2nd Mercosur Congress on Chemical Engineering

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4 Mercosur Congress on Process Systems Engineering

A KINETIC APPROACH TO ACCESSIBILITY IN FCC CATALYSTS

M. Falco1, E. Morgado2, N. Amadeo3, U. Sedran1,*
1
Instituto de Investigaciones en Catálisis y Petroquímica, INCAPE (FIQ, UNL – CONICET).
2
Centro de Pesquisas e Desenvolvimento Leopoldo A.M. Mello, PETROBRAS.
3
Departamento de Ingeniería Química, (FI, UBA).

Abstract. The process of catalytic cracking of hydrocarbons plays a key role in the refineries that is
expanding in the near future as a consequence of two main factors: the production of petrochemical raw
materials and the conversion of resid feedstocks. The mass transfer process of large molecules through the
catalyst pores and the higher content of contaminants are particular problems of the heavier feedstocks. The
need for specific resid catalysts also requires new characterization techniques. While the Akzo Accesibility
Index AAI measures the dynamic diffusion of hydocarbon molecules and explains the performance of
commercial catalysts, the experimental conditions used are far from those of the commercial process. In order
to consider the simultaneous diffusion, adsorption and reaction of large molecules, a new approach was
developed based on the conversion of 1,3,5 tri-isopropylbenzene (TIPB) as a test reactant over commercial
catalysts and active matrices with different pore sizes. A fluidized bed, stirred batch laboratory Riser
Simulator reactor was used. Alumina matrix components of various mean pore sizes (64, 85 and 201 Å) were
tested at 500 ºC and catalyst to reactant ratio of 2.34 with reaction times between 8 and 25 seconds. Main
products were propylene, di-isopropylbenzene, isopropylbenzene, benzene and a TIPB isomer. As expected,
the activity of these aluminas is much lower than that observed on compound (zeolite plus matrix)
commercial catalysts. A simple kinetic model assuming first order reaction determined that the ranking of
reaction rates was r201 > r85 > r64 , where the subscript refers to the mean pore size. Since the alumina
matrix samples differ mainly in their pore sizes, results can be associated to and considered representative of
the different accessibilities in the matrices.

Keywords: FCC, Accessibility, Resid cracking.

1. Introduction

Two main issues in the operation of modern refineries are the increasing demand to process heavier crudes
and maximize the yields of petrochemical raw materials, that impact heavily on the operation of fluid catalytic
crackers (FCC). Bottoms upgrading FCC catalysts containing active matrices, together with specific additives,
are being increasingly used with that aim (Maglio et al., 1994).
Some very important functions of the matrix are to provide the proper particle size and shape for the
circulation of the catalyst particles in the unit (Marcilly, 1996; Von Ballmoos and Hayward, 1991), to ensure the
best possible contact of reactant molecules with the zeolite component and to crack very large feed molecules
that can not enter the zeolite’s pores (O´Connor and Yanik, 1996). However, the activity of the matrix can lead
to selectivity problems because of the formation of coke and gas products (Dight et al., 1991; Silverman et al.,
1986). In order to improve the bottoms upgrading performance, many catalysts employ high alumina matrices
which are more resistant to the severe deactivation conditions of commercial operation (Otterstedt et al., 1988).
The mass transfer of large molecules through the catalyst pores and the higher content of contaminants are
particular problems of the heavier feedstocks (Yung et al., 2003). In this way, the need for specific resid catalysts
with diffusion properties suitable to handle this type of feedstock, also requires new characterization techniques.

*
To whom all correspondence should be addressed.
Address: INCAPE – Santiago del Estero 2654, 3000 Santa Fe – Argentina.
E-mail: usedran@fiqus.unl.edu.ar
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The concept of “accessibility” was developed to account for this catalyst property. While the Akzo Nobel
Accessibility Index test (AAI) measures the dynamic diffusion of hydrocarbon molecules and explains the
performance of commercial catalysts, the experimental conditions used are far from those of the commercial
process.
The AAI is a test based on the observation of the liquid phase diffusion of large organic molecules into the
catalysts. It is of dynamic character and provides an estimation of the catalyst architecture and accessibility by
measuring the mass transfer rate of hydrocarbons in the catalyst particles (Hakuly et al., 2001). The experimental
conditions do not allow for chemical reactions to proceed.
In order to consider the simultaneous diffusion, adsorption and reaction of large molecules, a different,
kinetic approach can be developed to assess accessibility based on the conversion of a test reactant. 1,3,5 tri-
isopropylbenzene (TIPB) molecules are voluminous, with a kinetic diameter of 9.4 Å (Roos et al., 1997), and
could be used as a test reactant over commercial FCC catalysts and active matrices.
Is the objective of this work to study the catalytic cracking of TIPB over commercial aluminas with different
mean pore diameters and accessibilities that can be considered representative of standard matrix components of
FCC resid catalysts. The behavior of commercial catalysts was used as a reference.

2. Experimental

Three different commercial boehmite samples (Sasol) were calcined at 600 °C during 1 h to form the
corresponding transition aluminas, which were characterized with respect to their textural properties, as shown in
Table 1. The specific surface areas were determined by means of nitrogen adsorption isotherms (BET method),
and the median pore diameters and pore volumes by mercury porosimetry. The AAI was determined following a
standard procedure (Hakuli et al., 2001).

Table 1. Properties of the catalysts used.

Catalyst
Properties A B C
2
Specific surface area (m /g) 202 159 94
Median pore diameter (Å) 64 85 201
AAI 28.9 45.6 34.6
Pore volume (ml/g)
30 - 1000 Å 0.44 0.45 0.67
1000 - 10000 Å 0.02 0.28 0.09

The experiments were performed in an internal recirculation, fluidized bed laboratory unit, the CREC Riser
Simulator reactor (de Lasa, 1992), which was specifically designed for FCC studies. An impeller rotating at very
high speed on top of the chamber that keeps the catalyst between two metal porous plates, induces the internal
circulation of the reacting mixture in an upwards direction through the chamber, thus fluidizing the catalyst.
When the reactor is at the desired experimental condition the reactant is fed through an injection port, and
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immediately after the reaction time is attained, products are evacuated and analyzed by gas chromatography. The
unit has been extensively and successfully used for catalyst evaluation, assessment of kinetic, diffusion and
adsorption parameters, and studies about reaction mechanism; additional descriptive details of the reactor can be
found (de la Puente and Sedran, 2000; Bidabehere and Sedran, 2001). The unit allows for the reproduction of
commercial conditions in the laboratory, such as temperature, catalyst to reactant ratios, fluidization and,
particularly, short contact times.
The reaction conditions were: temperature, 500 ºC, catalyst to reactant ratio of 2.34, and reaction times
between 8 and 25 seconds. The mass of catalyst was 0.4 g in all the cases. The reactant was 1,3,5-
triisopropylbenzene (TIPB, Fluka), used without further purification. The reaction products were analyzed by
on-line standard capillary gas chromatography, using a 30 m length, 250 µm diameter and 0.25 µm film tickness,
non-polar, dimethylpolysiloxane column. Product identification was performed with help of standards and GC-
MS analysis.
The coke content was assessed by a temperature-programmed oxidation and further methanation method
(Fung and Querini, 1992). The mass balances in the experiments closed to ± 5%.
The kinetic parameters for a first order conversion model were assessed through a conventional least-square
optimization method.

3. Results and Discussion

The physical properties of the alumina samples (refer to Table 1) show that they are typical for this type of
solid, and that they represent active matrices in FCC catalysts, particularly those present in resid catalysts. It has
been mentioned that, based on empirical observations, “optimum matrix properties” in resid catalysts are a
specific surface area of approximately 100 to 120 m2/g, with a mixture of meso- (about 60 Å mean pore size) and
macropores (about 200-400 Å mean pore size) (Magee and Letzsch, 1994).
However, the aluminas used differ significantly in their physical properties. Sample A has the smallest mean
pore diameter, about 64 Å, sample B has an intermediate value of 85 Å and sample C shows the largest value of
201 Å. As expected, the larger the mean pore size, the smaller the specific surface area, that ranged from 94 to
202 m2/g.
The differences in mean pore diameters are corresponding to the pore size distributions, as it can be shown in
Fig. 1. The distributions can be considered sharp, with sample B showing some pores of very large size.
The AAI test was developed to be applied to compound FCC catalysts, and the indexes usually range from 0
to 36 (Hakuli et al., 2001). The AAI indexes for these aluminas are in the upper limit of the method, or are even
larger, like in the case of sample B. However, such a high value could be the consequence of the pore size
distribution of this particular sample, that showed a significant contribution of pores in the macropore region
above 1000 Å, while the other samples do not. These macropores, that could be helping AAI to increase, are not
necessarily important concerning catalytic activity, because they would contribute moderately to the specific
surface area.

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2.4

2.2

2.0

1.8
A
1.6

1.4
dV/dLog(D)

1.2
B
C
1.0

0.8

0.6

0.4

0.2

0.0
10 100 1000 10000
Pore diameter (Å)
Fig. 1. Pore size distributions of alumina samples.

The conversion of TIPB has been used by different authors as a test reaction to represent the behavior of
heavy hydrocarbon feedstocks (Falabella et al., 1995; Al-Khattaf and de Lasa, 2000) or to test zeolite diffusion
properties (Al-Khattaf and de Lasa, 2002), due to the large size of the molecule, which has a kinetic diameter of
9.4 Å (Ross et al., 1997). The conversions obtained as a function of reaction time for each sample are shown in
Fig. 2; the profiles indicate that the activities are different.

20

18 C

16 B

14 A
12
Conversion (%)

10

0
0 5 10 15 20 25
Time (s)
Fig. 2. Conversion as a function of reaction time for the various alumina samples. Temperature: 500 ºC.

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Main products in the conversion of TIPB were propylene, benzene, isopropylbenzene, di-isopropylbenzene
isomers, and a TIPB isomer. Typical selectivity curves for the various products are shown in Fig. 3, where it can
be seen that, with the exception of the TIPB isomer, all the other products were stable. Propylene was the most
important cracking product, with molar balances closing to 98-99% if successive cracking steps leading to di-
isopropylbenzenes, isopropylbenzene and benzene that liberate each a propylene molecule, are considered. The
amounts of coke formed were always very small (not more than 0.15% coke on catalyst).

4
Yield (%)

0
0 4 8 12 16
Conversion (%)

Fig. 3. Product distribution in the conversion of TIPB on sample B. Temperature 500 ºC. (
) TIPB isomer; ()1,3 di-
isopropylbenzene; (▲) propylene; (◊) iso-propylbenzene; (▼) benzene; ()1,4 di-isopropylbenzene.

The activity of the samples can be defined by means of the value of the first order kinetic constant for the
conversion of the reactant; in the corresponding kinetic model it was assumed that the reactant is converted
directly into products, and that deactivation was not important, since the amount of coke formed is very low. The
results are summarized in Table 2. As expected, the activity of these aluminas is much lower than that observed
on equilibrium compound commercial catalysts, that also have a certain zeolite load that typically ranges from
10 to 18 %. Moreover, even though the acidic sites on these aluminas are essentially of Lewis nature (Parry, 1963;
Morterra and Magnacca, 1996), they are capable of producing cracking reactions. It can be assumed that the surface
active sites in the various catalysts are similar, since the chemical composition and nature of these aluminas is
the same, and the number of acidic sites in the catalysts, then, would be proportional to the specific surface area.
The values of the kinetic constants on a mass basis for the aluminas in Table 2 are compared with those for
standard equilibrium commercial catalysts that were obtained at 400 ºC (Falco et al., 2003). If these constants are
calculated on a matrix-free basis, that is, referred to the crystalline material in the catalysts, the differences are

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even more significant. However, it is possible to define a ranking of observed activities between the aluminas in
the order C > B > A.
These observations can be rationalized in view of the physical and chemical properties of the samples.
Because the alumina matrix samples differ mainly in their pore sizes, the results can be associated to and
considered representative of the different accessibilities in the matrices. Moreover, since the surface acidity of
these materials is expected to be proportional to their specific surface area, the total number of acid sites is in the
order opposite to that of the observed activities (refer to the values of the kinetics constant on a surface basis, k s ).
Thus, alumina C, with the largest mean pore size would have the highest accesibility followed by aluminas B
and A, respectively. It is to be noted that there is not a full agreement with the AAI values, but it has been
discussed that the AAIs assessed for these samples are in the upper limit, and possibly not reliable range, of the
method. Besides, alumina B shows an important contribution to its pore volume from very large pores which
might influence AAI, but that are not expected to contribute significantly to the catalyst activity. However, a
possible limitation in extrapolating these results with single aluminas to their effective catalytic performance
when embedded in the catalyst matrix may result.

Table 2. Kinetic constants corresponding to a first order conversion model.

Catalyst Temperature (ºC) 109 x ks (cm / s) 103 x k (cm3 / g s)
A 500 3.4 6.8
B 500 5.2 8.3
C 500 9.8 9.2
Commercial cats 400 - 45 – 65
Zeolite in commercial cats 400 - 291 – 758

4. Conclusions

The moderate conversion of 1,3,5 TIPB at 500 ºC over aluminas that can be considered representative of
matrices of commercial FCC catalysts showed a product distribution with a reduced number of products:
propylene, benzene, isopropylbenzene, di-isopropylbenzenes and an isomer of the reactant. The amount of coke
formed was very low. A simple kinetic study allowed assessing the first order kinetic parameters. They were one
or two orders of magnitude lower than those observed on equilibrium commercial FCC catalysts or on the zeolite
components, respectively, that were obtained even at milder conditions. However, a ranking can be defined for
the aluminas that shows that the larger the mean pore size, the higher the observed activity. Since the samples
differ only in their physical properties, this can be correlated with higher accessibility for the voluminous
reactant molecules for the catalysts with larger mean pore size. This approach proves to be simple and trustable
to determine true accessibility to the catalyst active sites, and could be very helpful in characterizing the
properties of matrices in resid FCC catalysts.

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