Catalysis Communications 8 (2007) 1197–1201

www.elsevier.com/locate/catcom

Seven-lump kinetic model for catalytic pyrolysis of heavy oil

Xianghai Meng, Chunming Xu, Jinsen Gao *, Li Li
State Key Laboratory of Heavy Oil Processing, China University of Petroleum, Changping, Beijing 102249, China

Received 25 August 2006; received in revised form 24 October 2006; accepted 26 October 2006
Available online 3 November 2006

Abstract

A 7-lump kinetic model is proposed to describe the catalytic pyrolysis of heavy oil. The kinetic model contains 15 kinetic constants
and one for catalyst deactivation. The experimental data were obtained in a confined fluidized bed reactor. The kinetic constants were
estimated by a special program compiled based on the Marquardt’s algorithm. The apparent activation energies were calculated accord-
ing to the Arrhenius equation. This model fits the experimental data well. The prediction shows that catalytic pyrolysis of Chinese Daq-
ing atmospheric residue should be conducted at low space velocity to produce much ethene and at space velocity around 15 h1 to
produce much propene and butene.
 2006 Elsevier B.V. All rights reserved.

Keywords: Kinetics; Model; Lump; Catalytic Pyrolysis; Heavy oil

1. Introduction
Catalytic pyrolysis of heavy oil has attracted great inter-
ests in recent years [1,2]. A characteristic of catalytic pyro-
lysis is that the reactions are coupled catalytically and
thermally [3]. The kinetics is important to the good under-
standing of the catalytic pyrolysis of heavy oil, as well as to
the design and simulation of the reactor, to the prediction
of the reaction behavior and to the optimization of the
operating conditions.
Lumping kinetics have been studied widely for fluid cat-
alytic cracking [4,5]. Considering the similarity of catalytic
cracking and catalytic pyrolysis, some researchers have
tried to describe catalytic pyrolysis by lumping the large
number of chemical compounds into groups of pseudo-
components, according to their boiling points and molecu-
lar characteristics. Xu [6] presented a 4-lump model for
deep catalytic cracking (DCC) technology. In this model,
dry gas and coke was considered as one lump. Meng
et al. [7] proposed a 5-lump model to describe the catalytic
pyrolysis of heavy oil, in which the lump of dry gas and
*
Corresponding author. Tel.: +86 10 8973 3993; fax: +86 10 6972 4721.
E-mail address: jsgao@cup.edu.cn (J. Gao).
coke was split into dry gas and coke lumps separately.
An 8-lump model was developed by Meng et al. [8] for
the catalytic pyrolysis of heavy oil, where the feed heavy
oil was split into non-aromatic carbons and aromatic car-
bons. Wang et al. [9] developed a 16-lump model for the
heavy oil contact cracking (HCC) process. This model
divided the pyrolysis gas into eight lumps (hydrogen, meth-
ane, ethene, ethane, propene, propane, butene and butane),
and contained 70 kinetic parameters and one parameter for
catalyst deactivation.
The main objective of this study is to develop a 7-lump
kinetic model for the catalytic pyrolysis of heavy oil. With
some assumptions, a mathematical model for the confined
fluidized bed reactor will be given, and kinetic parameters
will be estimated. And then the variation of product yields
with space velocity will be predicted and discussed.
2. Seven-lump kinetic model
2.1. Model description
Pyrolysis gas can be divided into liquefied petroleum gas
(LPG) and dry gas according to the boiling point and the
secondary reactivity. Unlike catalytic cracking, the desired

1566-7367/$ - see front matter  2006 Elsevier B.V. All rights reserved.
doi:10.1016/j.catcom.2006.10.036
1198 X. Meng et al. / Catalysis Communications 8 (2007) 1197–1201

Nomenclature

a deactivation constant, h1 rid disappearance rate of lump i, (mol/cm3) h1

/ deactivation function rif formation rate of lump i, (mol/cm3) h1
e void volume fraction of fluidized bed R gas constant, J/(mol K)
q gas density, g/cm3 RSO steam-to-oil weight ratio
qb catalyst bed density, g/cm3 SW space velocity, h1
Ci concentration of lump i, mol/ggas T reaction temperature, K
GV mass velocity at a cross-section, ggas/(cm2 h) tc residence time of catalyst, h
kij rate constant for the reaction of lump i to lump vji stoichiometric coefficient for the reaction of
j, (g/cm3)1 h1 lump j to lump i
L effective reactor length, cm VR valid volume of the reactor, cm3
Mi molecular weight of lump i, g/mol x reactor length at x cross-section, cm
M average molecular weight of gas mixture, g/mol X nondimensional reactor length
P reaction pressure, Pa yi yield of lump i, wt%
ri reaction rate of lump i, (mol/cm3) h1

products of catalytic pyrolysis are ethene, propene and catalytic pyrolysis of heavy oil. One limitation of this
butene. It was reported that the secondary cracking reactiv- model is that the kinetic parameters depend on the feed
ity of butane was different from that of butane [10]. There- and catalyst properties. One improvement for the model
fore, LPG can be considered as two lumps: propene plus is that the feedstock can be divided into several lumps, in
butene and propane plus butane. Similarly, dry gas can order to predict the cracking reactivity of various feeds.
be split into ethene and other gases (hydrogen, methane,
ethane, carbon oxide and carbon dioxide). Gasoline and 2.2. Kinetic model
diesel are by-products of the catalytic pyrolysis of heavy
oil, and the analysis shows that the main components in Cracking reactions could be considered as irreversible
gasoline and diesel are aromatics. Consequently, gasoline reactions. In order to simplify the kinetic model, first order
plus diesel can be considered as one lump, although they reactions were assumed for the cracking reactions. A math-
are usually considered as two lumps for catalytic cracking. ematical model for the confined fluidized bed reactor was
Coke is a significant by-product since coke yield is an used with the assumption of uniform porosity, plug flow
important parameter for the design of regenerator, and and quasi-steady state. A continuity equation in the reactor
its formation mechanism is different from those of other can be written as Eq. (1) [11,12].
products, so coke alone should be considered as a lump.    
The reaction network for the catalytic pyrolysis of heavy oqC i oC i
þ GV ¼ ri ð1Þ
oil is shown in Fig. 1. An advantage of this model is that it ot x ox t
can predict the yields of the desired products (ethane, pro-
For a first order reaction, the disappearance rate of
pene and butene) directly. Another advantage is that only
lump i (rid) is proportional to its molar concentration
16 kinetic parameters are used to describe the complicated
(qCi) and the mass density of catalyst to gas volume (qb/e).
qb
(Lump1) (Lump2) rid ¼ k i ðqC i Þ  / ð2Þ
e
Heavy k12 Gasoli ne
oil +diesel The formation rate of lump i from lump j (rji) is in direct
k15 k23
k13
k14 k25 proportion to the molar concentration of lump j (qCj), the
stoichiometric coefficient (vji) and the mass density of cata-
Propene k35
lyst to gas volume. The formation rate of lump i (rif) is the
Ethene
+butene sum of all rji.
(Lump3) (Lump5)
hX i q
k24 k16 k26 rif ¼ vji k j ðqC j Þ  b  / ð3Þ
k45 k36 e
Propane k46 The reaction rate of lump i (ri) is the subtraction of the
+butane Other gases
(Lump4) k17 (Lump6) disappearance rate from the formation rate.
k27 hX i q
ri ¼ rif  rid ¼ vji k j ðqC j Þ  k i ðqC i Þ  b  / ð4Þ
Coke(Lump7) e
Fig. 1. Reaction network of the 7-lump model. From Eqs. (1) and (4), we can get Eq. (5).
 X. Meng et al. / Catalysis Communications 8 (2007) 1197–1201 1199
    hX i q
oqC i oC i Stoichiometric coefficient,
þ GV ¼ vji k j ðqC j Þ  k i ðqC i Þ  b  /
ot x ox t e
Mj
ð5Þ vji ¼ ð17Þ
Mi
For the confined fluidized bed reactor, the residence time
Assuming the gas in the reactor to be the ideal gas, then:
of hydrocarbon is much lower than that of catalyst, so the
variation rate of hydrocarbon concentration with time is PM
much lower than that with reactor length. Therefore, the first q¼ ð18Þ
RT
term on the left-hand side of Eq. (5) could be neglected.
The average molecular weight of the gas mixture (M) is a
According to the definition of the mass velocity at a
variant, which varies with X. The average molecular weight
cross-section (GV) and space velocity (SW) [11]
can be calculated by Eq. (19) [11].
S W qb L Pn
GV ¼ ð6Þ i¼0 C i M i 1
e M¼ P n ¼ Pn ð19Þ
Replacing the reactor length at x cross-section by the non- i¼0 C i i¼0 C i

dimensional reactor length (X), Eq. (5) can be re-written as, Where, ‘‘i = 0’’ is considered as the influence of steam on
dC i 1 hX i the average molecular weight. For the proposed 7-lump
¼  vji k j ðqC j Þ  k i ðqC i Þ  / ð7Þ model, n is equal to six, since coke is not in the gas state.
dX SW
The mathematical equations of the seven lumps can be 3. Experimental
written as follows based on the reaction network of the
7-lump model and Eq. (7). Chinese Daqing atmospheric residue was used as the
dC 1 1 feed. The catalyst was CEP-1, a typical catalyst for cata-
¼  ðk 12 þ k 13 þ k 14 þ k 15 þ k 16 þ k 17 Þ  qC 1  / lytic pyrolysis process (CPP) technology. The properties
dX SW
ð8Þ of the feed and the catalyst have been published in an ear-
lier paper [3].
dC 2 1
¼  ½v12  k 12  qC 1 The experiments of catalytic pyrolysis were performed in
dX SW
a confined fluidized bed reactor at four temperatures from
 ðk 23 þ k 24 þ k 25 þ k 26 þ k 27 Þ  qC 2   / ð9Þ
600 to 700 C. The space velocity, the weight ratios of cat-
dC 3 1 alyst-to-oil and steam-to-oil, the flow rates of feeds and
¼  ½ðv13  k 13  qC 1 þ v23  k 23  qC 2 Þ
dX SW steam varied within 5–20 h1, 6–27, 0.2–1.6, 2–10 g/min
 ðk 35 þ k 36 Þ  qC 3   / ð10Þ and 1.5–6.0 g/min, respectively. For each experiment, var-
dC 4 1 iable grams of catalyst were loaded into the reactor with
¼  ½ðv14  k 14  qC 1 þ v24  k 24  qC 2 Þ
dX SW an effective volume of about 580 mL. A variable amount
 ðk 45 þ k 46 Þ  qC 4   / ð11Þ of distilled water was pumped into a furnace to form steam,
dC 5 1 which was used to fluidize the catalyst. The feedstock
¼  ½v15  k 15  qC 1 þ v25  k 25  qC 2 þ v35  k 35  qC 3 pumped by another pump mixed with the steam, heated
dX SW
to approximately 500 C in a pre-heater, and then entered
þ v45  k 45  qC 4   / ð12Þ
into the reactor, where heavy oil contacted with the fluid-
dC 6 1
¼  ½v16  k 16  qC 1 þ v26  k 26  qC 2 þ v36  k 36  qC 3 ized catalyst and reactions took place. The oil gas after
dX SW
reaction was cooled and separated into the liquid sample
þ v46  k 46  qC 4   / ð13Þ and the gas sample.
Coke is a solid deposit on the surface of the spent cata- An Agilent 6890 gas chromatograph with Chem Station
lyst, and its concentration can be calculated through a mass software was used to measure the volume percentage of
balance. components in the gas sample. The equation of state for
 the ideal gas converts the data to mass percentages. The
1 liquid sample was analyzed with a simulated distillation
C7 ¼  C1 M 1  C2M 2  C3M 3  C4M 4
1 þ RSO gas chromatogram to get the weight percentage of gasoline,
,
diesel and heavy oil. Coke content on the spent catalyst
C 5 M 5  C 6 M 6 M7 ð14Þ was measured with a coke analyzer.

Catalyst deactivation function, 4. Results and discussion

/ ¼ expða  tc Þ ð15Þ
4.1. Kinetic constant determination
Concentration of lump i,
y i =M i The kinetic constants of the 7-lump model listed in
Ci ¼ ð16Þ
1 þ RSO Table 1 were estimated by a special program compiled in
1200 X. Meng et al. / Catalysis Communications 8 (2007) 1197–1201

Table 1
Kinetic constants of the 7-lump model
Parameter Unit Reaction temperature, (C)
600 630 660 700
k12 (g/cm3)1 h1 2.64 · 104 4.22 · 104 6.48 · 104 1.02 · 105
k13 (g/cm3)1 h1 3.09 · 104 5.08 · 104 7.63 · 104 1.06 · 105
k14 (g/cm3)1 h1 9.46 · 103 1.19 · 104 1.41 · 104 1.74 · 104
k15 (g/cm3)1 h1 8.05 · 103 1.26 · 104 1.96 · 104 3.18 · 104
k16 (g/cm3)1 h1 5.32 · 103 9.89 · 103 2.04 · 104 4.50 · 104
k17 (g/cm3)1 h1 9.99 · 103 1.27 · 104 1.69 · 104 2.29 · 104
k23 (g/cm3)1 h1 6.86 · 102 1.36 · 103 2.23 · 103 3.46 · 103
k24 (g/cm3)1 h1 8.79 · 102 1.87 · 103 2.55 · 103 3.59 · 103
k25 (g/cm3)1 h1 1.92 · 103 2.86 · 103 5.22 · 103 7.94 · 103
k26 (g/cm3)1 h1 1.65 · 103 2.83 · 103 5.51 · 103 8.57 · 103
k27 (g/cm3)1 h1 2.10 · 103 4.85 · 103 7.63 · 103 1.04 · 104
k35 (g/cm3)1 h1 9.54 · 102 1.58 · 103 3.16 · 103 6.63 · 103
k36 (g/cm3)1 h1 2.13 · 102 4.71 · 102 1.43 · 103 4.59 · 103
k45 (g/cm3)1 h1 1.75 · 102 3.93 · 102 1.07 · 103 2.92 · 103
k46 (g/cm3)1 h1 1.76 · 102 3.71 · 102 1.58 · 103 4.92 · 103
a h1 39 50 67 96

Matlab language based on Marquardt’s algorithm. The fre-
quency factors and the apparent activation energies listed
in Table 2 were calculated according to the Arrhenius
equation.
The kinetic constants for the cracking of the feed are
much higher than those of gasoline plus diesel, propene
plus butene and propane plus butane. This indicates that
it is the cracking reactions of the feed that primarily take
place for the catalytic pyrolysis of heavy oil. And this also
explains that the proportion of the secondary cracking
reactions of intermediate products to the total cracking
reactions is low.
The apparent activation energies for the cracking reac-
tions of the feed are smaller than those of gasoline plus
diesel, propene plus butene and propane plus butane.
This shows that the secondary cracking of intermediate
products is more sensitive to reaction temperature than
the cracking of the feed. The apparent activation energy
for the catalytic cracking of hydrocarbon ranges from 42
to 125 kJ/mol, and that for the thermal cracking ranges
from 210 to 290 kJ/mol [13]. Most of the apparent acti-
vation energies determined in this research are near or
above 100 kJ/mol. This explains that thermal cracking
plays a significant part for the catalytic pyrolysis of
heavy oil, which shows good agreement with the reaction
mechanistic pathway for the catalytic pyrolysis of heavy
oil [3].
The calculated apparent activation energies are close to
those reported in literature [4,8,14], but are higher than
those for the catalytic cracking reactions at conventional
operating conditions [5,15]. The main reason is that the
reaction temperature for the catalytic pyrolysis of heavy
oil is about 150 C higher than that for the conventional
catalytic cracking.

4.2. Effect test of the 7-lump model

Table 2
Frequency factors and apparent activation energies of the 7-lump model
The comparison of the experimental yields (points) and
Parameter Frequency factor Apparent activation energy the model-predicted yields (line) is shown in Fig. 2, for the
Unit Value (kJ/mol) catalytic pyrolysis of Daqing atmospheric residue at
k12 3 1
(g/cm ) h 1
1.43 · 1010
96 660 C. The predicted yields are close to the experimental
k13 (g/cm3)1 h1 5.60 · 109 87 ones. This indicates that the 7-lump kinetic model can fit
k14 (g/cm3)1 h1 3.41 · 106 43 the experimental data well, and the predicted results are
k15 (g/cm3)1 h1 5.41 · 109 97
reliable.
k16 (g/cm3)1 h1 6.88 · 1012 153
k17 (g/cm3)1 h1 3.55 · 107 59
k23 (g/cm3)1 h1 4.82 · 109 114 4.3. Prediction of product yields with space velocity
k24 (g/cm3)1 h1 5.82 · 108 96
k25 (g/cm3)1 h1 2.99 · 109 104 Fig. 3 shows the predicted variation of product yields
k26 (g/cm3)1 h1 2.30 · 1010 119
with space velocity, keeping reaction temperature, cata-
k27 (g/cm3)1 h1 1.14 · 1010 111
k35 (g/cm3)1 h1 1.93 · 1011 139 lyst-to-oil weight ratio, steam-to-oil weight ratio and res-
k36 (g/cm3)1 h1 3.17 · 1015 221 idence time of catalyst constant at 660 C, 16, 0.6 and
k45 (g/cm3)1 h1 2.07 · 1014 202 0.0083 h, respectively. As space velocity increases, the
k46 (g/cm3)1 h1 6.47 · 1016 244 yields of ethene, coke and other gases decrease, and
a h1 2.98 · 105 65
those of gasoline plus diesel, propene plus butene and
 X. Meng et al. / Catalysis Communications 8 (2007) 1197–1201 1201

35 favors much ethene production. But to produce much

Gasoline+diesel
Propene+butene propene and butene, the space velocity should be about
30 Ethene 15 h1.
Propane+butane
Predicted yield, wt%

25 Other gases 5. Conclusions

Coke
20 A 7-lump kinetic model for atmospheric residue cata-
lytic pyrolysis is proposed. The model contains heavy oil,
15 gasoline plus diesel, propene plus butene, propane plus
butane, ethene, other gases and coke as lumps. The model
10 has 15 kinetic constants and one for catalyst deactivation.
Experimental data obtained in a confined fluidized bed
5 reactor were used to estimate kinetic constants and appar-
5 10 15 20 25 30 35 ent activation energies. The predicted yields agree well with
Experimental yield, wt% the experimental results. The prediction shows that cata-
Fig. 2. Comparison between the experimental yields (points) and the lytic pyrolysis of Daqing atmospheric residue should be
predicted yields (line) at 660 C. conducted at low space velocity to produce much ethene
and at space velocity about 15 h1 to produce much pro-
pene and butene.
30 Propene+butene
a
References
Predicted product yield, wt%

20 Gasoline+diesel
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