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ON A Pt-Al203 CATALYST
759
760 G. B. MARIN and G. F. FROHENT
2.3 Conditions
The catalyst used in this investigation was the com-
mercial reforming catalyst CK 306 of Cyanamid-Ketjen
(Akzo Chemie), having a surface area of 179m21g and
containing 0.59% Pt and 0.67% Cl.
Preliminary runs permitted to determine that internal
transport limitation was negligible with particle sizes
smaller than l.Omm. Hence, the catalyst was crushed
and sieved to O.&l.0 mm size. The absence of interfacial
Fig. 2. Details of tubular reactor. partial pressure and temperature gradients was checked.
761
Table 2. Initial selectivities for isomers, Me-cyclopentane- and benzene-formation from the five hexanes
Bifunctional ring closure would require the formation of Hydrocracking proceeds through transition of a pri-
a primary carbenium ion, which is less stable. The Me- mary into a more stable secondary carbenium ion:
cyclopentane formation from n-hexane on the other
hand is consistent
of n-hexaue through
with the possibility
a secondary
of C5-ring closure
carbenium ion. The x0->* +l+/
absence of benzene formation from n-hexaue can be
explained in the same way as the absence of Me-cyclo- Other cracking paths of the intermediate carbenium ions
pentane formation from the Me-pentanes. demand a transition to a less stable methylcarbenium ion.
Cyclohexane was not detected. With pure n-hexane The above considerations tead to the reaction network
feed the Me-cyclopentane to benzene ratio varied, as the shown in Fig. 3 in which all the steps proceed by a
n-hexane conversion increased, from 16000 to the equil- classical bifunctional mechanism. Figure 3 also gives the
ibrium ratio of 0.55. This would point towards Me- first order rate coefficients determined in a preliminary
cyclopentane as an intermediate in the dehydrocy- kinetic analysis by means of linear regression. The rela-
clization of n -hexane. tive reaction rates for isomerization agree with those
Distributions of the cracked products in the reforming derived by Christoffel[4] for a network which is less
of the five hexanes are shown in Table 3. Some inter- complete, however, since it does not consider benzene
ference due to the fast isomerization reactions is obser- formation. The high isomerization rates between the
ved. These product distributions cannot be rationalized Me-pentanes, and between the di-Me-butanes is
through hydrogenolysis, i.e. cracking on the Pt function. explained by the intervention of secondary and tertiary
They are consistent with hydrocracking, i.e. bifunctional carbenium ions and suggests the possibility of simplify-
cracking. With 2,3-di-Me-butane, e.g. the non-selective ing the reforming reaction network by lumping. The
hydrogenolysis of the C-C bonds would yield 20% of lumping criterion of Kuo and Wei[l41 has been applied
propane. to the five isohexanes using the isomerization rate
Table 3. Composition of the C3 fraction obtained from the five hexanes (at W/F&
Reforming of C6 hydrocarbons 763
If 0.16
(6.01
12.43
0.44
(1 .I)
Fig. 3. Reaction network and first order reaction rate constants (with I values between brackets) at 420% 10 bar
and molar I&/hydrocarbon inlet ratio of 10 (units: IO-‘kmollkg cat.hr.bar).
dCC Rc = 7 rci. (9
ar=Rc 0)
with initial and boundary conditions: Since the interstitial velocity, U, is about 0.5 m/s and no
appreciable deactivation occurs over time periods of the
x=0 at z=O, t?O order of seconds, the non steady-state term in (1) can be
neglected. The partial differential equations (I), (2) are
Cc=0 at ISi, OSzlz, then reduced to a set of ordinary differential equations:
Table 4. Maximum deviations in mole fractions caused by lumping of the Ma-pentanes, and the di-Me-butanes
when pure hexanes arc fed
-!!E._=R eqns (6) and (7). Details about the integration procedure
along t = constant (6) will be given in the corresponding section. With one
d+
( uco > response only, the minimization of (8) was reduced to the
minimization of the sum of squares of the residuals
d&_&
along w = constant (7) between observed and calculated coke contents.
dt FHCO
To facilitate the estimation of the activation energy in
withx=Oat W/FHa=O,t=O the Arrhenius equation, the latter was reparameterized as
follows:
Cc = 0 at t = 0. 0 5 WIFH.c+, I WJF,c,.
k=Aoexp(-&)= AQexp( -& (f-k)]
Under non-deactivating conditions only the continuity
equations for the gas phase components have to be (9)
considered, of course.
With T,,, the average temperature of all experiments.
3.3 Parameter estimation and model discrimination Equilibrium constants were calculated from the free
procedure energy data tabulated in API-project No. 44, 1974.
The data analysis was performed as outlined by
Froment [ 1 l] and Hosten[ 121. Maximum likelihood
parameter estimates B were obtained by minimization of 3.4 Kinetics of reforming reactions in the absence of
the objective function S(6): coking
From a closer look at the underlying mechanism it is
clear that the reaction kinetics can only obey first order
with respect to the hydrocarbon partial pressure when
the total pressure and the hydrogen to hydrocarbon ratio
where v is the number of responses, n the number of is constant. Bamage et al.[2] accounted for this pressure
performed experiments and wt, the (j, I) elements of the dependency by expressing the pseudo-first order rate
inverse of the covariance matrix of the experimental constants as hyperbolic functions of the partial pres-
errors on the responses Y. The covariance matrix was sures. In the present study the Hougen-Watson approach
determined from an unweighted (wrl = 1) preliminary was applied.
parameter estimation. S(g) was minimized by means of a Isomerization, dehydrocyclization and hydrocrackiig
generalized Marquardt routine. The parameter estimates were found to be enhanced by additional chloriding of
were tested for significance by means of their t values. the catalyst. Isomerization appeared to be independent
The significance of the global regression was expressed of total pressure. It may be concluded from these
by means of the ratio of the mean regression sum of observations that the rate determining steps for the
squares to the mean residual sum of squares[ 131. The reforming reactions occur on the acid Al~203 function, as
adequacy of the models was tested by an analysis of already concluded by Hosten and Froment[l5] from
residuals. Discrimination among rival models was based their study of the isomer&&ion of n-pentane. If ad-
on this statistical testing, whenever it was not possible by sorption or desorption of the olefins were the rate
direct process observation or physico-chemical laws. determining steps feeding one of the isohexanes would
The differential method was used for the kinetic lead to primary formation of all the isohexanes. Table 2
analysis of the reforming reactions. Hence the response shows this is clearly not so. Therefore, the surface
vector Y consisted of the production rates R of up to 7 reactions on the AbOrfunction are rate determining.
independent components: the cracked products, 2,2-di- Both single and dual site mechanisms were considered
Me-butane, 2,3-di-Me-butane, ZMe-Pentane. 3-Me-pen- in deriving possible sets of Hougen-Watson rate equa-
tane, Mecyclopentane, and benzene. n-Hexane, and tions for skeletal isomerization. ring closure of n-hexane
hydrogen were obtained from the C- and H-mass and ring expansion of Me-cyclopentdne. For the hydro-
balances. Experimental production rates were deter- cracking reactions possible intervention of HZ through a
mined by fitting the conversion vs WIFH~o curves by Rideal mechanism was also considered. The set of rate
means of analytical expressions, followed by differen- equations corresponding to a single site mechanism for
tiation according to eqn (6). The raw data under deac- the first group of reactions and a dual site Bideal
tivation conditions were obtained in the form of x vs mechanism for the hydrocracking are given below, by
process time plots with W/Fw, as parameter. Cross way of example.
plotting led to plots of x vs W/F,.=,,. To eliminate effects (i) skeletal isomerization: A-L P B-L
of deactivation, introduced by sampling at different
process times, each of the individual x vs W/FHco curves rte = ~:-&~-PJK..--B)IP~II
had to be constructed for a unique process time. This
required interpolation on the original I vs process time (ii) ring closure of n-hexane: nH_L G MCP + L
plot [7].
The coking rate equations were determined by means r&,n = k%MCdPH - P~~PPHIK~H--McP)/-IQ
of the integral method of kinetic analysis. The estimates
of the coke contents were obtained by integration of (iii) ring expansion of Me-cyclopentane:
Reforming of C6 hydrocarbons 765
Table 5. Reaction rate equations, parameter estimates and t values (between brackets) obtained by analysing the
data corresponding to zero coke content of the catalyst. Lumped Me-pentanes, and di-Me-butanes
f2 33 “
1k;=car.hr%n0l)
W’FHCa
Fig. 4. Conversions at 479.4-C, 10.0 bar, y = 20.05 and n-hexane feed. Reaction rate equations from Table 5.
Experimental: points; computed: full lines.
3.4.2 With Me-pentanes as well as di-Me-butanes con- 3.5.1 The deactiuation function. Coke deposition causes
sidered individually. Next, 2-Me-pentane and 3-Me-pen- a deactivation of the catalyst, resulting in a decrease of
tane, as well as 2,2-d&Me-butane and 2,3-di-Me-butane the reforming reaction rates. This can be accounted for
were considered separately. This increases the number by introducing a deactivation function @Ifor each of the
of responses and data up to resp. 7 and 2065. Cracking of so called main reactions:
n-hexane or 2,3-di-Me-butane was not considered. Two
activation energies for the skeletal isomerizations were
used: one for the isomerizations without change in the
degree of branching, The coking rates themselves may, of course, also decay
by coke deposition:
ErA = EZMP--3~. = Ez.m~e-+.~DMB
Table 6. Reaction rate equations, parameter estimates and t-values obtained by analysing the data corresponding to
zero coke content of the catalyst. The two Me-pentanes and the di-Me-butanes are considered separately
-E/RT
RING CLOSURE : ro - A: e (Pn”-P,,,P,/K,,-,,9)/tPar)
A: lkmol/kq car.hr) e(kJ/mol)
-E/riTp ,=
aYDROCRRCK*N‘ : zn = R: e
A
Fig. 6. Conversions at 419.1”C, 10.0 bar, y = 10.01 and 2,3-di-Me-butane feed. Reaction rate equations from Table 6.
Experimental: points; computed: ful1 lines.
encccri. r,, _ 1
Fig. 7. Coke content and deactivation function, &H--L(P= C&L,, 1,) = d In (I+ >
*f (14)
e-“nH - MPcC. From electrobalance: points; computed: full *f
lines.
To eliminate the effect of the starting value of a, an
iterative optimization of S(8) was performed. The itera-
tion was stopped when two successive sets of parameter
parameters values: estimates agreed within the desired accuracy.
Both the Me-pentanes and the di-Me-butanes were
f&O= 8.,22 1om2kg lumped in the parameter estimation, so that 2715 data
kg cat.hr points, divided over 5 responses were to be treated. No
hydrocracking of di-Me-butanes was considered. The
ffnrr--~~ = 254.8 a; LX,== 223.4 e.
activation energies for isomerization, ring expansion and
hydrocracking were set equal to one another. To reach
Since the other reforming reactions also proceed by a convergence, it was necessary to set the constants KH_
dual site mechanism, it seemed logical to introduce one and KP..WP in the adsorption term at their values from
common deactivation function and one common deac- Table 5. Table 7 shows the resulting parameter estimates.
tivation constant a for all of them: The agreement with those grven in Table 5 is good.
The deactivation constant is smaller than the one
(13) obtained from the electrobalance experiments. This is
Reforming of CS hydrocarbons 769
Table 7. Reaction rate equations, parameter estimates and r-values obtained by analysing data collected with and
without catalyst deactivation. Lumped Me-pentanes, and di-Me-butanes
Fig. 8. Coke contents. Reaction rate equations from Tables 7 and 8. Continuity equations (6) and (7). Experimental:
numbers; computed: full lines.
770 Ii. B. hiNUN and G. F. FROMEN
attributed to the different pretreatment of the catalyst. responding run No. 1 (viz. Table 1). This can be attri-
3.5.3 Coking kinetics. Figure 8 represents the observed buted to the higher Me-cyclopentane and benzene partial
coke content profiles at the end of each of the 5 deac- pressures of run No. 2.
tivating runs performed in the tubular reactor. The molar The parameter estimation and model discrimination
H/C ratio in the coke went down to 0.75 at increasing procedure for the coking reaction rates is schematically
reaction temperatures, indicating coke formation by represented in Fig. 9. To avoid the iterative integration of
dehydrogenated species. The existence of coke profiles the set of differential equations (6). (7) during the mini-
even under isothermal conditions is in agreement with mization of the sum of squares of the residuals between
Froment and Bischoff’s[S] prediction. The ascending the observed and calculated final coke contents, a grid in
coke content profiles suggest coking from reaction the (z, 1) plane is defined by:
products, but since the coke content is not zero at the
inlet of the bed, some coke must originate from a feed
component, or from a component in equilibrium with it,
i.e. appearing in the reaction sequence before the rate
determining step. The feed of run No. 2 (viz. Table I) with W, the cumulative weight of catalyst up to the
contained 3.0% of cyclohexane, which immediately section i, and t,(j = 1, 21) dividing the total duration of
dehydrogenated into benzene and caused a temperature the run in such a way that changes in conversions:
drop over the first sections of the bed. The final coke
contents of this run were higher than those of the cor- X = X(Zi, tj) - X(Zi, tj+l)
CALCULATI3N OF DEACTIVATION
Cc(zi,tj) CONSTANT a
I,
i
CALCULATION OF KINETIC PARAMETERS
(6)
SUM OF SQUARES
are equally distributed. Intermediate coke contents are to the 4 deactivation runs with 99% n-hexane feed, due
calculated in the grid points by means of the inter- to the non isothermal behaviour of the tubular reactor
polation formula (14). Next, the continuity equations for during run No. 2. Several mechanisms of coke formation
the independent gas phase components (6) can be in- were postulated. The best global regression of the four
tegrated along f = tl, yielding the partial pressures ~(4, coke content profiles was obtained with the rate equa-
t,). Using these partial pressures the continuity equation tions given in Table g. The first rate equation cor-
for the coke can be integrated and coking parameters can responds to the condensation between Me-cyclopen-
be estimated. The resulting set of parameters does not tadienes as rate determining step in the coke formation:
necessarily lead to calculated final coke content profiles
that correspond with the_ experimental. Therefore the 2MCP=- + CP,.
calculated coke contents Cc(zi, t,) are compared with the
experimental and correction factors are derived from The second corresponds to condensation of Me-pen-
this. Multiplying the calculated coke contents with the tadienes with benzene:
corresponding correction factors:
MP+- + Bz + Cm_
C&z;, ri) = &(t, r,) (3c(zi, Diolefins were indeed detected by chromatographic
C&i, tf)
analysis. Under the most severe deactivation conditions
leads to new intermediate coke contents. With these the their concentration in the gas phase was as high as 1
calculation of ~(4, ti) and the estimation of the coking mole %. Significant estimation of more than two simul-
parameters is repeated. The procedure is stopped when taneous contributions to coke formation was not possible
two successive sets of parameters agree within the with the data collected in this work. Introducing the
desired accuracy. The parameter estimation was limited adsorption terms of Tables 5 and 7 into the coking rate
Fig. 10. Conversions at 479.2”C, 16.0 bar, y = 20.02 and o-hexane feed. Reaction rate equations from Tables 7 and
8. Experimental: points; computed: full lines.
772 G. B. MARINand G. F. FROMENT
Fig. 11. Conversion into Me-pentanes in different catalyst sections during deactivation ran No. 5 of Table 1.
Reaction rate equations from Tables 7 and 8. Experimental: numbers corresponding catalyst sections; W/FHC~(kg
cat./kmol.hr)= 1.13, 2.22, 4.02, 6.66, 9.31, ll.%, 14.63, 17.81, 21.28; computed: full lines.
Fig. 12. Experimental YS calculated conversions. Reaction rate equations from Tables 7 and 8.
equations gave a poorer fit, even when the powers of the calculated one in Fig. 12. The absence of systematic
driving forces in the rate equations were considered as deviations reflects the adequacy of the rate equations.
supplementary parameters.
5. CONCLUSIONS
A FINALRFSUL.T.5 The Ca fraction of naphtha exhibits the main reform-
Figure 10 compares experimental and computed con- ing reactions: isomerization, ring closure, ring expansion
versions for a set of reaction conditions in which deac- foHowed by dehydrogenation and hydrocracking.
tivation can be neglected. Calculated deactivation and The reaction network and the rate equations developed
coke contents after 10 h are indeed negligible for these in this work are consistent with the classical bifunctional
conditions. Figure 11 shows the observed and computed reforming mechanism. Surface reactions of carbenium
decrease of Me-pentane conversions during deactivation ions on the ALO functions are rate determining and
run 5. Computed coke contents are shown in Fig. 8. The occur by a dual site mechanism. The high rates of
computations were performed by numeirical integration isomerization between the Me-pentanes and between the
of the coupled continuity equations for the gas phase di-Me-butanes, allows these to be lumped in the rate
components and for the coke, (6) and (7), using the rate equations. The introduction of a single deactivation
equations given in Tables 7 and 8. The complete set of function, exponentially decreasing with the coke content
experimental gas phase conversions is compared with the of the catalyst, allows a description of the reforming
Reforming of C6 hydrucarbons 773
reactions in the presence of coking. The amount of I’,, observed value of the jth response variable
experimental effort has been limited to a reasonable level during the ith experiment
by the construction of a tubular reactor with a special W
z axial reactor coordinate, z = -, m,
sampling device. The experimental and modeling ap- PEfi
proach followed in this work is believed to enable a
rigorous study of the reforming kinetics of naphtha. Greek symbols
a deactivation constant, kg cat-/kg cokes
Acknowledgolent-G. B. Mario is grateful to IWONLIRSIA for Y hydrogen/hydrocarbon inlet ratio, mollmol
a Fellowship over the years 1976-1979. I- adsorption term in Hougen-Watson rate
equations
NOTATION void fraction of the bed, m,‘lm’
A0 frequency factor I vector of parameters
Bz benzene PB bulk density of the catalyst bed, kg cat./mr3
c coke pr fluid density, kg/mP
CC coke content, kg coke/kg cat. 4 deactivation function
CH cyclohexane n cross-section of reactor, m,’
CP coke precursor
C; cracked products Subscripts
DMB lumped di-Me-butanes A,&... with respect to A, B, _ _
2,2 DMB 2,2-di-Me-butane A - B reaction A + B
2,3 DMB 2,3-di-Me-butane m mean
E activation energy, kJ/mol t total
4 molar Bow rate of jth component, kmol/hr 0 inlet condition
FHC hydrocarbon molar flow rate, kmollhr
F, total molar flow rate, kmollhr Superscripts
H hydrogen 0 in absence of coke
k reaction rate coefficient ZZ oletin
K equilibrium constant, constant in the adsorp- 2= diolefin
tion term calculated
L active site
M molecular weight, kglmol
MCP REFERFNCES
Me-cyclopentane
MP lumped Me-pentanes [II Graziani K. R. and Ramage M. P., Am. Chem. SOC. Symp.
Ser. 1978 65 282.
2MP 2-Me-pentane
[21 Ramage M. P., Graziani K. R. and Krambeck F. J., Chem.
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n number of experimental conditions [31 Chevalier F., G&net M. and Maurel R., Proc. 6th Inf. Gong.
tlH n-hexane Cat& Vol. 1, p. 478. London, 1976.
PI partial pressure of jth component 141 Christoffel E. G., Ind. Bngng Chem. Proc. Res. Den. 1979 18
143.
Pt total pressure, bar
[51 Mills G. A., Heinemann H., Mill&en T. i-I. and Oblad A. G.,
rA--B reaction rate of ASB, kmol/kg cat.hr Ind. Engng Chem. 1953 45 134.
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cat.hr [81 Froment G. F. and Bischoff K. B., Ckem. Engng Sci. 1961
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components 105.
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Rijksuniversitcit Gent 1978.
t process time Draper N. R. and Smith H., Applied Regression Analysis.
I131
tf process time at end of deactivation run Wiley, New York I!366
T temperature, “K [I41 Kuo J. C. W. and Wei I., Ind. Engng Chem. Fundls I%9 8
Y interstitial velocity, mdhr 124.
number of responses appearing in S(e) 1151 Hosten L. and Froment G. F., Ind. Engng Chem. Proc. lX?s.
Dev. 197110 280.
4 weight of catalyst at reaction i, kg cat.
[ 161 Froment G. F., Proc. 6th Int. Congr. Catal., Vol. 1, p. 10.
Wt total weight of catalyst charge, kg cat. London 1976
xi fractional conversion of component j I171 Froment G. F., Catalyst Deactiuation (Edited by Delmon B.
x vector of independent fractional conversions and Froment G. F.), p. 12. Elsevier, Amsterdam 1980.