Catalysis Today 93–95 (2004) 723–727

A new approach of coke characterization on metal and support for

Pt/Al2 O3 by combination of Al2 O3 and Pt/SiO2
Sunee Srihiranpullop∗ , Piyasan Praserthdam
Department of Chemical Engineering, Center of Excellence on Catalysis and Catalytic Reaction Engineering,
Chulalongkorn University, Bangkok 10330, Thailand

Abstract

The main goal was to study the distribution and probability of chain growth of coke by the combination of Pt/SiO2 representing the
metal sites with 100–120 mesh mixed with Al2 O3 60–80 mesh representing the acid sites. TPO, ESR, IR and Soxhelt extraction analyzed
with GC-14B were employed for coke characterization. From the effects of time, temperature, H2 /HC ratio and modification of catalysts,
it was found that probability of chain growth on both sites were the same. However, the greater accumulation was occurred on the support.
This offered transformation on the gas phase of coke intermediates from the metal, which was primarily responsible for producing the coke
precursors. The roles H2 and promoter was more sensitive to reduce coke and probability of chain coke, especially the effect of K promoter.
© 2004 Elsevier B.V. All rights reserved.

Keywords: Coke; A physically mixed catalyst; Distribution and probability of chain growth of coke

1. Introduction is the criteria. To achieve this objective, the coke deposition

Catalytic reforming has become one of the most important
industrial applications of catalysis. Desired reactions are fa-
vored by high temperature and low pressure conditions that
also favor coke formation [1,2]. Analysis by temperature
programmed oxidation (TPO) generally indicated two types
of coke. The first one burns at low temperatures (poly-
meric carbon), which is associated with the metallic phase.
The second type burns at high temperatures (amorphous
phases/graphitized carbon), corresponded to the support
[3,4]. However, the coke deposition completely separated
on both the metal and the support site has not been inves-
tigated sufficiently so far. Thus, coke formation is studied
through a physically mixed system (Pt/SiO2 represented the
metallic site and Al2 O3 represented the support site). The
main goal was to determine the probability of chain growth
(usually called alpha value) of coke formation on both sites
using Schulz–Flory distribution. Theory of Schulz–Flory
distribution presents the relationship between carbon atoms
and weight fraction or hydrocarbon distribution [5]. That the
rate-determining step of coke formation is polymerization
∗Corresponding author. Fax: +662 639 1830.
E-mail address: suneell@hotmail.com (S. Srihiranpullop).
on catalysts must be recovered by a Soxhelt extraction and
then analyzed through GC/MS in order to better understand
the deactivation process of catalyst.
2. Experimental
The experiments were carried out using reagents as fol-
low: H2 PtCl6 ·6H2 O (Wako), SnCl2 ·2H2 O (Fluka), KNO3
(Merck), Al2 O3 type NKH-3 (Sumitomo) and SiO2 (Merck).
Alumina and silica support were grounded to the require
mesh sizes of 60/80 and 100/120, respectively. The Pt cata-
lyst, the Pt–Sn catalyst and the Pt–Sn–K catalyst were pre-
pared by impregnation based on SiO2 and were calcined
in air at 500 ◦ C for 3 h. The coked catalyst was performed
the dehydrogenation with 10% n-hexane in N2 . The ratio
of physically mixed catalysts of the Pt-based catalyst and
Al2 O3 was 1:1.
The beginning, 0.2 g of the catalyst was packed in quartz
tube (6 mm in diameter). Next, the catalyst was in situ re-
duced in hydrogen with the flow rate of 100 cm3 /min at
500 ◦ C for 1 h. Then, the normal reaction condition was ad-
justed to 475 ◦ C and then the reactant was flowed to the
system with the flow rate of 60 cm3 /min and the H2 /HC ra-
tio of 0 for 120 min. On the other hand, the effects of time

0920-5861/$ – see front matter © 2004 Elsevier B.V. All rights reserved.
doi:10.1016/j.cattod.2004.06.067
724 S. Srihiranpullop, P. Praserthdam / Catalysis Today 93–95 (2004) 723–727

Table 1
The amount, carbon density and probability of chain growth of coke
Effect % C of Coke Carbon density Probability of chain growth

Metal Support Metal Support Metal Support

Time (min)
10 0.28 1.47 2.27 × 105 1.45 × 106 0.29 0.32
30 0.31 1.64 3.73 × 105 2.28 × 106 0.38 0.38
60 0.31 2.10 4.70 × 105 2.33 × 106 0.38 0.47
120 0.36 2.50 8.55 × 105 3.02 × 106 0.67 0.65
Temperature (◦ C)
300 0.28 1.61 8.00 × 104 6.47 × 105 0.20 0.27
400 0.30 1.64 3.27 × 105 1.82 × 106 0.24 0.29
475 0.36 2.50 8.55 × 105 3.02 × 106 0.67 0.65
H2 /HC ratio
0 0.36 2.50 8.55 × 105 3.02 × 106 0.67 0.65
3 0.29 1.34 4.50 × 105 3.04 × 106 0.25 0.31
5 0.27 1.31 6.17 × 105 4.00 × 106 0.24 0.25
10 0.26 1.09 5.43 × 105 3.47 × 106 0.26 0.26
Type
Pt 0.36 2.50 8.55 × 105 3.02 × 106 0.67 0.65
Pt–Sn 0.32 1.73 5.18 × 105 2.07 × 106 0.36 0.29
Pt–Sn–K 0.21 1.26 3.17 × 104 1.83 × 106 0.29 0.29

(10–120 min), reaction temperature (300–400 ◦ C), H2 /HC
ratio (0–10) and modified catalyst (Pt–Sn and Pt–Sn–K cat-
alysts) were also studied. Finally, the coke on the mixed
catalyst was separated by sieve to the Pt-based catalyst and
Al2 O3 with different sizes for TPO, IR, ESR and Soxhlet
extraction analysis.
3. Results and discussions
3.1. Characterizations of carbon deposition, Cx Hy species
and the extracted composition of coked catalysts
It was found that the physical mixtures of Pt/SiO2 with
100–120 mesh size and Al2 O3 with 60–80 mesh size be-
have like Pt/Al2 O3 . This is confirmed by our previous work
[6]. Considering this research, coke was built up on both
the metal site and the support site as listed in Table 1. Coke
accumulation was extremely found to take place on the sup-
port. On behalf of TPO results as illustrated in Fig. 1, the
two peaks around 300 and 425 ◦ C were corresponding to
coke oxidized at the metal phase as reported elsewhere [7].
However, coke accumulated over support sites shows only
a peak around 525 ◦ C. Moreover, the amount of coke radi-
cals on both sites as presented in Table 1 is parallel to the
TPO results. That is most of carbon radicals generated on
the support sites.
The IR spectra of coke samples are illustrated in Fig. 2.
One intense band was detected at approximately 1610 cm−1
which is noticed on both sites. Normally, this band in

Fig. 1. Example of TPO of carbonaceous deposits produced on: (A) the metal site and (B) the support site at 475 ◦ C and H2 /HC = 0 with various times
on stream; (䊏) 120 min, (䊊) 60 min, (䉱) 30 min, and (䉫) 10 min.
 S. Srihiranpullop, P. Praserthdam / Catalysis Today 93–95 (2004) 723–727
Fig. 2. Example of IR spectra obtained after coking at various times over (A) the metal site and (B) the support site.
this region is specific to stretching mode of aromatic sys-
tem [8]. Whereas, there was a significant presence of the
characteristic group of C=C stretching in aromatic ring at
1540 cm−1 on the support site. No IR adsorption bands of
aliphatic hydrocarbons at 2960 and 2800 cm−1 for CH3
and 2930 cm−1 for CH2 were observed for both sites of the
coked catalysts. Thus, only aromatic ring structure can be
identified.
The chemical compositions of coke on the support and
metal sites were extracted by toluene for 24 h and then were
analyzed by capillary column (DB1) for the study of coke
distribution. As described in Fig. 3 and Table 2, it is noticed
Fig. 3. Example of chromatograph of the extracted coke.
725
that the soluble coke was mainly composed of C8 –C12 . How-
ever, the extracted coke on the metal sites was more consti-
tuted of a lower C content (C8 –C10 ) while the C12 fragments
was dominantly presented on the support sites. Additionally,
the total amount of soluble coke was more extracted on the
support sites similar to TPO, ESR and IR results.
3.2. The probability of chain growth
From previous results, coke formation is taking place both
on the metal and on the support sites. Although many re-
searchers studied so far, how the metal and support sites were
deactivated that is not clear. Concerning the Schulz–Flory
theory, the probability of chain growth of coke (α value)
as shown in Table 1 is calculated from the plot of carbon
compositions of the extracted coke. Interestingly, the close
probability of chain growth on both sites was found. It was
attribute to support the transportation of intermediate coke.
The soluble coke molecules were therefore intermediates in
the formation of insoluble coke, which was constituted of the
higher polynuclear aromatics [9,10]. Although coke forma-
tion cannot be avoided, the addition of H2 and promoter is
more sensitive to reduce coke accumulation and probability
of chain coke as illustrated in Table 1, especially the effect
of K promoter. It seems due to the ensemble and electronic
effects [11].
3.3. The relationship of coke formation between the metal
and support site
As mentioned above, the existence of aromatic structure
predominate in coke was confirmed by TPO, ESR and IR re-
sults. It was also found that the similar C8 –C12 structure of
extracted coke as coke precursor was presented on both sites.
The carbon structures of extracted coke were corresponded
726 S. Srihiranpullop, P. Praserthdam / Catalysis Today 93–95 (2004) 723–727

Table 2
Carbon composition of extracted coke
Effect Metal Support

C8 C9 C10 C11 C12 C8 C9 C10 C11 C12

Time (min)
10 57.14 19.74 13.58 1.05 0.00 271.58 213.28 79.28 8.80 0.00
30 136.93 37.76 12.88 4.30 0.00 67.76 36.38 9.05 4.28 0.00
60 110.01 21.41 14.30 4.89 0.00 63.26 308.14 205.28 5.49 0.00
120 284.77 335.36 107.36 12.18 199.08 47.26 431.80 235.78 1.01 115.16
Temperature (◦ C)
300 221.01 121.18 41.88 2.52 0.00 68.73 18.63 9.79 1.09 0.00
400 256.85 32.69 9.41 1.95 0.00 180.6 28.23 12.63 3.83 0.00
475 284.77 335.36 107.36 12.18 199.08 47.26 431.80 235.78 1.01 115.16
H2 /HC ratio
0 284.77 335.36 107.36 12.18 199.08 47.26 431.80 235.78 1.01 115.16
3 415.82 212.30 62.51 4.27 0.00 214.59 143.31 56.21 4.45 0.00
5 159.92 69.96 25.59 1.36 0.00 282.61 138.64 42.32 2.97 0.00
10 138.07 98.55 235.78 1.60 0.00 408.72 388.60 173.57 4.72 0.00
Type
Pt 284.77 335.36 107.36 12.18 199.08 47.26 431.80 235.78 1.01 115.16
Pt–Sn 250.49 123.88 32.61 7.65 6.03 338.17 361.74 156.05 6.95 0.00
Pt–Sn–K 183.76 70.12 21.53 6.41 1.33 378.77 452.21 198.01 5.54 6.64

Fig. 4. Coke formation model.

to the aromatic coke as reviewed above. It is attributed to
many researchers who said that C5 and more than carbon
atom is the main structure of coke precursors [12–14]. The
coke precursor is intermediate and is able to be transported
by the gas phase from the metal site to the support site. More-
over, the same probability of chain growth of coke indicates
that coke is made by the same kind of reactions (especially
polymerization) accounted for the aromatic coke formation.
Therefore, a possible reaction for the coke formation is given
in Fig. 4.
Initially the coke precursor generated on the metal site
and then migrated by either gas phase or surface diffusion to
acid site. Consider the cooperative effect of the physically
mixed catalyst, the transportation of coke precursors by gas
phase reaction may reasonable leading to coke formation
with the same probability of chain growth of coke on both
sites. However, coke accumulation is more concentrated on
the support site because the heaviest components, C12 , were
more deposited on the support site leading to more complex
structure and higher amount of coke.
4. Conclusion
Using the physically mixed catalysts and theory of
Schulz–Flory distribution, we can get the better knowledge
 S. Srihiranpullop, P. Praserthdam / Catalysis Today 93–95 (2004) 723–727 727

of coke formation on the metal and support sites. We realize References

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