REFORMING OF Cg HYDROCARBONS

ON A Pt-Al203 CATALYST

G. B. MARINt and G. F. FROMENT*

Laboratorium voor Petrochemische Tech&k, Ftijksuniversileit, Gent, Belgium

(Received 17 August 1981; accepted 10 November 1981)

Abstract-Isomerization, dchydrocyclization and hydrocracking of C6 hydrocarbons on a commercial reforming

Pt-Ah& catalyst were studied in a tubular reactor. The temperature was varied from 420 to SOO’C, the pressure
from 1.6 to 16 bar, the molar Hdhydrocarbon inlet ratios from 1.5 to 20. Reaction rate equations of the
Hougen-Watson type, corresponding to a bifunctional mechanism, were found to describe the experimental data.
Parameter estimates for the reforming reactions were obtained by application of a generalized least square criterion
to the calculated and observed production rates of the gas phase components. Electrobalance experiments showed
that both the reforming reaction rates and the coking rate decrease exponentially with coke content. Multiplying
the reaction rates with one common exponential deactivation function allowed the prediction of the observed
conversions by one single set of kinetic parameters. The cokmg rate equation was derived by fitting the fmal coke
content profiles obtained in the tubular reactor. The main contribution to coke formation was attributed to
Me-cyclopentadienes.

1. INTRCKtUCTlON 2. EXPERlMENTAL SEIXION

The catalytic reforming of naphtha is one of the major
refinery processes, designed to increase the octane 2.1 Equipment
number of naphtha or to produce aromatics. Reforming The experimental set-up is shown in Fig. 1. The reac-
reactors operate adiabatically at temperatures between tor, shown in Fig. 2, consists of two tubes. The inner
460 and 5WC, total pressures between 7 and 40 bar and tube (o.d. 31.2mm; i.d. 27.7 mm; length 1350mm) is
molar H+/hydrocarbon ratios between 3 and 8. The res- suspended at the top of the outer tube by means of a
trictions on the addition of anti-knock components have welded ring. A central tube (o.d. 2.1 mm; i.d. l&mm;
led to the use of lower HZ partial pressures favouring length 1350 mm) is welded to the intet device. At its
aromatics production. Coking, however, is also increased lower end a net retains the catalyst charge. A Ni-Cr
by these lower pressures. thermocoax slides inside the central tube. Along it eight
To date, few comprehensive kinetic studies of the tubes (o.d. 1.2 mm; i.d. 0.8 mm) with different lengths
reforming reactions have been published. The most im- (325, 425, 525, 654, 785,915, 1045 and 1175 mm) are also
portant and most recent are those of Graziani and welded to the inlet device. They allow high pressure
Ramage[l] and Ramage ef al.[2]. The developed rate sampling of the gas flowing through the reactor. In this
equations are essentially empirical and restricted to start- way complete conversion versus W/FHC, curves can
of-cycle activity of the catalyst. easily be determined without changing the flow rate or
Isomerization of the hexanes has been described using the amount of catalyst. On-line gas phase analysis was
first order kinetics by Chevalier et al.[3] and performed on two columns: a squalane capillary column
Christoffet141. The relative magnitude of the first order (i.d. 0.25 mm: length 50m) connected to a flame ion-
rate constants was consistent with the classical bifunc- ization detector and a di-(2ethyl-hexyl)
tional mechanism proposed by Mills et al. [5]. Lambrecht sebacatelchromosorb P packed column (i.d. 4mm;
et al.[6] and De Pauw and Froment[7] investigated the length 4m), connected to a katharometer. The coke
kinetics of the isomerization and cracking of n-pentane content of the catalyst was determined after unloading in
coupled with coking. Following Froment and Bischoff [8, the way already described by De Pauw and Froment[7].
91 the deactivation of the catalyst was related to its coke The electrobalance experiments were performed on a
content. The latter was a function of the process vari- Cahn instrument, type R. G. A heated Valco sixteen way
ables, such as partial pressures of reactants and valve allowed storage of effluent gas samples and sub-
products, temperature, etc. sequent analysis on a OV-101 capillary column (i.d.
This paper reports on a detailed study of the kinetics 0.25 mm; length 50 m) connected to a flame ionization
of C6 hydrocarbons reforming, in the presence of coke detector.
deposition and catalyst deactivation, using a commercial
monometallic reforming catalyst. 2.2 Procedure
To preheat the gas stream the first 150-270mm of the
*Author to whom correspondence should be addressed.
tubular reactor were filled with inert packing. The
tPresent address: Chemical Engineering Department, Stanford remaining part consisted of 9 catalyst sections, alternat-
University, Stanford, U.S.A. ing with inert packing to achieve isothermal operation. In

759
760 G. B. MARIN and G. F. FROHENT

Fig. I. Experimental set-up.

addition, dilution of the first catalyst sections with inert

particles up to a volume ratio of I5 was necessary for
experiments at low pressure. The catalyst was dried in
the reactor at 495°C under a N2 stream (1 mol/hr) when
6.4 wt.% water was desorbed. Subsequent reduction was
obtained at 540°C under a HZ stream (I mol/hr) during
15 h. After this pretreatment, the catalyst still exhibited a
high hydrogenolysis activity, causing hot spots during
start-up. This hydrogenolysis activity was suppressed by
adding 450 wt. ppm sulphur as thiophene to the n-hexane
and feeding 0.5 mol n-hexane/hr at 42O”C, 10 bar and a
molar Hdn-hexane ratio of 10. Stabilization of a fresh
(lb charge was achieved after 32 h on oil. Since sulphur was
stripped off by sulphur-free feed, it was continuously
added during the experiments. More details about the
- sulphiding procedure are given elsewhere[lO].
The experimental program under non-deactivating
conditions was carried out one one and the same batch
of catalyst. After stopping the hydrocarbon feed, the
catalyst was purged with Hz (2.5 mol/hr) at reaction
temperature and atmospheric pressure. A standard test
for the reproducibility of the catalyst activity and selec-
tivity was carried out periodically.
No hot spots were experienced in the electrobalance
experiments, owing to the small amount of catalyst.
Hence, pretreatment was confined to drying and reduc-
tion.

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

Most of the experiments were carried out with n- 3. KlNElTC ANALYsrS

hexane (99%; Johan Haltermann, Antwerp). The

hydrocarbon feed was dried over molecular sieves.
Hydrogen (0, <2ppm; HZ0 120 ppm) was further To identify the reactions that are taking place on the
purified by passing it over Pt-Al203 at 300°C and over catalyst, conversion versus W/&c0 curves were deter-
molecular sieves at room temperature. mined at 42O”C, 10 bar and a molar Hz/hydrocarbon ratio
Deactivation due to coking could only be neglected at of 10 for each of the five hexanes. It can be seen from
high hydrogen partial pressures. In all, twenty-seven Table 2 that the following isometitions do not occur:
conversion vs W/F&, curves were determined in the
tubular reactor at total pressures ranging from 10 to 16
bar, molar H+/hydrocarbon inlet ratios from 10 to 20 and %
temperatures from 420 to 480°C. Twentythree of those Z/L
curves were determined with pure n-hexane feed, the
remaining four with each of the Me-pentanes and the m/tv
7
di-Me-butanes. Hydrocarbon flow rates varied from 0.5
to 2.5 mol/hr. The catalyst weight was 141 g. Y== *
Five runs under deactivating conditions were carried
out in the tubular reactor. For each of them a fresh None of these reactions can result from a single 1,
catalyst batch was used. After the standard pretreatment, 2-alkyl shift in a classical threefold coordinated car-
the run extended for 10h. The experimental conditions benium ion. This is neither the case for:
are given in Table I. Runs I, 3, 4 and 5 were performed
with 99% n-hexane. For run No. 2 technical hexane was
used. The sulphur content of the feed was adapted to
maintain the HJHzS ratio of the pretreatment to a fixed
value. Hence the non-negligible initial formation of 2-Me-pen-
The isomerization of n-hexane into Me-pentanes in the tane from 2,2-di-Me-butane is imputed to the rapid
presence of coking was studied at atmospheric pressure isomerization of 2,2-di-Me-butane into 2,3-di-Me-butane
and 490°C by means of the electrobalance technique, and subsequent f-Me-pentane formation. Table 2 also
using about 0.165 g of catalyst. Hydrocarbon flow rates shows initial selectivities for Me-cyclopentane and ben-
varied from 0.2 to 0.5 molelhr and molar HZ/hydrocarbon zene. The absence of Me-cyclopentane formation from
ratios from 0.8 to 3.4. The reactor was operated in a the Me-pentanes indicates the suppression of Pt
differential way. catalyzed ring closure by sulphidation of the catalyst.

Table 1. Experimental conditions of the deactivation runs

762 G.B. MAFCIN andG.F. FROMENT

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).

coe5cients of Frg. 3. The maximum errors caused by where:

lumping are given in Table 4. These are negligible, except
for pure di-Me-butane feeds. F,Mm
(3)
u=-G
3.: Continuity equations
The continuity equations for the gas phase com- j element of R
ponents and for the coke can be written as:
R, =
7 wi
FJ -40
XJ = - j element of x (4)
(1) FHC0

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

Feea 2.2 one 2,3 LIMB 2 HP 3NP Cl”

 G.B.MAFCIN and G.F. FROMENT

-!!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

MCP’L * CH-L butanes. Both the Me-pentanes and the di-Me-butanes

were lumped to reduce computing times. Only adsorption
of the hexanes was taken into account. The activation
energies for the skeletal isomerization and those for the
(iv) hydrocracking: A-L + L + Hz-t cracked products hydrocracking were taken to be equal. Cracking of n-
hexane was not considered. The total number of
rb-c5 - = kD,_c~p.Jl’z parameters amounted to 10. The best global regression
was obtained by the set of rate equations corresponding
to a dual site mechanism for all the single reactions of
where r is the adsorption term accounting for the
the network, HZ being involved in the hydrocracking.
coverage of the Al203 sites by the reacting species:
With this set, more detailed expressions for the ad-
sorption term were tested, which included the adsorption
of components other than the hexanes also. The ad-
sorption constant of Me-cyclopentanes was the only one
that could be determined significantly at the 95% level.
A third adsorption constant could be estimated by
The constants Kc?. KHer. Khacp and KcH are really distinguishing between the adsorption of the n-hexanes
products of adsorption and equilibrium constants. and that of the isohexanes. At the 95%-confidence level
A total of eight such sets of reaction rate equations no significant difference was obtained, however: Kn~ =
were derived. Discrimination among them was im- 12.0 2 2.4 vs KIH = 8.8 2 1.4. Hence, no distinction was
possible by direct process observation and had to be made further on. No temperature dependence of the
achieved by statistical testing. Parameter estimation was constants in the adsorption term could be determined.
based upon a data set comprising the results of the The rate equations arrived at are presented in Table 5.
experiments in the absence of deactivation and the The significance of the frequency factor for the hydro-
values obtained by extrapolation to zero process time of cracking of the lumped di-Me-butanes is low. Differences
the experiments under deactivating conditions. Including between activation energies for isomerization, ring
the latter runs broadened the range of partial pressures expansion and hydrocracking are hardly signficant.
sufficiently to permit an accurate determination of the Figure 4 compares observed and calculated conversions
dehydrocyclization rate and adsorption constants. by integration of the continuity equations (6) for typical
3.4.1 With lumping of Me-pentanes and di-Me- non-deactivating conditions.

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

CES Vd. 37. NO. J--H

766

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

and one for the isomerizations whereby the degree of

branching does change, As pointed out by Froment[t6, 171, these deactivation
functions are preferabIy related to the real cause of the
deactivation, which is the coke content of the catalyst,
and not to process time, as is usually done.
The deactivation functions for the isomerization of
Hence, 5 activation energies, 10 frequency factors and 2
n-hexane to Me-pentanes and for coking were deter-
constants in the denominator were estimated. All 17
mined by means of electrobalance experiments. Several
parameters were significantly determined. Differences
empirical expressions were statistically tested. An
between the activation energy for isomerization with
exponentially decreasing function, $ = em”“‘, gave the
change in the degree of branching, E,^, the activation
best fit for both the isomerization and the coking data.
energy for hydrocracking EA-~~, and the activation
Differences between the values of the deactivation con-
energy for ring expansion EM~P--Brr were not significant,
stants CZ,,~-~~ and uC were found to be marginal, in-
however. A parameter estimation with only three activa-
dicating that the isomerization and coking occur on the
tion energies yields the results given in Table 6. Experi-
same type of active sites and that both involve the same
mental conversions are compared with those obtained by
number of these.
integration of the continuity equations (6) in Fig. 5 and 6.
Time integration of the continuity equation for coke
(7), yields,
3.5 Kinetics of the reforming reactions in the presence of
coking
Cc = 5 In(l + crcRCof). (12)
So far the reforming kinetics were studied at negligible
coke contents of the catalyst. To enlarge the validity of
the developed reaction rate equations, data collected In (12) &” is the rate of coke production corresponding
under coking conditions were added to the set already to the feed composition. Figure 7 compares experimental
used to determine the kinetics of main reactions. results with those calculated for the following set of
 Reforming of C6 hydrocarbons 767

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

ISOWBRIZATIONS 1 re = I\: e-=‘RT (P*-Pg/R*_B) / lP,r)

n: (kmol/kg cat.hr) B(kJ/mol)

ne-_ 2WP 1.715 lOl0 (14.7, 147.3 (35.3)

na ------3MP 1.510 IOlD (15.1) 147.3 (35.3)

2MP =t3MP 8.766 lo8 (12.5) 125.2 ~19.0~

2MP zrzE2.3Dl4B 8.587 IO9 (13.4) 147.3 (35.3,
2,3?mBs==2,2DlB I.029 109 115.2) 125.2 119.0)

-E/RT
RING CLOSURE : ro - A: e (Pn”-P,,,P,/K,,-,,9)/tPar)
A: lkmol/kq car.hr) e(kJ/mol)

4.004 101’ (6.7, 264.6 (19.1,

nH-YCP + H2

PING EXPANSION : ro = n: -E’RT(PnCp-P,,P~/K,.p_Bz) 1 (PHF)

A: ,kmol,kg cat.hc, E ,kJ,mol,

PKPSBE + 3H2 8.496 10ZO (14.1) 147.3 135.3,

-E/riTp ,=
aYDROCRRCK*N‘ : zn = R: e
A

I:(kmol/kg ~at.bdr.hr) E ,kJ,mol,

2MP + El2 -2c; 6.759 ICP (14.9) 147.3 (35.3)

3HP + H2-2C; 9.494 109 (14.0) 147.3 (35.3)

2,2DIIB + fx2--2cg I.076 109 (10.8, 147.3 (35.3,

COnnoN ADSORPTION TERN :

I- = (l+KHex (PnH+Pnp+PDHB) /P, +y$CpPnCp/PH’ 2

768

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.

The same formula and constant were used to express the

RUN “r 3
deactivation of the coking.
3.5.2 Kinetics of the main reactions. The kinetics of the
main reactions determined in the absence of deactivation
were checked by means of experiments in the same
tubular reactor, but under coking conditions. To check
whether or not the uncoupling by (10) is permitted, the
kinetic parameters were redetermined. The calculation of
the objective function S(e) now requires the knowledge
of the coke content of the catalyst at intermediate
process times, cr. Unlike the electrobalance reactor, the
tubular reactor altows the coke content to be determined
after unloading the catalyst only. Intermediate coke con-
tents were obtained using eqn (12) with R,z’(z, tj) cal-
culated from the observed coke contents at the end of a
run:

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

by (14) FROM TABrAE 7

I,
i
CALCULATION OF KINETIC PARAMETERS

ecei.tj’ bY OF MAIN REACTIONS

INTEGRATION OF FRO” TABLE 7

(6)

SUM OF SQUARES

Fig. 9. Parameter estimation procedure for coking reaction rates.

 Reforming of C6 hydrocarbons 771

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

Table 8. Reaction rate equations for coke formation

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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R ideal gas constant, kJ/mol”K rnt. Svmo. Chem. React. Enww. 82-19. Amsterdam 1972.
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RI 30 789.
cat.hr [81 Froment G. F. and Bischoff K. B., Ckem. Engng Sci. 1961
RC coke production rate, kg coke/kg cat.hr 16 189.
R vector of production rates of the independent [91 Froment G. F. and Bischoff K. B., Ckem. Engng Sci. 1962 17
components 105.
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ith reaction Llll Froment G. F., A.1.Ck.E.J. 1975 21 1041.
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coke/kg cat)2 reaktietrchniek Aggregcwtsproefschtift kogn ondenvijs,
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.