = CO2
(Tables 2 and 4), -- Predicted profite obtamed by ustng the
tuned model parameters. COX = CO (Tables 2 and 3)

0 IO 20 30 40 50 60 iv 60
Olstanca ma#sumd from the mactor inlet, EITI
653-
Fu 1 Temperature profiles for T, = Tc = 693K and Pnl =
001 atm - Expenmental profile, ----- PredIcted profile
obtamed by usmg tbe tuned model parameters, COX = CO2
(Tables 2 and 4). -- Predtcted profile obtamed by using the
tuned model parameters, COX = CO (Tables 2 and 3)

-0 IO 20 30 40 50 60 70 60
Distance measured from the reactor Inlet. cm

Rg 4 Temperature profiles for T, = Tc = 733K and PAI =

0 OI atm - Expenmentai profile, ----- Predicted profile
obtamed by usmg the tuned model parameters, COX= CO*
(Tables 2 and 4). -- PredIcted profile obtained by usrng the
tuned model parameters, COX = CO (Tables 2 and 3)

Distance measumd from the moc&r Inlet. cm

Fqg 2 Concentration profiles for TI = T, = 693K and PAI =

001 atm x o-xylene, Cl o-tolualdehyde, 0 phthahde, V Fig 5 Temperature profiles for T, = Tc = 753K and PAI =
phtbahc anhyhde, -- PredIcted profiles obtamed by ustog 001 atm - Expenmental profile, ---- Predrcted profile
the tuned model parameters A, B. C and D refer to o-xylene, obtamed by usmg the tuned model parameters, COX = CO2
o-tolualdehyde, phthahde and phthahc anhydrtde respectwely, (Tables 2 and 4), -- Prekted profile obtamed by usmg the
COX = CO (Tables 2 and 3) tuned model parameters, COX = CO (Tables 2 and 3)
 Predwtlon of packed-bed catalytic reactor performance 1327

_- were tuned after placmg the followmg constramts on the

transport parameters
0’
I/
y
-0
--+Ly.__ -
_ --
u < 3 45 x lo-’ cmz ttc “c

k,^ < 3 x 1o-4 cm*g;e;e atrn

35x10-3<h,<5x10-3cmz ;$ “c

V0 The search was termmated when the value of the objet-

/
tlve function fell below 6 The results are summaruzd m
/ Table 4 The predlcted profiles obtamed from the tuned
estimates gve a satisfactory fit over a Hnde range of
operating conditions m the one mch diameter tube, as
can be seen from Figs 1, 3-5 and 7-9 The over all heat
transfer coefficient tends to the upper hmlt of the con-
straint imposed on It This limit was estimated from the
reported temperature profile and outlet composition of
the reaction mixture (2) The higher value of CJISlargely
responsible for reducmg the oblective function below 8
The molecular dlffuslvlty of o-xylene from the G&land
Mstmea -umd from tha reactor inlet, cm equation [21] was found to be underestimated compared
with that obtamed by the more reliable Lennard-Jones
FU 6 Concentration profile for rI = Tc = 713K and PAr = potential method[22] and thus could possibly explam a
001 atm x o-xylene, Cl o-tolualdehyde. 0 phthahde, V near 30% Increase m k,” The margmal increase m hf IS
phthabc anhydrrde, -- PredIcted profiles obtamed by usmg
the tuned model parameters A, B. C and D refer to o-xylene,
well Hrlthm the scatter m the published data Further-
o-tolualdehyde, phthahde and phthahc anhydnde respectwely, more, the predicted hot spot temperature and the tem-
COX = CO (Tables 2 and 3) perature profiles are insensitive to both kgx and hf, as

Table 4 9 Parameter model-“Redox format” E = carbon &oxide

-3
U ) Cdl 2 63 x 10 3 43 x 10-3
-3
hf 1
) cm 2 set oc 3 75 x 10-3 3 87 x 10

kX gmo1e 2 09 x lo+ 2 89 x lo-&

g cm2 set atm

3 ) 0 975 1 966
-0
s2 ; 1 015 1 807
)
glTlCJ1.S cl 296 0 760
ii"
gm set atm
3 ;
-0
% ; 1 010 3 182

9 1 r)50 3 281
5 ;

2" 13560' 13560"

1 :
Kin ) 135601 13560'
2
Go :- Cal
13560' 13560'
gmole
3 )
EV 135EOq 13560'
4
;
i" ) 13560' 13560'
= 1
k= p gmo*e 2 x 10 -6 7 019 x 10 -6
a 02 gm set
1328 K CWANDRASEKHARAN
and P H CALDERBANK

a2
*g--o_ Cl
-_
0.0
01- _ -:A-\ *
C NC c,JY -‘,’ - _
** -_z_------__
0 ----____
_L

,
t 09 -‘,
\
3
-ix
3 OS- \
\
8 ‘\\ v
__--
zo7-
\ 4-H’
E c-
\ x V.-
iS \
- 06 - .@
\ /
S \ v .’
\
,
1 os- , ,*-
\ I’
E : ,’
\ #
8 04- I

t
Jj Q3- Y’v
,’ ‘\*
g 02- \
/’
is 8.
r’V
‘.
Ol- ’ *.
.d x --__
--__ A

*o
-,*
10 m 30 40 50” 60
- -__
70--80
_.d
Distance msasumd from fhe reoctaq Ink& cm Dtstance mwsumd fram the reactor inlet. cm

Fq 7 Concentration profiles for TI = Tc = 693K and PAI = Rg 9 Concentration profiles for T, = Tc = 713K and PAI =
001 atm x o-xylene, Cl o-tolualdehyde. 0 phthahde, V 001 atm x o-xylene, Cl o-tolualdehyde, 0 phthahde, V
phthahc anhytide. ---- PredIcted profiles obtamed by usrng the phthahc anhydnde. ----- Predicted profiles obtamed by usmg the
tuned model parameters A, B, C and D refer to o-xylene, tuned model parameters A. B, C and D refer to o-xylene.
o-tolualdehyde, phthahde and phthahc anhydnde respectively, o-tolualdehyde. phthahde and phthahc anhydnde respectrvely,
COX = CO2 (Tables 2 and 4) COX = CO* (Tables 2 and 4)

was found by settmg both c and II, to high values This influenced to a larger extent by the presence or total
msensltwlty to interphase gradients occurs m spite of a absence of interphase gradients Marginal variations III

maxlmum predicted temperature dzfference of 32’C be- ~~ and h, have, however, practically no effect on the
tween the catalyst surface and the bulk phase Even for predicted concentration profiles The results are sum-
the extreme case TI = Tc = 753K, the predicted hot spot mansed in Figs 10 and 11
temperature is not affected by either increasing only II, From the foregoing It IS clear that the presence of a
or both k,” and /I~ by about 30% However, when U IS large number of adjustable parameters gives conslder-
decreased by 23%, the predicted hot spot temperature able flexlbdlty m tunmg the data to handle the two
increases by 28°C The concentration profiles of the
mtermediates, o-tolualdehyde and phthahde, are
/\
673 -
/ 1
764-

744-

IO 20 30 40 50 60 70 60
Distance mearumd from the reaclvr tnbt. cm
0 IO 30 40 50 70 60
Distance mearumd from the reactor inlet. cm F@ 10 Influence of transport parameters on the predicted tem-
perature profile T, = Tc = 753K. PA I = 0 01 atm. COX = CO,,
l?g 8 Effect of doubhng mass velocrty at the reactor mlet Refer Tables 2 and 4. ------ k,‘, k, and U as given m Table 4,
TI=644K, Tc=691K, U=383xlO-‘cal/cm’ set “C, kSz= ------ k.1 and U as given m Table 4. only II~IS Increased by
m, h,=m, - Expenmental profile, --- Predicted profile 29%, ---- kg= IS Increased by 28% and h, by 29%. U as
obtamed by usmg the tuned model parameters, COX= Co2 given m Table 4, --- k.” and h, as given m Table 4. U
(Tables 2 and 4), -- PredIcted profile obtamed by usmg the IS decreased by 23%. kg* and h, set to high values,
tuned model parameters, COX = CO (Tables 2 and 3) U as gven In Table 4
 PredIction of packed-bed catalytw reactor performance 1329

FIock[23] observed a low activation energy for k,

(-5 kcal/gmole) while Pant and Chanda[24] quote a
value which JS much lower than that observed by
Canadian workers [26,27] Recently, Wamwnght and
Hoffman[7] have found the rates of reactions over a
Mama based catalyst to exhibit hardly any temperature
dependency More recent studies by one of the
authors [ 141 on a tubular wall coated reactor showed that
J 08
E, has a value of 25 9 kcal/gmole below 450°C for pure
=s5 07
vanadium pentoxlde catalyst Usmg this value, along
.E
with the fixed actlvatron energies of all the other five
0 06 steps, U, k,” and !z, as m Table 4, the 6 pre-exponential
c
2
factors were vmed to obtam the best fit The mmlmum
Ee 05 value of the objective function was found to be four
times higher than that obtamed by fixmg the actlvatlon
g 04
energy of k., at zero Also the tuned estimates gve too
::
t 03
high a hot spot temperature (932K) when extrapolated to
P predict the temperature profile for a feed inlet tem-
g 02 perature of 753K It IS therefore concluded that E, must
E
have a low actlvatron energy, though not necessardy zero
01
and the use of kinetic parameters, as detaled m Table 4,
provides a reasonably good prediction of the field
00
0 0 20 30 40 50 60 70 00 profiles m a I m diameter tube The low value of k,
Distance -red fmm the moctor ink?. cm
mevltably introduces a greater dependency of rates on
Fw 11 Influence of transport parameters on the predIcted concen- oxygen pa&al pressure at the reactor inlet This was the
tratlon profiles T, = Tc = 753K, P,, , = 0 01 atm. COX = COz. case rn the pilot plant reactor, as observed by a general
Refer Tables 2 and 4, ------- k*=. kf and U as gwen m Table 4.
damping of the temperature profile when a part of the tad
--- kg=and U as gwen m Table 4. only h, IS Increased by 29%.
- kcr IS Increased by 28% and hf by 29%, U as gwen m Table gas was recycled to reduce the oxygen concentration at
4, -- k,” and h, as gwen m Table 4, U ISdecreased by 23%. the reactor inlet by about 50% The laboratory kmetrc
kg=and k, set to lugh values, U as gwen m Table 4 measurements, however, reveal very little oxygen
dependency of the rates over the temperature 440-500°C
The vu-tual mvanancy of the combined selectivity to Cs
extreme cases of E bemg taken as carbon monoxide or hydrocarbons even when the catalyst 1s lrreverslbly
as carbon dloxlde The presence of an addItIonal kmetlc deactivated by usmg a xylene feed of 1 5% by volume
parameter, namely the reoxldatlon rate constant of the (Fig 12) can be regarded as due to catalyst smtermg and
catalyst or the oxygen adsorption rate constant, the consequent reduction m the oxygen adsorption rate
effectively reduces the Jmtial rate of xylene dlsap- constant The use of a high xylene concentration at the
pearance which would be higher if hnear kmetlcs (& = reactor inlet offers potential scope to increase the
1) were used, as shown m Table 5 It should be noted productive capacity of existing plants The precise
that near the mlet remon, even a margmal decrease m explosion limits of arr-xylene mixtures need to be m-
heat generation. as JS effectively achieved by mtroducmg ves-ated further, along with the possible long term
mtermedlates m the network, will have an overall dam- effects of catalyst deactlvatlon near the mlet remon
pmg effect on the temperature profile It may be noted caused partly by the use of a high xylene partial pressure
that the foregoing analysis was made by fixing a zero and by packed-bed dynamics which can result m catalyst
actlvatlon energy for the reoxidation rate constant temperatures nsmg above theu permitted limits during

Table 5 Companson of mltlaI dtsappearance rates of o-xylene c -) m, h, +=, P,, 1 = 0 01 atm

Inrtial rates gpDole

gm *ec

= 693% TI = 753?X
TI

Redox f-t
E = carbon dioxide 1 11 x 10-6 1 49 x 10-6
Table I)

Redox format
E = ca~bonmnoxide 1 21 Y 10 -6 1 70 x lo+
Table 3

Linear kinetics -6 -6
Table 2 130x10 2 86 x 10
1330 K CHANDRASEKHARAN
and P H CALDERBANK

number of parameters, even when the catalyst IS m a

non-deactivated state, the low value of k, with a smaIl
temperature dependency can be looked upon as an ap-
proximate was of accountmg for deactlvatlon effects

NOTATION
specific area of catalyst, cm3/g
heat capacity of the feed stream,
Cal/g “C
pellet diameter, cm
reactor tube diameter, cm
estimate of actlvatlon energy of rate
constant s, cal~gmole
estimate of actlvatlon energy of oxygen
adsorptlon or reoxtdatlon rate constant
k,, callgmole
mass velocity, g/cm’ set
13ktar.a measured from ti reactor inlet. cm
mterphase heat transfer coefficient,
Fuz 12 Elfect of mcreasmg 0-xylene partial pres- Cal/cm’ set “C
sure at the reactor mlet to 0 015 atm IF,= Tc = 693K, - estimate of pre-exponential factor of k,,
Expenmental profile, 1 Unsteady stat& 2 Steady state, 3 gmole/gm set atm
Steady state with PAI reduced from 0 015 atm to 0 01 atm, ----
interphase mass transfer coefficient.
PredIcted profile obtained by using the tuned model parameters,
PAI = 0 015 atm and COX = CO2 (Tables 2 and 4), - Predlc- gmole/cm’ set atm
ted profile obtamed by usmg the tuned model parameters, PA I = average molecular weight of the feed
0 015 atm and COX = CO (Tables 2 and 3) stream, gm/gmole
storchlometnc coefficient (subscripts I, 2,
etc refer to the steps m the network)
partial pressure, atm (subscnpts A, B,
the start up Use of a tubular-wall-coated-reactor fol- etc refer to the components, suffix I
lowed by the conventional packed-bed reactor could refers to the mlet condltlon, super-
reduce temperature gradients near the Inlet remon and scripts 0 and s refer to the observed
prolong the life of the catalyst value and catalyst surface condltlons
respectively
CONCLUSIONS average oxygen partial pressure, atm
The performance of a large packed-bed reactor could total pressure, atm
be predIcted fairly well by a kmetrc model havmg the net disappearance rate, gmolelg set
‘Redox format’ The presence of a large number of (subscripts A, B, etc refer to the com-
kinetic parameters made tt difficult to obtam a precise ponents, subscrlpts 1, 2, etc refer to
estimate of the actlvatlon energies of the rate constants the steps m the network)
from the pllot plant measurements, although the reactor estimate of pre-exponential factor of s,
model with tuned kmetlc parameters possessed a gmolejgm set atm
reasonable extrapolative power m the region of low temperature, K (superscrlpts 0 and s
parametnc sensmvlty, provided u-reversible catalyst refer to the observed value and the
deactlvatlon does not take place The very low value for catalyst surface temperature respec-
k, found necessary to explam the performance of the tlvely, subscripts I and C refer to the
reactor IS hkely to be due to loss of active sttes or mlet condltlon and coolant temperature
dlffuslon of oxygen Ions from the bulk lattice to the respectively)
surface becommg rate controlhng as a consequence of overall heat transfer coefficient,
temperature induced stractural modification of the cata- cal/cm* set “C
lyst Since the degree of deactwatlon ~111be more severe weight factors, atm* or OC* (subscnpts A,
near the inlet zone than at the tall end of the bed, the B, etc refer to the responses)
actlvlty profile of the catalyst IS dependent on the axial co-ordinate, cm
developing temperature profiles which are themselves refer to o-xylene, o-tolualdehyde,
influenced by the mltlal actlvlty of the fresh batch of phthahde, phthahc anhydrlde and car-
catalyst, the mlet condltlons of the fixed-bed and on bon oxide respectively
packed-bed dynamics The deactivation effects can be
either reversible or IrreverslbIe depending on the past Greek symbols
hlstory of the catalyst A certam amount of empuical YI GdW&iM -ebb)),
approxlmatlon IS mevltable m modellmg a krnetlc net- gmole cmJg set atm
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 PredIctIon of packed-bed catalytic reactor performance 1331

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