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A surging demand for benzene and xylene as raw materials for synthetic resins
and fibers Sn recent years has st~muJat~d severaf de~eJ~pme~ts in converting
taluene to benzene and xylene via disproportionat~on or dea~k~lat~on processes,
These d~spr~portionation or dealkyla~ion processes are normally carried nut in
the vapor phase aver solid acid catalysts at elevated temperatures. The dis-
proportionat~o~ of toluen~ produces benzene and xyfene as the main products~
Some by-p~oduc~s~ such as light paraffins, C9* alkylben~enes and pofycyclic-
aromatic compounds, are also formed. Mordenite C1,21, rare-earth exchanged X
teolite [3,4J and cation-exchanged Y zeolite C5,61 all possess high activity for
the reaction, unfortunately, many of these catalysts show low selectivity for
disproportionation as a result of crack-fngand hyd~odealkylation, F~r~hermore~
their activities decline quickly due to coke deposition and all but cease within
a fe% hours, ~~co~~ngl~~ deve?o~en~ of new toluene d~sproportionatjon cata-
lysts has shifted to the use of composite catalysts [7-101. Oliver and Inove
summar~2ed industrial toluene disproportio~ation research and pointed out that
vapor phase systems with solid catalysts have significant economic advantages
tll3. Successful c~erc~a~ processes have been claimed by S~n~~ajr/~~la~tic
Richfield [113 and Toray rndustrial/~niversaJOil Products [12,133. SeJective
40
EXPERIMENTAL
A once-through up-flow fixed-bed reactor was used for the activity tests. The
reactor is a vertical stainless-steel tube with an inside diameter of 1.8 cm.
The catalyst bed, packed with 30 g of catalyst (3.5 mm dia. spheres), was first
heated to the reaction temperature under a nitrogen flow of 50 ml min -' to
remove any contamination. The reactions were then studied under the following
conditions: temperature, 743-803 K; pressure, atmospheric; WHSV, 0.76. During
each run, samples were taken at intervals and analyzed by an FID gas chromato-
graph with a 8 ft x l/8 in. o.d. stainless-steel column packed with 5% DIDP/5%
Bentone 34 on 100/120 Chromosorb W HP under the following conditions: oven
-1
temperature, 373 K; flow rate, 20 ml min N2; injection volume, 0.5 ul. Exhaust
gas from the reaction and the coke on the used catalyst were subjected to PONA
(paraffin, olefin, naphthene and aromatics) and elemental analyses respectively
for material balance calculation. The minor components in the effluent were
analyzed and identified by GC-Mass spectra and PONA tests. Three kinds of
commercial catalysts, Cat-A, Cat-B, and Cat-C were used in the performance tests.
The characteristics of these catalysts are shown in Table 1. The feedstock of
toluene used in the experiments is a product of the Chinese Petroleum Corporation
and has a purity of 99.9% +.
Cat-A Cat-B &at-&
Catalyst
Composition
Fe203/wt% 0.2
T~~~/~~~ 1.0
ia203/wt?% l-2 0.5 0.3
Physical properties
TIME ON STREAM, hr
system, the reactions were carried out at constant WHSV with different feed
rates and different amounts of catalysts. Figure 1 shows the plot of toluene
conversion vs. time on stream for the toluene disproportionation reaction over
the commercial catalyst Cat-B. Since the curves obtained for two different feed
rates are coincident, it can be concluded that the external mass transfer
limitation is negligible during the test. The results also imply that the
deactivation of the catalyst does not affect the occurrence of external mass
transfer limitation.
Another method of evaluation of the external mass transfer limitation is to
calculate the partial pressure of gas at the surface of the catalyst particles
in fixed bed reactors. This method was developed by Yoshida et al. C32J. Using
this method, in the present reaction system, the modified Reynolds number was
1.42, the rate number varied from 3.23 x 10m3 to 8.0 x 1o-4 in the reaction
period, and the Schmidt number was estimated to be 0.68. By using these data
the partial pressure gradients were estimated and found to vary from 3.6 x low3
to 0.9 x 10-3, indicating that there was no significant external mass transfer
limitation in the given reaction system.
In order to test intraparticle mass transfer limitation, the reactions were
also carried out over the same kind of catalysts with various diameters. The
results are shown in Figure 2, where the curves arecoincidentinitially but
43
diverge slightly'towards the end of the run. This indicates that there is no
significant intraparticle mass transfer limitation for the evaluated catalysts
in the following performance tests. The slight divergence of the plots indicates
a little intraparticle mass transfer limitation due to slight pore-plugging
which occurs only after severe coking. Since the operational conditions for
c~mercial application and our experimental mode? did not cause severe coking,
the intraparticle mass transfer limitation can be neglected in the present work.
o Cat -A
r Cat--B
l Cat-C
I I I I
0.5 I.0 1.5 2.0
TIME ON STREAM, hr
Y-,. = kCTma
(1)
- $ = kda"
(2)
44
intercept =ln kr
TIME ON STREAM, hr
yT = kCTa
(3)
_ da
= kda
X (4)
45
(5)
a = a eekdt
0
For the constant plug flow of fluid, the performance expression combined with
w'FT,O =
J
'T
o
dXT=
YT s
'T
0
dXT
kaCT
-1
= kaCT o
,
s
'T
'T,O
dCT
CT
(7)
(8)
were varied from 743 to 803 K. Figure 5 shows the conversion of toluene VS.
time on stream.
The reaction rate constant k and catalyst deactivation rate constant kd are
expressed in the Arrhenius form,
46
TABLE 2
Reaction and catalyst deactivation rate constants of commercial CatalyStS at
773 K.
TIME ON STREAM, hr
k = k’ e-Ea/RT (10)
0
-Ed/R7
kd = kfl,o e (12)
where E, and Ed are the activation energies of the main reaction and catalyst
deactivation respectively.
Plots of In k and In kd against l/T are shown in Figure 6. As can be seen,
astraightlinewasobtainedforthcplotoflnkvs.l/Tandacurveforlnkdagainst
l/T. Therefore, In k against t/T follows an Arrhenius law, whereas In kd against
t/T does not. The curve of ln kd against l/T can be approximated to two straight
line plots, as shown in Figure 6, with one straight line plot representing a
higher activation energy than the other.
1.25 1.30 1.35
1 /TX mOCK-'1
coke formation in the two reaction regions is due to two different kinds of pre-
cursor. From GC-Mass analysis of the effluent, minor components were identified
and accounted for as shown in Figure 7. The majority of components are poly-
A+S + (12)
e SA
o+s e + sO (13)
se = St - s* - so (14)
dSe
-[kACA + kGCC]Se
TE= (15)
da -E '/RT
-Ck;CAe A + k" C'e-Et?RT] a
X= 0 0 (16)
where E;\ and E;1 are the adsorption activation energy of the precursors A and 0
respectively.
Since the numbers of aromatic rings and methyl groups do not change during the
disproportionation reaction, we assume that the concentrations of precursors A
and 0 are independent of the disproportionation reaction, and therefore C
and
A
Co can be expressed in terms of the empirical equations
49
(17)
CA = kP, (CT,D)ml (,)~~,-EP~/RT
where E,,,and Ep2 represent the activation energy of the formation of precursors
A and 0 respectively; 'Iis space time.
In our case, CT,O and T are constant, therefore substituting equations (17) and
(18) inti equation (16) gives
_EAjRT -EO/RT
da = -[KAe + KDe la ( 19)
n
where KA = kprki (CT O)ml (~)~l, K. = kp2k; (CT D)mz(~~2,EA=~~ f EP,,ED=E,j+ EP2
Therefore, in the catalyst deactivation mathemaiical model, the temperature-
dependent kd should be taken as
-EA/RT -ED/RT
kd = KAe + Koe (20)
0 msv=o.50
50 A wHSV=O.76
OS n wI-Isv= 1.00
*
oz 40
m
z
2 30
2
s
w 20
wz
2 10 -experiment
a ----computer sw3lat ion
38
34
30
26
22
18
REACTION TEMPERATURE, K
the fluid varies from Point to point along the flow path; Consequently, the
(23)
vely; a(T) is the fractional catalyst activity and a function of the reactor
length 1.
9s = $ = catalystmoving rate
A- (24)
dt = A dl
F (251
da
= ($ 1 kda(ll
di (26)
Incorporating equations (lOI and (20) into equations (23) and (26) with the
boundary conditions, l=O, a=1 and CT=CT Q, the optimal operation temperature for
certain Qs can be calculated by compute; simulation. Theresults are shown in
Figure 9. These indicate that the higher the catalyst flow rate, the higher the
Optimal operation temperature for toluene conversion at constant Q, and the
higher the steady-state conversion_
52
CONCLUSION 3
The optimal operation temperatures for the reaction at constant QL* loo m /
,.,,.
with values of ~~ at 110, 190, 270 and 350 m3/hr were found to be 7B8y 803,
813 and 825 K, and gave a toluene conversion Of 28.5%, 34.6%~ 37.5% and 39*5%
respectively. From the simulation data shown in Figure 9, we ak0 brunt that ill
the reaction conditions: temp. = 758 K, WHSV = 0.76, QL = 100 m3/hr and Q, =
190 m3/hr the reaction gave 28.3% toluene conversion, while the actual
commercial plant running at the same conditions gave 27.0% conversion, The
difference between the semi-empirical model and plant operation for toluene
conversion is less than 5%.
ACKNOWLEDGEMENTS
The authors wish to express their sincere thanks to Dr. J.L. Fan for her help
in GC-Mass analysis and Mr. D.S. Hwang of the xylene plant at the Kaoshiung
Refinery of the Chinese Petroleum Corporation for many fruitful discussions.
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53