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Procedia Engineering 102 (2015) 1758 – 1765

The 7th World Congress on Particle Technology (WCPT7)

Regeneration Kinetics of Spent FCC Catalyst via Coke Gasification

in a Micro Fluidized Bed
Yuming Zhanga,b,*, Guogang Suna, Shiqiu Gaob, Guangwen Xub
a
State Key Laboratory of Heavy Oil Processing, China University of Petroleum-Beijing, Beijing 102249, China
b
State Key Laboratory of Multiphase Complex Systems, Institute of Process Engineering, Chinese Academy of Sciences, Beijing 100190, China

Abstract

In the present study, the spent fluid catalytic cracking (FCC) catalyst is regenerated via coke gasification instead of combustion
in a micro fluidized bed reactor to investigate its reaction characteristics and kinetic parameters. The reaction rate first increased
with carbon conversion ratio and then slowly decreased when reaching the peak. H2 and CO was found to be over 70 vol.% in the
gasification gas. Two reaction models, homogenous model (HM) and shrinking core model (SCM) were used to calculate the
kinetic parameters of catalyst regeneration, finding that HM had better fitting relevance for the data than SCM. The activation
energy from these two models was close to each other, that is, about 150 kJ·mol-1 for the coke gasification over FCC catalyst.
© 2014Published
© 2015 The Authors. Published
by Elsevier by isElsevier
Ltd. This Ltd. article under the CC BY-NC-ND license
an open access
Selection and peer-review under responsibility of Chinese Society of Particuology, Institute of Process Engineering, Chinese
(http://creativecommons.org/licenses/by-nc-nd/4.0/).
Selection and
Academy ofpeer-review under responsibility of Chinese Society of Particuology, Institute of Process Engineering, Chinese Academy
Sciences (CAS).
of Sciences (CAS)
Keywords: FCC catalyst; Steam gasification; Micro-fluidized bed; Regeneration kinetics.

1. Introduction

Fluid catalytic cracking (FCC) process plays a key role in refinery in terms of converting heavier feedstocks (i.e.,
vacuum gas oil, atmospheric residue and vacuum residue) into transportation fuels, such as diesel and gasoline[1].
Conventionally, the spent FCC catalyst is reactivated via coke combustion in the fluidized bed regenerator. It will
generate excessive heat in the system because of its high coke yield when treating heavy oil. External catalyst cooler

* Corresponding author. Tel./fax.: +86-10-89734820.

E-mail address: yumingzhang@gmail.com (Y. Zhang)

1877-7058 © 2015 Published by Elsevier Ltd. This is an open access article under the CC BY-NC-ND license
(http://creativecommons.org/licenses/by-nc-nd/4.0/).
Selection and peer-review under responsibility of Chinese Society of Particuology, Institute of Process Engineering, Chinese Academy of Sciences (CAS)
doi:10.1016/j.proeng.2015.01.312
 Yuming Zhang et al. / Procedia Engineering 102 (2015) 1758 – 1765 1759

or boiler should be applied to extract the heat and maintain the heat balance of the operation, which leads to great
waste of carbon resources and high SOx and NOx emissions during coke combustion. On the other hand, hydrogen
is usually of great deficiency in the refinery, especially processing heavy oil into light oil products [2]. As a result,
the oil cracking combined coke gasification process is proposed, that is, to gasify the deposited coke on the spent
catalyst using steam to produce syngas.
Previous studies on catalyst regeneration are mainly involved in removing coke via air combustion[3,4], and little
publications on FCC catalyst regenerating via coke gasification are found. However, reaction characteristics and
kinetics on carbonaceous materials[5,6], such as coal and biomass, have been widely studied using TG analyzer. The
samples are confined in a fixed bed and its reaction kinetics is obtained from the weight loss data under the specified
reaction atmosphere and temperature program. As a result, TG analysis could hardly reflect the real reaction
behavior of the spent FCC catalyst regeneration process in the fluidized bed.
The micro fluidized bed reactor analyzer (MFBRA) developed by IPE, CAS, is highly suitable for investigating
steam-involved gas-solid reactions [7] and has been used in studying biomass pyrolysis, char gasification and
graphite combustion etc.. The fluidization operation could enhance heat and mass transfer and suppress the diffusion
effect. Gas products are quickly entrained out of the reactor and measured with an on-line mass spectrometer (MS),
further using the data processing software for the reaction kinetics. This study is devoted to investigating the
regeneration characteristics and kinetics of FCC catalyst in MFBRA by simulating the possible catalyst regeneration
conditions.

2. Experimental section

2.1. Apparatus and operation

The schematic diagram of micro fluidized bed reaction system was shown in Figure1, mainly consisting of the
gas-supply and steam-generation unit, the fluidized bed reactor, the pulse feeding and the product analysis part. The
mixture of argon and steam was used as the fluidizing gas. Steam also served as the gasification reagent during the
reaction process. Argon was the purging gas during the interval of each experiment and used as the calibrating gas
during the gasification reaction. Partial oxygen would be introduced into the system as the gasification reagent
together with steam. The micro fluidized bed reactor was made of quartz tube and had an inner diameter of 20 mm
and a total length of about 160 mm. The reactor was divided into three sections by two gas distributors, that is, a
preheating part filling with inert Al2O3 balls, a reaction area with fluidizing medium (inert silica sand with particle
diameter of 100-150 μm) and a purification part for diminishing fine particles. Silica sand was acid-washed, filtered
and calcined to remove the impurities before using as the fluidizing medium.

Presssure sensor Evacuation

Mass
Gas cooler spectrometer
Gas filter-drier
Water collector

Computer
Fluidizing
medium Sample container

Thermocouple Eletromagnetic valve

Furnace
Mass flow meter

Reactor
Mass flow meter Gas valve Gas cylinder
Three-way valve

Steam generator Pump Water tank

Fig. 1. Schematic diagram of micro-fluidized bed reactor analyzer.

1760 Yuming Zhang et al. / Procedia Engineering 102 (2015) 1758 – 1765

Silica sand of 4 g was put in the reactor as bed materials and about 150 mg coke containing catalyst was set in the
pulse-feeding container. When the temperature was reached, the sample was instantly injected into the middle of
high-temperature silica sand. The gasification products were quickly stripped out of the reactor by the upward
fluidizing gas, then purified and detected by the on-line MS. The composition of the produced gas was monitored
until the response lines of MS become stable. Gas composition and concentration was determined using the internal
standard method with the calibrating gas. Each experiment was repeated three times to ensure the relative error less
than 3% and the average value of three experiments were used to calculate the kinetic data.

2.2. Materials and analysis

The coke-containing FCC catalyst was prepared by cracking heavy oil with the fresh catalyst in a fluidized bed,
as detailed in our previous publications[8,9]. The coke content on FCC catalyst was about 2.75 wt.%. The main
composition and properties of FCC catalyst are given in Table 1.

Table 1. Composition and properties of FCC catalyst.

XRF analysis of catalysts (wt.%)
Components Al2O3 SiO2 Na2O Re2O3
Concentration 54.15 37.71 0.25 5.37
Bulk density Sauter Mean Surface area Pore volume Average pore
(kg·m-3) diameter (um) (m2·g-1) (cm3·g-1) diameter (Å)
824.3 62 235.2 0.13 48.7

The carbon content of the spent catalyst was measured with a coke analyzer (CS-344, LECO). The composition
of FCC catalyst was determined using the X-ray fluorescence (XRF) spectrometry (AXIOS), and their particle size
distribution was determined with the laser particle size analyzer (Malvern Mastersizer 2000). An automatic BET
analyzer (Autosorb-1, Quantachrome) was used to measure the specific surface area and pore structure of the
catalyst. The MS (PROLINE AMETEK) was adopted to monitor the real-time gas variation during gasification
process.

2.3. Data processing

The coke on the catalyst was mainly converted into H2, CO, CO2 and CH4 in the gasification reaction, and their
corresponding concentration could be calibrated according to the response value of the MS. So the carbon
conversion value of coke gasification was defined by calculating the carbon-containing gas species (i.e., CO, CO 2
and CH4) in the syngas, as shown in Eq. (1).
t t FAr u (C CO C CH4  C CO2 )
³ t 0
(
22.4C Ar
u 12)dt
(1)
X u 100%
t tg FAr u (C CO C CH4  C CO2 )
³t 0
(
22.4C Ar
u 12)dt

where X (%) is the conversion ratio, t (min) and tg (min) represent the instant and the end of the reaction time,
respectively. FAr (ml·min-1) is the flow rate of argon. CAr, CCO, CCH4 and CCO2 (vol.%) stands for the volume
fractions of Ar, CO, CH4 and CO2, respectively.
Gasification rate R (min-1) is defined as differential of conversion X to gasification time t,
dX (2)
R
dt
 Yuming Zhang et al. / Procedia Engineering 102 (2015) 1758 – 1765 1761

3. Results and discussion

3.1. Regeneration characteristics of FCC catalyst

The effect of external diffusion on gasification reaction was determined at different gas flow rate in the pre-
experiments. The results showed that the external diffusion effect of gasification could be negligible in the
temperature range of 800-950 ć when the flow rate of argon and steam was 200 ml/min and 0.3 g/min, respectively.
Figure 2 shows the gas concentration varied with time in the regeneration reaction of coked FCC catalyst at 900 ć.
The main gas components for the coke steam gasification were H2, CO, CO2 and CH4, and their corresponding
concentration first increased and then slowly decreased to zero at the end of the experiments. However, the time
needed for different gas species reaching the peak differed from each other and their release sequence could be
proximately summarized as: CH4<CO=H2<CO2. The completion time of coke gasification in the micro fluidized bed
was about 4-5 min according to the MS curve.

40
Concentration (%)

30
H2
CO
20 CO2
CH4
10

0
0 2 4 6 18 20
Time (min)

Fig. 2. Gas concentration versus time for steam regeneration of spent FCC catalyst at 900ć.

Literature study[10] showed that the properties of coke deposited on the catalyst were different from the
condensed coke of coal char or petroleum coke. The coke component on the catalyst usually has the H/C ratio of
0.3-1.0. Cerqueira et al. [11] indicated that there are four main types of coke identified in catalytic cracking of
residue oil, that is, reaction or catalytic coke, dehydrogenation or metal coke, Conradson carbon coke and soft coke
(i.e., incomplete stripping and entrained hydrocarbons). Methane is not easy to be produced by the carbon steam
gasification at low temperature (< 1000 ć), so the relatively high content of CH4 in the syngas is probably from the
breakage of condensed nucleus of aromatics due to the coke composition. The cleavage of aromatic compounds is
easier to be conducted than the heterogeneous reaction of carbon-steam gasification, thus resulting that CH4 reaches
the maximum value shorter than that of other gas species. The main reactions for coke steam gasification are
carbon-steam gasification (Eq. 3) and water gas shift (Eq. 4) reaction. Higher temperature will facilitate the steam
gasification of coke and meanwhile generate more H2 and CO. After the heterogeneous carbon-steam reaction, CO
will further react with steam to produce CO2 via the homogenous reaction (Eq. 4). The reaction procedures and
characteristics determine the time sequence of gas emission. The volume percentage of each gas component could
be obtained via integrating the area of the MS curve. The results showed that H 2 took about 52 vol.% in the syngas,
and the sum of H2 and CO was up to 75 vol.%. This kind of syngas could be potentially used as the hydrogen source
for hydroprocessing the liquid oil in the refinery.
C+H2OCO+H2 ᇞH0=118.9 kJ·mol-1 (3)
0 -1
CO+H2O CO2+H2 ᇞH =-45.2 kJ·mol (4)
Figure 3 shows the carbon conversion with time (X-t) and gasification rate with carbon conversion (R-X) in the
regeneration of coked FCC catalyst. High gasification temperature facilitated coke-steam gasification and thus
shortened the completion time needed for coke gasification. Figure 3a shows that about 45 min was necessary for
1762 Yuming Zhang et al. / Procedia Engineering 102 (2015) 1758 – 1765

the coke gasification over FCC catalyst at 800 ć, while the completion time decreased to less than 10 min at 950 ć.
For each specified gasification temperature, the gasification rate first increased with carbon conversion ratio and
then slowly decreased, and reached the maximum at the carbon conversion ratio of 5-20% (Fig. 3b). Sahimi et al.
[12] indicated that the difference of the initial pore volume was the main reason for the occurrence of the maximum
gasification rate. In the cracking reaction of heavy oil, coke molecules can be heterogeneously distributed over the
surface or diffused into the inner pores of the catalyst particles. At the beginning of gasification, steam first contacts
with the coke on the surface of catalyst and the outside of pores. With the on-going of coke steam gasification, most
pores would be open via removing coke at the external surface (pore mouth), thus greatly enhanced the gasification
rate via increasing the contacting surface between coke and steam. Coke content of the catalyst will gradually
decreased with the proceeding of coke-steam gasification, thus resulting in lower gasification rate.

(a) 100 (b)

70
800ć
60
850ć
Conversion X ( %)

80
50 900ć
60 950ć

R (min )
40

-1
800ć
30
40 850ć
900ć 20
20 950ć
10
FCC catalyst
0 0
0 10 20 30 40 50 0 20 40 60 80 100
Time (min) Conversion X (%)

Fig. 3. (a) Carbon conversion with time and (b) gasification rate with conversion of FCC catalyst regeneration at different temperatures.

3.2. Model description of gas solid reaction

There is hardly any reaction function model reported specifically on the catalyst regeneration via coke-steam
gasification. However, the reaction kinetics of coal char and petroleum coke gasification has been fully studied [13,
14]. The typical reaction models for coke gasification are mainly involved in the shrinking core model and
homogenous model, respectively. Shrinking core model (SCM) assumes that the gasification reaction occurs only on
the surface of spherical reactant particles, and the un-reacted core would shrink gradually in the reaction process.
The reaction order of SCM is 2/3. When controlled by the chemical reaction, SCM could be expressed as,
dX (5)
k (1  X )2/3
dt

The integral equation form is,

3[1-(1-X)1/3] = kt (6)
Homogenous model (HM) makes the hypothesis that the active sites evenly distribute inside the solid particles,
and the size of the particles remain to be constant in the reaction process, while only the particle density uniformly
changes. The reaction order of HM is 1. When the chemical reaction is the control step, HM could be written as,
dX
k (1  X )
dt (7)
The integral equation form is,
ln(1-X) = kt (8)
where X, t and k are the reaction conversion ratio, reaction time and reaction rate constant, respectively. The
reaction rate constant k can be expressed via Arrhenius equation in Eq. (9). Applying logarithm to the Eq. (9) and
 Yuming Zhang et al. / Procedia Engineering 102 (2015) 1758 – 1765 1763

expanding k leads to Eq. (10)

E (9)
k = A exp(- )
RT
E (10)
ln k ln( A) 
RT
where A, E, R and T are the pre-exponential factor, activation energy, gas constant and temperature in K,
respectively. The value of lnk is linear with 1/T at a fixed temperature, allowing the determination of activation
energy E from the slope of the correlation line and also the pre-exponential factor A.
The kinetic parameters of coke gasification on the FCC catalyst were calculated using the SCM and HM, as
shown in Fig. 4. The calculated reaction rate constant k and the linear correlation coefficient R2 was presented in
Table 2. For all the curves the value of R2 reached 0.90, while the HM had much higher fitting relevance (R2>0.95)
than that of SCM. As mentioned above, SCM suggests that the particle size of reactants uniformly decreases during
the reaction process, while HM assumes that the particle size is constant in the course of reaction. Coke distributed
as a thin layer on the catalyst. The size of catalyst particles hardly changed even removing all the coke during the
gasification reaction, which was more close to the assumption of HM. During the kinetic study of petroleum coke
gasification in the micro fluidized bed, we observed that the R2 value of SCM was higher than that of HM, which
was different from the results for coke gasification over FCC catalyst. The fine char particles pyrolyzed from coal,
biomass or heavy oil (i.e., petroleum coke) usually have similar properties (i.e., composition) in the outer surface
and inside cores, and will react with gasification reagent on the surface and then shrink uniformly as the reaction
proceeds. Apparently, the reaction process of coal char or petroleum coke is more close to the assumption of SCM,
thus resulting in higher R2 value of SCM than that of HM. This justified from another perspective that the
characteristics of coke gasification could be distinguished from each other in the different reaction systems.

(a) 2.0 (b) 2.5

1.6
2.0
3[1-(1-x)^ ]
1/3

1.2
800ć 800ć
-ln(1-x)

1.5
850ć 850ć
0.8
900ć 1.0 900ć
950ć
0.4 950ć
Model: SCM 0.5 Model: HM
FCC catalyst FCC catalyst
0.0
0 5 10 15 20 25 30 35 0.0
0 5 10 15 20 25 30 35
Time (min) Time (min) 
Fig. 4. (a) Shrinking core model and (b) homogeneous model for FCC catalyst regeneration at different temperatures.

Table 2. Reaction rate constant k and R2 for FCC catalyst regeneration with SCM and HM.

Temperature SCM HM
(ć) k (min-1) R2 k (min-1) R2
800 0.0487 0.9858 0.0706 0.9939
850 0.1072 0.9384 0.1579 0.9796
900 0.2212 0.9137 0.3268 0.9639
950 0.3333 0.9015 0.4966 0.9561
1764 Yuming Zhang et al. / Procedia Engineering 102 (2015) 1758 – 1765

3.3. Regeneration kinetics of FCC catalyst

The kinetic parameters were obtained from the correlation of lnk and 1/T according to the Arrhenius equation (Eq.
9), i.e., for the activation energy E and pre-exponential factor A. Figure 5 demonstrates that the reaction data are
subjected to a good linear fitting of lnk with 1/T for coke gasification over FCC catalyst using HM, meaning that
coke gasification in the examined conditions is mainly controlled by the chemical reaction. The calculated value of
E and A was listed in Table 3, and the activation energy from SCM and HM had good repeatability, that is, about
150 kJ·mol-1 for the FCC catalyst regeneration. The differences of pre-exponential factor (A) between SCM and HM
are mainly caused by the reaction assumption of these two models. The reaction characteristics for spent FCC
catalyst regeneration could be investigated using MFBRA and meanwhile obtained its kinetic parameters, thus to
provide some basic data of catalyst regenerating via coke gasification.

-0.5

-1.0

-1.5
lnk

-2.0

-2.5

-3.0
0.00081 0.00084 0.00087 0.00090 0.00093
-1
1/T (K )

Fig. 5. Arrhenius equation plot for the kinetic parameters of FCC catalyst regeneration using homogeneous model.

Table 3. Kinetic parameters of FCC catalyst regeneration with SCM and HM.
Kinetic parameter E (kJ·mol-1) A (min-1)
Reaction model SCM HM SCM HM
Value 149.41 151.37 4.31×10 5
7.73×105

4. Conclusions

The regeneration characteristics and kinetics of spent FCC catalyst were investigated in a micro-fluidized bed
reactor analyzer (MFBRA). Coke gasification with steam over the FCC catalyst could produce high-quality syngas,
with the contents of H2+CO up to 70 vol.% in the syngas, and simultaneously for catalyst regeneration. Coke
gasification rate R on the catalyst was enhanced at high reaction temperature, and the gasification rate first increased
to a peak and then slowly decreased with the increasing of carbon conversion ratio. Shrinking core model (SCM)
and homogenous model (HM) were used to describe the coke gasification reaction kinetics of FCC catalyst. It was
found that HM had better fitting relevance for the reaction data than that of SCM, and the activation energy obtained
from these two models was close to each other. The activation energy of coke gasification for FCC catalyst was
about 150 kJ·mol-1. MFBRA could be a useful tool to investigate the reaction kinetics of gas solid reaction, and
fundamentally justify the feasibility of spent FCC catalyst regeneration via coke gasification.

Acknowledgements

The study was conducted with the research programs supported by Science Foundation of China University of
Petroleum, Beijing (No. 2462013YJRC021), National Instrumentation Grant Program (2011YQ120039), National
Basic Research Program of China (973 Program, NO. 2012CB224801). Acknowledgements are also extended to
Mr. Deping Yu for his help on the experiments.
 Yuming Zhang et al. / Procedia Engineering 102 (2015) 1758 – 1765 1765

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