Fuel Processing Technology 91 (2010) 714722

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Fuel Processing Technology

j o u r n a l h o m e p a g e : w w w. e l s ev i e r. c o m / l o c a t e / f u p r o c

Coke deposition mechanism on the pores of a commercial PtRe/-Al2O3 naphtha

reforming catalyst
Morteza Baghalha , Mohammad Mohammadi, Arian Ghorbanpour
Department of Chemical and Petroleum Engineering, Sharif University of Technology, Azadi St., Tehran, 11365-9465, Iran

a r t i c l e i n f o a b s t r a c t

Article history: Coke deposition mechanism on a commercial PtRe/-Al2O3 naphtha reforming catalyst was studied. A used
Received 10 December 2008 catalyst that was in industrial reforming operation for 28 months, as well as the fresh catalyst of the unit
Received in revised form 26 January 2010 were characterized using XRD, XRF, and nitrogen adsorption/desorption analyses. Carbon and sulfur contents
Accepted 1 February 2010
of the fresh and the used catalysts were determined using Leco combustion analyzer. The pore size
distributions (PSD) of the fresh and the used reforming catalysts were determined using BJH and Comparison
Keywords:
Plot methods. The Comparison Plot method produced the most reasonable PSDs for the catalysts. Through
Coke deposition
Naphtha reforming
comparison of the PSDs of the fresh and the used catalysts, it was revealed that coke deposited on both
Octane number micropores and mesopores of the catalyst at a constant thickness of 1.0 nm. The constant coke thickness on
BJH the catalyst pore walls in the naphtha reforming process (temp. 500 C) implies that coke deposition
Comparison plot method reaction is the slow controlling step in comparison to the fast mass transfer rate of coke ingredients into the
Alumina pores. The bulk density of the deposited coke on the used catalyst was calculated as 0.966 g/cm3.
Pore size distribution 2010 Elsevier B.V. All rights reserved.
Nitrogen adsorption/desorption
Catalyst

1. Introduction PtRe alumina-supported catalysts. The measurements were made

Platinumrhenium catalysts supported on chlorinated alumina are
widely used in industry for the catalytic reforming of naphtha. The
catalytic function of platinum is dehydrogenation. The chlorine-
promoted alumina support of these catalysts provides the required
acidic sites. The addition of Re to Pt/Al2O3 signicantly reduces the
catalyst deactivation rate [1]. Before suldation, the Re promoter of the
catalyst may be found: (a) in the reduced form alloyed with platinum,
(b) in an oxidized form stabilized by the support, or (c) as a combination
of both of the above [1]. Due to the high hydrogenolysis activity of
metallic rhenium, catalysts containing this metal are treated with sulfur
prior to use in order to passivate this high activity. If an inactive metal
such as Sn is added instead of Re, no such pre-treatment with sulfur is
required. For this reason ReS compound is often considered to be an
inert dilutant which modies the reforming catalyst in a similar manner
to Sn [1]. Fast deactivation of the reforming catalysts may be caused by
the segregation of platinum and rhenium [2]. This segregation may
occur due to either poisoning of the PtRe matrix or dehydroxylation of
the alumina surface during pre-treatment or regeneration. Anderson
et al. [3] further conrmed the stability effect of Re in the reforming
catalyst by measuring the infrared spectra of CO adsorbed on Pt, Re and
Corresponding author. Tel.: +98 21 6616 4577; fax: +98 21 6616 4391.
E-mail address: baghalha@sharif.edu (M. Baghalha).
before and after coking by exposure to heptane at 683K. The coking
severity was in the order of Pt greater than PtRe greater than Re [3].
According to the mechanism of coke formation, aromatic compounds
are produced by the cyclic condensation of relatively reactive aliphatic
compounds that have been formed on the catalyst, and eventually
polymerized to asphaltenes to become precursors of the refractory hard
coke. Consequently, the structure of the refractory coke is believed to be
highly poly-aromatic [4]. The asphaltene aromaticity in the feed is,
therefore, an important factor that is highly correlated with the coke
deactivation mechanism of a catalyst [5]. It is believed that the strong
acid sites of the catalyst support are involved in the coke formation
mechanism [6]. Due to their highly aromatic character, coke species
strongly adsorb on the acid sites, which leads to the reduction of the
catalyst activity.
To regenerate the spent reforming catalysts, hydrogen is rst
circulated through the reformer, causing sulfur desorption. Chlorine is
normally added during this hydrogen treatment step to enhance S
desorption and to increase the chlorine content of Al2O3 to avoid the
formation of excessive SO2 4 poison during the subsequent coke-
burning procedure. During this regeneration step, sulfur deposited on
the metals is removed as SO2 that is partially oxidized to SO3. This, in
turn, readily reacts with Al2O3 and forms Al2(SO4)3, causing permanent
deactivation of the alumina support. Treacy [7] has shown that the
active metals in the catalyst pores agglomerate during operation or
regeneration. Hence, in the subsequent step of regeneration, namely

0378-3820/$ see front matter 2010 Elsevier B.V. All rights reserved.
doi:10.1016/j.fuproc.2010.02.002
 M. Baghalha et al. / Fuel Processing Technology 91 (2010) 714722
oxychloration, the metals must be re-dispersed using circulating gases.
During this step, the presence of Cl and H2O in the circulating gases can
also displace some of the previously formed SO2 4 . Before reformer start-
up, the oxidized metals must be reduced with H2 [8].
Liu et al. [9] performed laboratory reforming tests with different sizes
of catalyst particles under otherwise constant conditions to check for
pore diffusion limitations. They found minimal effect of particle size on
reforming and coking reaction rates. This was consistent with their
estimated effectiveness factor of about 0.9 for 1.6-mm extrudates at
772K. They assumed that the coking kinetics model is based on the
premise that site coverage is the sole cause of reforming catalyst
deactivation. In their other works, Liu et al. [10,11] found that the coking
rate is linear in C5N (ve-membered naphthenes). C5N is the major coke
precursors in n-heptane reforming over an unsulded PtRe/Al2O3
catalyst under conditions close to those of a commercial reformer
[10,11]. They found that there is a distinction between coke depositing
on clean sites (monolayer coke) and coke depositing on already coked
sites (multilayer coke). As a result, the total coke concentration would be
the sum of the monolayer and multilayer coke concentrations. This
model would predict that the actual monolayer coke coverage is never
complete in a nite time. At the same time, multilayer coke formation
would accelerate. Liu and co-workers calculated that after a signicant
portion of the active sites are coked, the rate of multilayer coke build-up
would slow down.
Obviously, Liu et al. [9] have used one of the most comprehensive
modeling approaches to predict the mechanism and kinetics of coke
deposition on the naphtha reforming catalysts. Even for this detailed
modeling approach, their calculations is only based on the measure-
ments of coke ingredient concentration in the naphtha stream passing
through the reactor, as well as the bulk coke concentration accumulated
on the catalyst. Some of the most detailed information about coke on the
catalyst may be obtained through pore size analyses of the catalyst
before and after coke deposition. In the present work, we used the PSD
analyses of a fresh and its used naphtha reforming catalysts to predict
the coke deposition mechanism by analysing the coke thickness on the
pore walls as a function of the pore sizes.
2. Pore size distribution theories
The PSD is an important characteristic for porous media such as the
heterogeneous solid catalysts. Varieties of methods have been
reported by researchers to identify the pore size distribution of
porous materials. One of the experimental analysis that supply raw
data for PSD analysis is the nitrogen physical adsorption at 77K [12].
These methods include: MP [13], Jaroniec-Choma [14], Horvath-
Kawazoe [15], DFT [16], BJH [17], and Comparison Plots [18]. Among
these methods, BJH and Comparison Plots are the methods that are
suitable for the range of mesopores. Each method determines the pore
size distribution based on a unique approach. These two methods
were implemented to determine the PSD of our fresh and its
corresponding used naphtha reforming catalysts. These are briey
described in the following subsections.
2.1. BJH method
In this method, the pore size distribution is determined by means
of analysis of nitrogen desorption data [17]. The applied computa-
tional algorithm is the procedure of Barret et al. [17]. Nitrogen
molecules adsorb on pore walls through a multilayer lm at lower
pressures. At higher pressures, nitrogen molecules ll the pores
through capillary condensation mechanism. The relative pressure that
pore lling takes place by capillary condensation can be calculated
from Kelvin's equation, Eq. (1).
2VL
RT ln P = P0 = 1
rk
715
Where rk is the mean radius of curvature for any given liquid
vapor interface shape. In the case of adsorbing Nitrogen with the
assumed contact angle = 0 (complete wetting), and assuming a
hemispherical shape for the liquidvapor interface that forms in a
cylindrical pore, rk(the mean radius of curvature) will be the pore
radius. Also in Eq. (1), R, T, , and VL are gas constant, temperature,
surface tension, and liquid molar volume, respectively. By using
Eq. (1), the pore radius (rk) in which the capillary condensation is
actively occurring can be determined as a function of the relative
pressure(P/P0). Eq. (1) can be simplied into the following form:
9:574
rk A = 2
lnP = P0
Eq. (2) can be obtained from Eq. (1), assuming: T = 77.35K,
= 8.88 mN/m, and VL = 34.76 cm3/mol. At each relative pressure,
the average nitrogen multilayer lm thickness (the lm adsorbed on
pore walls), t, is calculated from Eq. (3).

1
13:99 2
t A = 3
0:034logP =P0
The amount of nitrogen desorbed can be expressed as the sum of
the amount resulting from pore evacuation and of the amount
corresponding to the decrease of t in the pores which already lost their
capillary condensate. In this method, a cylindrical pore model is
assumed. Pores are treated as non-intersecting, open-ended capillar-
ies that function independent of each other during adsorption or
desorption of nitrogen. The method is useful for determining the pore
size distribution in porous samples containing pore sizes in the range
of 1.5 to 100 nm in radius. When applying this procedure for solids
containing pores larger than 100 nm in radius, the accuracy is reduced
considerably.
2.2. Comparison Plot method
The Comparison Plot method [18] is an important achievement in
characterizing porous structures using adsorption data since the
theory of BrunauerEmmettTeller (BET) [19]. Comparison Plots can
provide pore structure information in a clear and reliable manner
without introducing any major assumption.
The Comparison Plot method is based on comparing the adsorption
data of the porous sample with that of a nonporous reference
substance. From the N2 isotherm on a nonporous reference solid, a
relationship between the statistical thickness of the adsorbed lm (t)
and the relative pressure P/P0 is obtained. The adsorption by the
sample at various relative pressures is then plotted against the
thickness of the adsorbed lm on the nonporous reference at the same
relative pressure. In the present work, we used an empirical equation
that correlates the t values on the nonporous surfaces as a function of
nitrogen relative pressure. For instance, Eq. (4) shows the relation for
activated alumina [18].
h i
2
t = 3:510:20 = log x + 1:49 = 1000log x 0:04 log x 4
2 2
0:32 log x + 2:44 x + 2:24 x
where x is the relative pressure of nitrogen.
By only considering the tangent curve of a Comparison Plot, the
PSD of a mesoporous or microporous solid can be qualitatively
obtained. However, to drive the quantitative pore size distribution,
the adsorption data is calibrated using an established relationship
between the statistical thickness of the adsorbed lm and the pore
size of samples with uniform pore structure and known pore sizes (as
measured by such techniques as XRD and TEM), such as alumina
716 M. Baghalha et al. / Fuel Processing Technology 91 (2010) 714722

pillared clay [18]. Eq. (5) is the best equation that has been obtained
by tting experimental data [18].

2
D = 0:653 0:572 t + 10:764 t 5

where D is the mean pore diameter.

Using Eqs. (4) and (5), the terms dVt/dt and t were converted to
dV/dD and D, respectively. The tangent curves with the variable D are
capable of providing important PSD information that can be used for
comparing the structures of a series of samples with similar surface
properties or examining the structure evolution.

3. Experimental

The catalyst deactivation of a commercial naphtha reforming

process of a petroleum renery in Iran was investigated. The process
consists of 4 catalytic reforming reactors in series. A fresh and its
corresponding used sample of the commercial naphtha reforming
catalysts were obtained from the renery. The spent catalyst had been
in continuous use in the reforming reactor number 1 for the duration
of 28 months. The PtRe/ alumina naphtha reforming catalysts were
tested by XRF and XRD analyses to obtain their elemental and
crystalline structures, respectively. Carbon and sulfur contents of the
fresh and the used catalysts were determined using Leco combustion
analyzer. The two catalysts were also characterized by the nitrogen
adsorption/desorption analyses. The volatile components of the
catalysts were removed (i.e., de-gassed) prior to the nitrogen
adsorption/desorption analyses at 100 C under vacuum pressure for
48 h. The nitrogen adsorption and desorption experiments were
carried out at the normal boiling temperature of nitrogen at 77K.
4. Results
Due to the continuous coking and deactivation of the reforming
catalysts during operation, the process temperature had to be
constantly increased with time (Fig. 1) to compensate for the
deactivation and hence, to maintain a rather acceptable octane
number of the reformed product stream, as shown in Fig. 2. Most
reforming reactions are exothermic; hence, the temperature increase
across each reforming reactor represents the catalyst activity in that
reactor. Plant data has shown that the temperature difference across
the 1st reactor dropped to nearly zero after 28 months of operation.
This is when the reforming process was shut down for catalyst
Fig. 2. Octane number of the reformed naphtha stream at the exit of reforming reactor
number 4 as a function of time-on-stream.
replacement. As a result, it is expected that the used catalyst that was
obtained from this unit was completely deactivated.
Fig. 3 shows the XRD pattern of the fresh reforming catalyst. The
peaks conrmed that the main crystalline matrix was gamma
alumina. The normalized carbon-free and sulfur-free chemical
compositions of fresh and spent catalysts, as measured by XRF are
reported in Table 1. Alumina makes the major component of the
catalysts. As expected, the other important components of the catalyst
were identied as Pt, Re, and chlorine. The carbon and sulfur contents
of the fresh and the spent catalysts, as measured by Leco combustion
analyzer, are reported in Table 2. The BET surface area and the total
pore volume of the fresh catalyst and the used (coke-free basis)
catalyst are also reported in Table 2.
The carbon content of the used catalyst is signicantly high. This is
believed to be the main cause of the catalyst deactivation. As reported in
Table 2, the used catalyst shows some higher sulfur content, as
compared to the fresh catalyst. This may also be a source of catalyst
deactivation. Borgna et al. [20] studied the simultaneous deactivation by
coke and sulfur of Pt/Al2O3 and PtRe/Al2O3 catalysts using n-hexane
reforming with thiophene as the poison species. They found that sulfur
and carbonaceous deposits accumulated essentially on the metallic
fraction and affected the catalyst activity for both Pt and PtRe metal
acid catalyzed reactions. The PtRe/Al2O3 activity was signicantly
decreased by both deactivation processes. They also noticed [20] some

Fig. 1. Naphtha inlet temperature to the reforming reactor number 1 as a function of Fig. 3. The XRD pattern of the reforming catalyst. The peaks marked with A represent
time-on-stream. -alumina phase.
 M. Baghalha et al. / Fuel Processing Technology 91 (2010) 714722 717

Table 1
Normalized carbon-free and sulfur-free chemical composition of fresh and spent
catalysts, as measured by XRF.

Component Wt.%

Al2O3 98.42
SiO2 0.20
Cl 0.63
CaO 0.04
TiO2 0.14
Fe2O3 0.05
Re 0.26
Pt 0.26

changes in the catalyst selectivity that would be interpreted in terms of

selective deactivation by coke and sulfur of individual reaction
pathways involved in the reforming mechanism [20]. Furthermore,
during the coke-burning step of the catalyst regeneration process, sulfur
deposited on PtRe metals is removed as SO2. This, in turn, is partially
oxidized to SO3 and readily reacts with Al2O3 and forms Al2(SO4)3,
causing some permanent deactivation of the alumina support. Hence,
sulfur accumulates on the catalyst as Al2(SO4)3 at the end of each Fig. 4. The nitrogen adsorption and desorption isotherms for the fresh reforming
regeneration cycle and gradually degenerates the catalyst activity [8]. catalyst.
For the current spent catalyst with sulfur content of only 0.12 wt.%, as
reported in Table 2, the deactivation mechanism by sulfur poisoning
seems unlikely.
4.2. Comparison Plot method
The measured nitrogen adsorption/desorption isotherms for the
fresh and the spent catalysts are shown in Figs. 4 and 5, respectively.
According to this method, using Eqs. (4) and (5), the cumulative
Va on the ordinate of the diagrams represents the adsorbed gas
pore size distributions for the fresh and used catalysts were obtained
volume. Due to the sharp slope of the curves at very low pressures
and shown in Fig. 9. The differential pore size distributions based on
(near zero), some micropores exist in the catalyst sample, although
this method, after data smoothing, are shown in Fig. 10. As the data in
their volume is rather small. Intermediate and low slopes at
Fig. 10 shows, the radius of the pores with the greatest abundance is
intermediate pressures suggest the existence of mesopores (capillary
4.2 nm for the fresh catalyst and 3.3 nm for the used catalyst.
condensation region). The slope is not sharp when approaching P/
P0 = 1, which implies that macropores are not present. Nitrogen
5. Discussion
isotherms of both fresh and the used catalysts were analyzed by the
two mentioned PSD methods.
5.1. Interpretation of pore size distributions of the catalysts

In Fig. 11, the differential pore size distributions of the fresh

4.1. BJH method
catalyst based on the two applied methods are compared. As it is
observed, the differential distribution curves based on BJH and
Cumulative pore size distribution based on the BJH method is
Comparison Plot methods and their relevant pore sizes of the greatest
shown in Fig. 6. The differential pore size distribution based on BJH
abundance for the fresh (as well as the used) catalyst are rather
method is also shown in Fig. 7. Due to the point-by-point nature of the
similar.
experimental data in Figs. 5 and 6, the curves in Fig. 7 are not smooth.
For better comparison between the fresh and the used catalysts, it is
essential to t a smooth function through each set of the nitrogen
adsorption/desorption data of Figs. 4 and 5, and subsequently repeat
the BJH method with the smooth continuous data. The results for the
differential pore size distribution based on BJH method after data
smoothing are shown in Fig. 8. From the smooth curves of Fig. 8, it can
be observed that the pore with the greatest abundance has a radius of
4.8 nm and 3.3 nm for the fresh and the used catalysts, respectively.
The total pore volume as measured by the adsorbed liquid nitrogen
volume for the fresh and the used catalysts are 548 mm3/g and
279 mm3/g (or 336 mm3/(g coke-free basis for the used catalyst)),
respectively.

Table 2
Carbon and sulfur contents of the fresh and the spent catalysts, as measured by Leco
combustion analyzer. The BET surface area and the total pore volume of the fresh and
the used (normalized based on the coke-free basis) catalysts are also reported.

Component Fresh Used

S, wt.% 0.05 0.12

C, wt.% 0.05 17.0
BET surface area m2/(g coke-free basis) 220.4 179.5
Fig. 5. The nitrogen adsorption and desorption isotherms for the used (not rormalized)
Pore volume cm3/(g coke-free basis) 0.548 0.336
reforming catalyst after 28 months of industrial operation.
718 M. Baghalha et al. / Fuel Processing Technology 91 (2010) 714722

Fig. 6. The cumulative pore size distribution based on the BJH method.
Fig. 8. The differential pore size distribution based on BJH method (after data
smoothing).
To verify and compare the results obtained by the BJH and the
Comparison Plot methods, it is noteworthy to consider that BJH assumed that during the operation, a uniform cylindrical shell of coke
method is based on the Kelvin equation that is not valid for is formed on the wall of any given pore. Now, consider the denition
micropores. It is known from Fig. 4 that the catalyst contains some of the differential pore size distribution function of the fresh catalyst,
small fraction of micropores. On the other hand, the Comparison Plot f(r), as follows:
method has been established based on calibration of adsorption data
for both micropores and mesopores. Therefore, the Comparison Plot dV
f r = dV = f r dr 6
method is considered the more precise method between the two dr
discussed methods for the prediction of pore size distribution of
porous alumina as the catalyst support. Where, V is the total pore volume. Hence, dV is the volume of pores
After selecting the most appropriate method for PSD prediction, a with the sizes between r and r + dr. The size range of these pores, after
theoretical coke thickness model was developed to predict the coke deposition, becomes r and r + dr with the reduced pore volume
behavior of coke deposition on the used catalyst pore walls. The of dV. Hence, the differential pore size distribution function of the
coke thickness relation as a function of the pore size for the used used catalyst, f(r), is dened according to Eq. (7).
catalyst must be able to relate the PSD predictions of the fresh and the
  dV  
used catalysts as shown in Fig. 10 (these PSDs are based on f

r =

dV = f r dr

7

Comparison Plot method, after data smoothing). dr
To relate the pore size distribution functions of the fresh and the
used catalysts, it is assumed that the catalyst pores are parallel Dividing Eq. (7) by Eq. (6) produces:
capillary tubes with variable radius r and length L. This is a reasonable 0  1
! !
assumption for alumina as the catalyst support [12]. It is further dV f r dr
=@ A 8
dV f r dr

Fig. 7. The differential pore size distribution based on BJH method (before data
smoothing). Fig. 9. The cumulative pore size distribution based on the Comparison Plot method.
 M. Baghalha et al. / Fuel Processing Technology 91 (2010) 714722 719

convert to coke. To develop a relation between r and r, an unsteady

state mass balance for the component coke may be written as Eq. (11).

dr
2rL = rA 2rL Vm 11
dt

where rA represents the coke deposition rate, in units of moles of coke

per unit surface area per unit time. Vm is the molar volume of coke.
Simplifying Eq. (11) results in:

dr
= rA Vm 12
dt

To mathematically model the coke thickness relation, the two

previously mentioned mechanisms of coke deposition process are
separately considered here.
A. Reaction-controlled mechanism:
In this case, it is assumed that coke deposition process is controlled
Fig. 10. The differential pore size distribution based on Comparison Plot method (after by a slow coke formation reaction. Hence, the mass transfer rate of
data smoothing). coke ingredients is fast and their concentrations are uniform at all
times for all sizes of pores. As a result, rA is assumed constant.
The differential volume dV is associated with n pores of fresh catalyst Integration of Eq. (12) in this case, results in:
with radius r. After coke deposition, the differential volume and the radius

of these n pores of the used catalysts are reduced to dV and r, Thickness of coke deposited = T = rr = rA Vm t 13
respectively. Therefore, the ratio of dV to dV can be calculated as follows:
! ! ! !2 Since rA was assumed constant, according to Eq. (13), the thickness of
dV nr2 L r2 r coke deposition at any given time is independent of radius r, i.e., T is
= 9
dV nr 2 L r2 r constant for all pore sizes after a specic period of time. Therefore:

Replacing Eq. (9) into Eq. (8) produces: r = rT 14

  !2 
f r  Differentiation of Eq. (14) at any given time, knowing T is a constant
r dr value, results in:
10
f r r dr

dr = dr 15
From Eq. (10), it is obvious that the differential pore size
distribution functions of the fresh and the used catalysts are Replacing Eq. (14) and Eq. (15) into Eq. (10) produces:
mathematically related if a relation between r and r is known. r  
and r are related by a coke thickness model. The coke thickness and f r rT 2
16
pore size relation is important, since it provides useful information on f r r
the mechanism of coke deposition on the pore walls during the
industrial reforming operation. For instance, coke formation rate (and Based on Eq. (16), the differential pore size distribution of the used
hence, its thickness) inside the catalyst pores may be controlled by the catalyst f(r) is obtained if the differential pore size distribution of the
coke formation reaction or by the mass transfer rate (that depends on fresh catalyst f(r) is known. In our case, we have experimentally
the pore size) of coke ingredients diffusing into the pores where they measured and obtained the distributions of both the fresh and the used
catalysts, i.e., f(r) and f(r), respectively, as shown in Fig. 10 (based on
the Comparison Plot method). Hence, Eq. (16) is used to verify the
mechanism of coke deposition. The constant thickness of coke, T,
deposited on the pore walls is an adjustable parameter that was
obtained by the following constraint:
 

Total pore volume of the used catalyst = f r dr 17
3
= 336 mm = g carbon  free used catalyst

Fig. 11. Comparison of the two applied methods for the fresh reforming catalyst.
After a trial and error method, the constraint of Eq. (17) was met
where T=1.0 nm.
The modeled differential pore size distribution function of the used
catalyst f(r), so obtained, is shown in Fig. 12. In this gure, the
measured differential pore size distribution function of the used
catalyst is also shown. From this gure, it is clear that the predicted and
the measured distribution functions of the used catalyst virtually
superimpose on each other with good precision. As a result, the
mechanism of coke deposition must be kinetically controlled by a slow
coke deposition reaction. For the comparison purposes, the other
possible coke deposition mechanism is also discussed below.
720 M. Baghalha et al. / Fuel Processing Technology 91 (2010) 714722
Fig. 12. The experimental and the predicted differential pore size distribution curves for
the used reforming catalyst, based on the coke reaction rate control (PSDs are based on
Comparison Plot method).
B. Mass transfer-controlled mechanism:
The other coke deposition mechanism as controlled by the slow
mass transfer of coke ingredients into the pores was also
considered to verify the effect of the mechanism on the PSD
function of the used catalyst.
In this case, the slow mass transfer rate of coke ingredients into the
pores of the catalyst is proportional to their diffusion coefcients
into the pores, which, in turn, is proportional to the pore radius r,
according to the Knudsen equation, Eq. (18).
s In the previous section, it was concluded that the constant coke
2 8RT
Dk = r 18
3 M
Where, R is the universal gas constant (J/kmol K), T is the
temperature (K), and M is the molecular weight of the gas (g/mol).
As a result, the overall rate of coke deposition, rA in Eq. (12), is
proportional to the pore radius, r.
rA = k r
Where k is the proportionality constant. Replacing Eq. (19) in
Eq. (12) and its integration for the case B, results in:
r
= Expk Vm t
r
At any given time, the right-hand side of Eq. (20) is constant. Hence,
regardless of the pore size, the ratio of the pore radius after coke
deposition to its original un-coked radius is a constant value (for
convenience, we call this ratio ); i.e.:
r
= 21
r
Obviously, if mass transfer of coke ingredients controls the overall
process, the rate of coke deposition is greater at the pore entrance
and diminishes toward the end of the pore [21]. However, for
simplicity of calculations, r in Eq. (21) is assumed to be the average
thickness of coke in each pore. Differentiation of Eq. (21) for any
given time, results in:
dr = dr
Replacing Eq. (21) and Eq. (22) into Eq. (10) produces:
 
f r
23
f r
Based on Eq. (23), the predicted differential pore size distribution
of the used catalyst f(r) for the case of mass transfer-controlled
mechanism was obtained from the measured differential pore size
distribution of the fresh catalyst. The constant value of in Eq. (23)
is an adjustable parameter that was obtained by the constraint of
Eq. (17). The constraint of Eq. (17) for the case B was met where
= 0.768.
The predicted differential pore size distribution function of the
used catalyst f(r), so obtained based on the mass transfer-
controlled mechanism, is shown in Fig. 13. In this gure, the
measured differential pore size distribution function of the used
catalyst is also shown. From this gure, it is clear that the predicted
and the measured distribution functions of the used catalyst are
very different. As a result, coke deposition is not controlled by the
mechanism of mass transfer of coke ingredients. In comparison, it
was previously shown in Fig. 12 that the slow coke deposition
reaction mechanism was capable of correctly predicting the
differential pore size distribution function of the used catalyst.
5.2. Coke thickness and density from BET surface area measurement
As mentioned earlier, the measured BET surface areas for the fresh
and the used catalysts are reported in Table 2. The average BET surface
area, then, is:
220:5 + 179:4 2
200 m =g
2
thickness model correctly relates the PSDs of the fresh and the used
catalysts. Now, based on the average BET surface area of the catalysts,
and the pore volumes of the fresh and the used catalysts (also
reported in Table 2), the constant coke thickness value can be
independently calculated as follows:
6 3
0:548  0:336T10 m =g 9
1:06T10 m 1:06 nm
200 m2 =g
19
20
Fig. 13. The experimental and the predicted differential pore size distribution curves for
the used reforming catalyst, based on the coke ingredients mass transfer control (PSDs
22 are based on Comparison Plot method).
 M. Baghalha et al. / Fuel Processing Technology 91 (2010) 714722
The coke thickness value calculated here and the value calculated
in Section 5.1.A are within 6% of each other. Hence, this is another
indication that the constant coke thickness model correctly predicts
the coke spread mechanism on the used catalyst.
Furthermore, the coke bulk density on the used catalyst was
calculated as follows:
0:17 = 0:83 g coke=g fresh catalyst 3 6. Conclusions
0:966 g=cm
0:5480:336 cm3 coke = g fresh catalyst
Another approximate coke thickness assessment could also be
carried out as follows. The mean pore radius in a system of cylindrical
pores is given by: brN = 2Vp/S, where Vp is the pore volume and S is
the specic surface area. Now, the application of the data from Table 2
to the fresh and the used catalysts leads to the mean pore values of
4.97 and 3.74 nm, respectively. These values are close to those
corresponding to the maxima of the BJH pore size distributions and
about 1 nm larger than those corresponding to the maxima of the
Comparison Plot pore size distributions. This could stem from the
larger dissymmetry of the pore size distributions obtained by the
Comparison Plot method. On the other hand, the difference between
the mean pores sizes of the fresh and the used catalysts is found to be
equal to 1.23 nm which is not far from that of 1.06 nm calculated
above.
5.3. Comparison with other relevant works
Liu et al. [9] performed laboratory reforming tests and found
minimal effect of particle size on reforming and coking reaction rates.
Hence, they concluded that the coking kinetics controls the deposition
rate of coke. However, they assumed variable coke deposition rates for
different layers which could potentially mean non-uniform deposition
thickness. In contrast, we showed that the coke deposition followed a
reaction-controlled mechanism with a uniform constant coke thick-
ness of 1.0 nm over 28 months of industrial operation in our case.
In general, the mechanism and deposition rate of materials that
cause deactivation of catalysts depends on many factors, such as the
type of catalyst support and the active materials, the depositing
species and the temperature. For further verication of our ndings,
some of the relevant depositing materials that cause catalyst
deactivation are also considered here.
Vogelaar et al. [22] used Raman spectroscopy analysis to measure
coke distribution in spent NiMo gama-alumina hydroprocessing
catalysts. Although they tended to conclude otherwise, coke line-
scans of most of their spent catalyst samples have shown uniform
coke distribution across the cross section of the catalysts.
In a hydrodematalization (HDM) process, the slow diffusion of
large organometallic reactant molecules into the pores control the
deposition and hence, the deactivation process [23,24]. For instance,
Vogelaar et al. [25] measured the vanadium deposition proles on a
HDM catalyst after 300 and 700 h on stream. They found a non-
uniform vanadium deposition prole in a catalyst pellet due to mass
transfer limitations. As a result, a non-uniform pore-plugging
phenomenon occurs in the case of catalyst deactivation caused by
slow mass transfer of ingredients and fast deposition reactions such as
metal deposition.
We recently investigated the mechanism of coke deposition on the
potassium-promoted iron oxide catalyst during industrial ethylben-
zene dehydrogenation at temperatures near 600 C [26]. It was found
that the mesopores of the used catalyst were completely blocked by
hard coke, while the macropores of the catalyst were virtually
unaffected. This case also shows that even at the extreme tempera-
tures of 600 C, coke deposition is not limited by the mass transfer of
coke ingredients. Otherwise, more coke would have been observed on
the macropores.
721
These cases show that the relative rates of deposition reaction and
mass transfer of reactants in each system affect the distribution of
depositing material. In the present investigation of the used reforming
catalyst, we identied that the coke thickness was constant and
independent of the pore size. Hence, coke deposition in our reforming
catalyst was controlled by the slow coke formation reactions.
The BJH method produced wider PSD than the Comparison Plot
method. The latter was deemed to produce the more reasonable PSDs
for the fresh and the used catalysts. Our modeling results show that
coke deposited on the walls of the nano-pores of the catalyst at a
constant thickness of 1.0 nm. The prediction of constant coke
thickness on the catalyst pore walls implies that coke deposition
reaction is the slow controlling step in comparison to the fast mass
transfer of coke ingredients. For the hypothetical case of mass transfer
of coke ingredients as the slow controlling step, the predicted PSD of
the used catalyst was very different with the experimentally obtained
PSD of the used catalyst.
Acknowledgement
Financial support of Vice-Presidency of Research of Sharif University
of Technology is greatly appreciated.
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