Chemical Engineering Journal 168 (2011) 839847

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Chemical Engineering Journal

journal homepage: www.elsevier.com/locate/cej

Biomass pyrolysis in a micro-uidized bed reactor: Characterization and kinetics

Jian Yu, Changbin Yao, Xi Zeng, Shuang Geng, Li Dong, Yin Wang, Shiqiu Gao , Guangwen Xu
State Key Laboratory of Multi-phase Complex System, Institute of Process Engineering, Chinese Academy of Sciences, Beijing 100190, China

a r t i c l e

i n f o

Article history:
Received 6 November 2010
Received in revised form 19 January 2011
Accepted 27 January 2011
Keywords:
Micro-uidized bed
Reaction kinetics
Gassolid reaction analysis
Biomass
Pyrolysis

a b s t r a c t
A micro-uidized bed reactor (MFBR) was developed to enable (1) on-line pulse feeding and rapid heating
of particle reactant, (2) effective suppression of the interfacial diffusion via uidization, (3) minimization
of intra-particle diffusion through adoption of ne solid reactants, and (4) on-line monitoring the composition of efuent product gas using, for example, process mass spectrometer. Application of the MFBR
to biomass pyrolysis demonstrated that the reactor led the pyrolysis to have higher gas yield and less
remaining carbon than the test in TG, and at 1173 K the reaction nished in 10 s. The time span to release
an individual gas component appeared longest for H2 , shortest for CO2 and equivalent for CH4 and CO
in between. Reaction kinetics was investigated with respect to the formation of individual gas component and pyrolysis gas mixture. The resulting activation energy and preexponential factor with respect to
gas mixture were 11.77 kJ/mol and 1.45 s1 , respectively. These values were obviously lower than those
measured with TG and xed bed reactors, reecting the quick reaction nature enabled by the MFBR. A
consequent comparison revealed further the factors that affect the values of the kinetic parameters.
2011 Elsevier B.V. All rights reserved.

1. Introduction
Biomass is a widely available, renewable and CO2 -neutral
energy resource, which is increasingly used as an alternative for
fossil fuels [1]. Biomass pyrolysis is essentially important to the
utilization of biomass energy. It provides a viable way to produce
bio-oil and is also the rst step of chemical reactions involved in
all the other thermal conversion technologies, such as gasication.
Therefore, understanding the physical and chemical characteristics
of pyrolysis comprises one of the most critical issues required for
development of biomass thermal conversion technologies.
By far, thermogravimetric (TG) method has been generally used
to characterize the biomass pyrolysis process and deduce its reaction kinetics. It is done by measuring the mass loss of a sample held
in the TG cell during a specied heating program. Many researchers
have reported TG-measured kinetic data of biomass pyrolysis for
different biomass materials under different heating rates [27].
Nonetheless, testing biomass in TG suffers a serious drawback
resulting from the instability of the fuel which causes the composition and structure of the fuel sample to change quickly with
the temperature during heating the TG. Hence, the reaction characteristics and kinetic data obtained at relatively high temperatures
are in fact not regarding the original biomass but an intermediate with certain physiochemical changes at lower temperatures.
Meanwhile, the chemical processes in TG suffer seriously from the

Corresponding authors. Tel.: +86 10 82544886; fax: +86 10 82629912.

E-mail addresses: sqgao@home.ipe.ac.cn (S. Gao), gwxu@home.ipe.ac.cn (G. Xu).
1385-8947/$ see front matter 2011 Elsevier B.V. All rights reserved.
doi:10.1016/j.cej.2011.01.097

interfacial gas diffusion between the reactor space and the solid
sample inside the TG cell. Consequently, scientists designed various other reactors to study the kinetics and reaction features of
biomass pyrolysis. The typical ones include the mesh reactor [8,9],
self-stirred tank reactor [10], uidized bed reactor [11,12] and xed
bed reactor [13,14] in millimeters of inner diameter. These reactors, however, do not have standardized congurations and suffer
still the limitations caused by gas mixing and gas diffusion that are
present inevitably in such reactors.
In this study, a micro-uidized bed reactor (MFBR) was
employed to realize the isothermal reaction conditions and to minimize the interfacial diffusion limitations for gassolid reaction
analysis. The major advantages from using the MFBR were previously reported in Yu et al. [15]. Its involved fundamental idea is the
use of a micro-size uidized bed reactor to ensure the reactions
differential feature under the superior conditions allowed by uidization, including the minimized diffusion inhibition, on-line feed
of reactant sample, quick heating for isothermal conditions, and the
test at arbitrary temperatures and in various gaseous atmospheres.
These features granted by the MFBR are expected to overwhelm
the preceding drawbacks of TG so that the reaction analysis based
on MFBR would become a newly customized approach in addition
to TG. Intended to demonstrate the eligibility as well as superiority
of the MFBR for analyzing various gassolid reactions, the present
article is devoted to investigating the characteristics and accompanied kinetics of biomass pyrolysis in the MFBR. Biomass mass
pyrolysis represents a kind of quick reactions of unstable materials, which is inherently difcult to measure the kinetics in TG. By
using the new micro-reactor and its associated reaction analysis

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J. Yu et al. / Chemical Engineering Journal 168 (2011) 839847

Table 1
Properties of the tested beer lees (d.a.f.).
Particle size

Proximate analysis (wt.%)

Ultimate analysis (wt.%)

FC

O+S

75120 m

79.9

3.93

16.17

48.74

6.73

4.58

39.95

d.a.f.: dry ash free basis; V: volatile; A: ash; FC: xed carbon.

approach, it is expected to result in a deep insight into the biomass

pyrolysis behavior, kinetics and mechanism.
2. Experimental
2.1. Biomass fuel
Fig. 2. A schematic diagram of the experimental apparatus.

Beer lees from Beijing Beer Corporation was used as the biomass
fuel for test, and Table 1 presents the results of proximate and ultimate analysis for this fuel (from Ref. [16]). The volatile and xed
carbon contents are about 80% and 16%, respectively. Although the
fuel is rich in N, the study in the article is not closely related to this
feature. Fig. 1 shows the infrared spectrum of beer lees, suggesting that through the fermentation process the beer lees become
rich in O-containing groups including carbonyl, carboxyl and ether
groups, which would affect the release of CO2 and CO gases in pyrolysis. Without particular specication, the fuel particle size adopted
in this article was 75120 m.
2.2. Apparatus and procedure
Fig. 2 shows a schematic diagram of the experimental apparatus which consists of a fuel sample feeding system, a uidized bed
reactor of 20 mm in i.d. and an efuent gas cleaning and measuring system. Quartz sand of 0.25 mm in Sauter mean diameter was
used as the uidization medium particles in the reactor. The fuel
sample feeding system, driven by an electromagnetic valve that
releases about 10 mL gas per single pulse, injects a fuel sample into
the micro-uidized bed reactor (MFBR) in less than 0.1 s. The pulsed
gas was from a compressed gas stream at 0.2 MPa via a tube of 3 mm
in i.d. The total volume of reactor and tubes were about 20 mL. The
MFBR consists of two stages separated with porous plate, a lower
stage to receive the fuel sample for testing at the specied temperatures, and an upper stage to catch ne sample particles escaping
from the bottom stage. Previous study [17] has shown that bubbling
uidization of quartz sand prevailed in the MFBR under the tested
conditions of this article. The efuent gas was cleaned in a microlter lled with desiccant and in turn measured using an online
mass spectrometer (AMETEK, American). A computer monitored

the temperatures of the furnace and inside the MFBR, pressures at

the reactor inlet and outlet, carrier gas ow rate, actions of the sample feeding device and the output data from the mass spectrometer.
Experiment was performed generally with a procedure
described herein. Three grams of silica sand was put into each layer
of the MFBR, but when testing the C balance of the reaction occurring in the reactor by using air as the uidizing gas, the upper layer
was lled with -Al2 O3 particles that had the same average size and
volume as the silica sand to ensure the similar uidization conditions in both the stages. The adopted -Al2 O3 particles had a BET
surface area of 250 m2 /g and an average pore diameter of 7 nm.
For the tests in this article argon at ow rates of 100600 N mL/min
was employed to uidize the particles in the MFBR. The reactor was
heated in uidization state to set the temperature in the reactor to
be readily at 500900 C. Then, injecting 1050 mg beer lees into
the inside of the uidized hot quartz sand particles initiated the
desired pyrolysis reactions. After pyrolysis, combustion of residual char was carried out at 800 C by switching the uidizing gas
from argon to air. By integrating the measured CO2 concentration
diagram the C amount in the residual char was estimated. The C
balance for the reaction in the MFBR was measured by collecting
all the efuent gas during the reaction time using a gas bag and in
turn analyzing the gas composition in a micro-GC (Agilent 3000).
Pyrolysis kinetics analysis was based on the measured
time-dependent efuent gas concentration diagrams, and the analysis approach was detailed in the section Pyrolysis Kinetics
Analysis.

3. Pyrolysis behavior characterization

3.1. Carbon balance verication

Fig. 1. Functional groups of beer lees identied by infrared spectrum.

The approach measuring only the efuent gas (ow rate and
composition) makes it difcult to detect the mass balance of the
reaction occurring in the MFBR. Thus, air combustion of the fuel
at, for example, 800 C was conducted to analyze the carbon balance of the reaction in the reactor. In this case, the upper layer of
the micro-uidized bed (MFB) was loaded with high-surface area
mesoporous -Al2 O3 to capture large molecules and thereby to
minimize the formation of tar [18], which could ensure the carbon in the biomass fuel (beer lees) to be completely converted into
CO2 and CO to allow an accurate quantication. The result shows
that the released C via the gaseous product (combustion ue gas)
from the MFBR reached 97 wt.% to 105 wt.% of the C supplied into
the reactor via fuel. Table 2 summarizes some experimental data
for this justication, indicating essentially the good stability and
reproducibility of the measurement in the MFBR.

J. Yu et al. / Chemical Engineering Journal 168 (2011) 839847

841

Table 3
Product distribution with respect to tested beer lees at different temperatures.

Table 2
Test of carbon balance via combustion of beer lees in MFBR.
Sample
mass (mg)

Gas ow rate
(N mL/min)

Yield (C%)

20.5
23
30
20
25
30

100
200
300
400
500
600

103
105
97
101
98
99

Temperature [ C]
600

700

800

900

H2 [%]
CO [%]
CO2 [%]
C1C3 [%]
Total gas yield [%]

0.10
7.45
6.22
4.71
18.48

0.32
19.90
7.81
11.64
39.67

0.75
23.70
9.10
11.68
45.23

1.67
31.32
8.01
10.49
51.49

Remaining carbon [%]

10.23

9.49

6.40

5.84

3.2. Pyrolysis characterization in xed bed

3.3. Pyrolysis characterization in MFBR

Both xed bed and micro-uidized bed reactors were used to

investigate the pyrolytic characteristics of beer lees. The test in
a quartz xed bed reactor of 10 mm in inner diameter was carried out in an argon atmosphere under gradual heating to 900 C
at 10 C/min. The mass of beer lees was 0.5 g and the carrier gas
ow rate was 500 N mL/min. The efuent gas product was analyzed
using a GC with the plot-Q and molecule-5A columns. As shown in
Fig. 3, the evolution of gas components manifested some distinctive
features. Carbon dioxide (CO2 ) released early starting from 200 C
and reached a peak amount at about 300 C. This was followed by
the release of CO starting at about 280 C and with two peak concentrations at about 350 C and 850 C, respectively. Then, the release
of CH4 was started at 400 C and reached its peak around 520 C.
These gas releasing characteristics can be explained in terms of the
biomass structure and composition [19,20]. The main constituents
of beer lees are lignin, hemicellulose and cellulose [21,22]. Lignin
has a very complex aromatic structure, while hemicellulose is a
kind of polymer composed of 5- and 6-carbon sugars and cellulose
is a kind of polymer of glucose [23]. These different components
in the fuel have different decomposition temperatures according
to TG test [21,23,24], leading thus to the observed different release
proles for different gas species. The released gas amount appeared
more for CO2 , and this might be related with the abundant oxygencontaining groups in beer lees (see the FTIR spectrum in Fig. 1).
Hydrogen was released at rather higher temperatures comparing
to the other gas components because it was formed basically via
cracking the released volatiles which requires surely higher temperatures. In fact, there was not signicant release of H2 before
500 C and the peak release of H2 exhibited at 700 C approximately. The span for H2 release was also longer than for all the
other gas species. Furthermore, one can nd that the remaining
carbon (16.57 wt.%) was nearly equal to the xed carbon content of
the fuel (16.17 wt.%) shown in Table 1.

The pyrolysis of beer lees in the MFBR was performed at given

temperatures varying in 600900 C. The ow rate of the uidizing
gas (argon) was 300 N mL/min. The release patterns of the major
gas components are noticeably different from that shown in Fig. 3
for the xed bed reactor test at a slower heating rate (10 C/min).
As shown in Fig. 4, the time for completing the pyrolysis reaction
was greatly shortened in comparison with that in the xed bed
reactor, and it decreased obviously with elevating the temperature.
For different gas components there was a difference in the time to
start or end the gas release, but the difference was negligible in
comparison with that in Fig. 3. From Fig. 4 one can still identify
that CO2 started to release rst and at low temperatures, verifying
mutually the measurements in the tested two reactors. The data in
Fig. 4 suggest that in the MFBR the heating rate, which was shown
to be 100010000 C/s for ne particles in m at temperatures of
500900 C [15], was much higher than in the tested xed bed reactor. This caused in turn the lignin, hemicellulose and cellulose in
the fuel to pyrolyze almost simultaneously [25]. At temperatures
over 800 C, the pyrolysis reaction in the MFBR nished in 10 s, and
this completion time was much shorter than the experimental data
from uidized bed reactors in diameters of about 80 mm [26,27,29].
Hence, there was surely a fast differential pyrolysis reaction in the
MFBR, a result from the allowed high heating rate and minimized
mixing and diffusion inhibitions in the reactor.
The gas yield (in mass against fuel) was determined by sampling
the produced gas in the entire reaction time and in turn analyzing
the gas via a Micro-GC 3000. Table 3 shows the results obtained,
and it is obvious that the total gas yield increased from 18.48 wt.%
to 51.49 wt.% corresponding to the temperature rise from 600 C
to 900 C. The yield of CO, which took about 50% of the total gas
product, possessed a larger extent of increase with raising the temperature. The yield of CO2 varied little and remained in 8 wt.% or so
in the temperature range of 700900 C, indicating that the carboxyl or ester functional groups present in the fuel (see Fig. 1)
could decompose completely at temperatures above 700 C. The
yields of hydrocarbons (C1C3) increased from 4.71 wt.% at 600 C
to 11.68 wt.% at 800 C, but it further decreased to 10.49 wt.% at
900 C. This feature of variation indicates that raising temperature
promoted the cracking of tar to form hydrocarbons. The decomposition or cracking of hydrocarbons also increased, especially at
temperatures over 800 C, to increase the yield of hydrogen with
elevating temperature. Overall, there was a much higher total yield
of pyrolysis gas mixture for the reaction in the MFBR than that in
the xed bed reactor characterized in Fig. 3. This is surely related
to the much higher heating rate and more efcient mass transfer
in the micro-uidized bed reactor.
The remaining carbon after pyrolysis at different temperatures
was measured through combustion realized by switching the gas
entering the reactor from Ar to air at 800 C. The amount of C was
calculated from the released CO and CO2 . Table 3 shows that the
remaining carbon decreased from 10.23 to 5.84 wt.% corresponding to the temperature rise from 600 C to 900 C. These amounts

Fig. 3. Pyrolysis gas releasing characteristics in a xed bed reactor.

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J. Yu et al. / Chemical Engineering Journal 168 (2011) 839847

Fig. 4. Pyrolysis gas releasing characteristics in MFBR.

of remaining carbon were much smaller than those shown for the
xed bed test (Fig. 3) or the xed carbon content of the tested
biomass (FC in Table 1). The result complies with the release of
more volatiles disclosed above and demonstrates again that there
was better mass transfer and higher heating rate in the MFBR to
facilitate the pyrolysis reaction and the release of volatiles.
3.4. Parametric investigation in MFBR
Herein the progress of the pyrolysis reaction is analyzed in terms
of the conversion dened against the volume of the produced pyrolysis gas mixture. Thus, the conversion at the end of gas release was
100%. Fig. 5 shows the variation of the conversion with reaction
time at different uidizing gas ow rates that were below the terminal velocity of the employed silica sand. The time to nish the

Fig. 5. Total gas conversion versus reaction time in MFBR at different ow rates.

reaction decreased with increasing the ow rate and reached 10 s

at ow rates exceeding 300 N mL/min at 800 C. The reaction rate
can be calculated from the slope of the conversion curve in Fig. 5,
showing that the rate varied little when the ow rate was above
300 N mL/min. This critical gas ow rate represents actually the gas
velocity necessary to minimize the external diffusion inhibition on
reaction rate.
Fig. 6 shows the total pyrolysis gas yield as a function of the
gas ow rate at different temperatures (600800 C). The gas yield
increased with raising the reaction temperature and was affected
by the uidizing gas ow rate. For instance, at 600 C, the gas yield
was merely 3.38 wt.% at 100 N mL/min but this yield increased to
16.92 wt.% at 200 N mL/min. Similar to the demonstration in Fig. 5,
the gas yield varied little with the uidizing gas ow rate when the
rate was above 300 N mL/min. The plausible reason for the result
was that silica sand particles in the MFBR were not fully uidized
at 100 N mL/min and 600 C, thus leading to slow heating to the

Fig. 6. Product yields versus gas ow rates in MFBR.

J. Yu et al. / Chemical Engineering Journal 168 (2011) 839847

843

adopting small fuel particles, but the inuence becomes indistinctive as the particle size was below 120 m, implicating that the
inuence of the intra-particle diffusion would be negligible for the
fuels with sizes below 120 m.
4. Pyrolysis kinetics analysis
The pyrolysis kinetics of beer lees in the MFBR was analyzed
on the basis of the release characteristics of individual gas components and the pyrolysis gas mixture measured at temperatures of
500900 C for fuels with sizes of 75120 m. The adopted ow
rate of uidizing gas (Ar) into the MFBR was xed at 300 N mL/min
to ensure the minimized external and internal diffusion
limitations.
The conversion X of beer lees in pyrolysis was estimated by

t

Fig. 7. Inuence of fuel particle size on the pyrolysis gas conversion.

X(%) =

 tt0e
t0

fuel particles and having in turn the low gas yield (the corresponding supercial gas velocity being 0.014 m/s, below the minimum
uidization velocity of 0.022 m/s). At rather higher temperatures
(such as 800 C), the little variation of gas yield with gas ow rate
reveals actually that the inuence of uidizing gas velocity, which
represents the uidization conditions, on the gas yield surrounded
to the dominant effect of the reaction temperature. Fig. 6 shows
also the remaining carbon measured by analyzing the released
CO2 in combusting the remaining carbon. At 800 C the remaining carbon decreased to 5.62 wt.% from 8.50 wt.% in response to the
increase in the uidizing gas ow rate from 100 to 500 N mL/min.
This shows that raising the gas velocity in the MFBR facilitated
the release of volatiles, lowering consequently the remaining
carbon.
Fig. 7 shows the inuence of fuel particle size on the pyrolysis
gas conversion. The reaction completion time was shortened via

Ci udt
Ci udt

100,

(1)

where Ci denotes the concentration of gas species i or the pyrolysis

gas mixture, u refers to the ow rate of the efuent gas from the
MFBR, and t0 , t and te represent the different stages of pyrolysis at
time 0, t and the reaction end, respectively.
The kinetic parameters of biomass pyrolysis in isothermal process, as widely reported in the literature [9,1114], were calculated
generally using the shrinking core model. This model suggests
that the reaction rate be subject to the un-reacted surface area or
remaining amount of reactant, which is expressed with
dX
= k(T ) (1 X)n ,
dt

ln

 dX 
dt

= ln(k(T )) + n ln(1 X),

(2)

where n is the reaction order and k(T) is the reaction rate constant
dened by the Arrhenius equation according to
ln(k(T )) = ln(A)

E
RT

Fig. 8. Gas conversion versus reaction time in MFBR at different temperatures for individual gas component.

(3)

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J. Yu et al. / Chemical Engineering Journal 168 (2011) 839847

Fig. 9. Correlation of ln(dX/dt) and ln(1 X) for individual components in MFBR.

4.1. For individual gas component

Fig. 8 shows the pyrolysis gas conversion X of major gas components (H2 , CH4 , CO and CO2 ) versus reaction time at different
reaction temperatures. Here, the conversion 100% corresponds to
the largest gas yield at the end of pyrolysis. The reaction rate dened
from the slope of the conversion curve increased with increasing
temperature, but the degree of increment in the reaction rate was
different for each individual gas component (i.e., the difference in
the slope of the curve). It was largest for H2 , and then CH4 , CO
and CO2 in succession. These results indicate that the reaction temperature signicantly affected the formation of pyrolysis gaseous
products, especially for hydrogen.
Fig. 9 converts the data of Fig. 8 into the correlation of ln(dX/dt)
with ln(1 X). The entire curve for a given temperature can be
divided into three parts denoting three reaction stages (taking
the curve at 800 C as an example). The part (I) refers to the
sample heating stage, and as it would be, there was little difference among the tested different temperatures. In this stage,
the pyrolysis reaction, if occurred, was mainly on the particle
surface.
The pyrolysis on the surface would form a layer of carbon and ash
on the biomass particle, while the fuel particle could reach a steady
temperature via this stage. The pyrolysis reaction then shifted into
the second stage (II), the major phase to implement the decomposition. The higher the reaction temperature, the deeper the pyrolysis
was, leading to a wider stage II in Fig. 9. In this stage, the reaction
was mainly controlled by chemical kinetics because the fuel particles tested were in 75120 mm that allowed diffusion effect to be
negligible. In this stage the reaction rate varied more or less with
time (see Fig. 9), and this should be mainly due to the dynamic
change in the reaction surface area. Once the pyrolysis was nearly
completed, the curve in Fig. 8 tends to be horizontal, suggesting
that the reaction rate decreased to its minimum to denotes the
entry into the third reaction stage (III).

The data of the stage II in Fig. 9 were analyzed according to

Eq. (2) to dene the reaction order n and the rate constant k(T).
Table 4 summarizes the linear correlation coefcient R for all the gas
components, showing that it was above 0.99 for all the curves. The
reaction order was mainly between 1.4 and 1.7 at the tested temperatures (except for H2 ). For CO2 and CO it was concentrated on
1.7 and 1.6, whereas for H2 the order at 500 C was much different
Table 4
Reaction order and rate constant of different gas components.
Gas

T ( C)

ln(k(T))

H2

500
600
700
800
900

2.43
1.67
1.43
1.13
0.86

2.42
1.59
1.65
1.53
1.60

0.99
0.98
0.99
0.99
0.99

CH4

500
600
700
800
900

1.53
1.40
1.14
1.01
0.89

1.54
1.33
1.34
1.26
1.46

1.00
0.99
0.99
0.99
0.99

CO

500
600
700
800
900

1.39
1.32
1.08
0.91
0.76

1.56
1.75
1.52
1.65
1.71

0.99
0.99
0.99
0.99
0.99

CO2

500
600
700
800
900

2.01
1.40
1.21
1.10
1.01

1.71
1.53
1.72
1.71
1.85

1.00
0.99
0.99
0.99
1.00

Pyrolysis gas mixture

500
600
700
800
900

1.47
1.22
1.07
0.98
0.82

1.86
1.62
1.62
1.52
1.62

1.00
0.99
0.99
0.99
0.99

J. Yu et al. / Chemical Engineering Journal 168 (2011) 839847

Fig. 10. Linear tting of ln(k(T)) and 1/T for individual gas components in MFBR.

from the others and reached 2.42. These suggest that different gas
components have different formation mechanisms in the pyrolysis.
Fig. 10 re-correlates the rate constants k(T) in Table 4 to dene
the activation energy (E) and frequency factor (A) for the gas components H2 , CH4 , CO and CO2 . The obtained parameters were listed in
Table 5. All the correlation curves in Fig. 9 have good linearity above
0.97, and the resulting apparent activation energy E fell into a range
of 1030 kJ/mol. The activation energy represents the difculty for
forming the gas component. For H2 it has the largest activation
energy and this justies that it was more difcult to generate H2 in
pyrolysis. In comparison, the formation of CO2 is obviously easier
for it has the lowest activation energy.
4.2. For pyrolysis gas mixture

845

Fig. 12. Correlation of ln(dX/dt) and ln(1 X) for pyrolysis gas mixture in MFBR.

reaction order n and reaction rate constant k(T) from this gure (i.e.,
the stage II) according to Eq. (2) were listed up also in Table 4. The
reaction order for the pyrolysis gas mixture varied around 1.62, suggesting a good repeatability of the measurement in the MFBR. The
reaction orders in Table 4 for both individual gas components and
gas mixture clarify that the biomass pyrolysis reactions in the MFBR
do not follow the rst-order model, although this kind of model is
generally proposed by the kinetic measurements in TG [25].
The apparent activation energy E and frequency factor A were
also estimated for the pyrolysis gas mixture. Fig. 13 shows the
Arrhenius plot, exhibiting a good linear tting of ln(k(T)) and 1/T
with a correlation coefcient above 0.99. The derived E and A are
11.77 kJ/mol and 1.45 s1 , respectively. These two values, as discussed further below, are lower than many literature-reported
values obtained mainly in TG [28,3133] but close to those from
the tests in a relatively large-size CFB pyrolyzer [29,30].

Fig. 11 shows the pyrolysis gas conversion calculated for the gas
mixture. As it should be, the completion time of pyrolysis reduced
with increasing temperature, and comparing to Fig. 7 for individual
gas components the variation of the conversion curve with temperature appeared more regular in Fig. 11. This shows in fact a kind of
compensative or coupling effect among the formation reactions for
different individual gas components. For example, the slow formation of H2 is compensated by the quick formations of CO and CO2
to have thus the improved regularity of gas yield variation with the
reaction temperature.
Fig. 12 shows the correlation of ln(dX/dt) and ln(1 X) for the
pyrolysis gas mixture, and three reaction stages are similarly obvious as in Fig. 9 for the individual gas component. The derived

In order to clarify why the MFBR leads to the low values of E

and A shown above, Table 5 compares such two parameters from
a few literatures using different reactors and under different heating rates. In comparison with in TG, the tests of this work in MFBR,
Lv et al. [29] in a large-size CFB reactor and Zabaniotou et al. [31]
using a wire mesh reactor refer denitely to the quick heating conditions and the measurement at preset temperatures (isothermal
approach). Their heating rates were above 1000 C/s for the uidized bed reactors (this work and [29]) and 100240 C/s for the
wire mesh reactor. The resulting E and A were thus in the same

Fig. 11. Conversion based on pyrolysis gas mixture in MFBR.

Fig. 13. Kinetic parameters and linear tting of ln(k(T)) and 1/T in MFBR.

4.3. Kinetic data comparison

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J. Yu et al. / Chemical Engineering Journal 168 (2011) 839847

Table 5
Kinetic parameters measured in the MFBR and comparison with literature report.
Method

Source

Fuel

This study

Heating rate

Gas

Beer lees

100010,000 C/s

Olive wood

100010,000 C/s

At given T (fast heating)

Lv et al. [29]a
b

Programmed heating
(varied T)c
a
b
c

Zabaniotou et al. [31]

Pine sawdust
Cellulose

100240 C/s

Wang et al. [32]

Sawdust

520 C/min

Sonobe et al. [33]

Rice husk corncob

520 C/min

H2
CH4
CO
CO2
Mixture
CO
Mixture
Weight loss

Weight
loss

T [ C]

500900

700
250400
200600
200600

E [kJ/mol]

A [1/s]

28.25
12.49
12.36
10.91
11.77
24.45
15.12
17.90
11.14

7.92
1.47
1.60
1.32
1.45
4.81
0.71
862
99

160200
120200
120250

4.5E54.5E13
E12E15
E12E19

In a large-size uidized bed reactor.

In an electrically heated mesh reactor.
With commercial TG.

order, with E varying in 1020 kJ/mol and A in 1100 s1 . The data

of this work and that from Lv et al. were in particularly good consistence, supporting that both these studies used the same-type
reactor (uidized bed) and had the equal heating rate. The wire
mesh reactor [31] resulted in slightly higher E and also the larger
A, but they are in the same order with those from the uidized bed.
Thus, the higher E and A for the mesh reactor should be related to
its lower heating rate (than in uidized bed) and the reactor itself
which suffered more inhibitions from the gas diffusion than in the
uidized bed reactors.
The pyrolysis tests in TG have to be via programmed heating
method, and the heating rate is generally below 50 C/min (usually 520 C/min), much lower than the preceding rates realized
in the isothermal measurements. In Table 5, the reported E and A
for the TG tests were distinctive high, with E in 120250 kJ mol1
and A in orders of 105 1015 s1 . Comparing to the other measurements in Table 5 at preset temperatures and with high heat rates
of hundreds of C/s, we can suggest that the kinetic data of biomass
pyrolysis be subject to serious inuences of the heating rates and
the measurement approach, which is either isothermal (at preset temperatures) or non-isothermal (programmed heating). While
the isothermal approach at heating rates of hundreds of C/s lead to
the activation energy E in 1020 kJ/mol and the frequency factor A
of 1100 s1 , the programmed heating at low rates of 1020 C/min
would result in much higher E and A which are possibly valued to
about 200 kJ/mol and 105 1015 s1 , respectively.
Table 5 claries also that both E and A compensatively vary to
make small A correspond to low values of E. The activation energy
represents essentially the difculty to start a reaction, while the
frequency factor A indicates the occurred effective collision of reactant molecules. When a lower E denotes a reaction that is easier to
start and occur, less collision of reactant molecules should thus be
entailed to allow a small A. For MFBR, its low activation energy and
frequency factor demonstrate that the biomass pyrolysis is easier
to occur than in TG. This is in consistence with the features of the
MFBR that there are high-rate heating to fuel particles and minimized diffusion inhibition on the reaction. Furthermore, the tested
biomass fuel sample is in micrometers and micro-grams to maintain the differential characteristics of the reaction. Consequently,
the MFBR, in comparison with TG, would be a viable reactor that
enables the isothermal differential analysis of gassolid reactions,
especially the fast reactions like pyrolysis for investigating the reaction characteristics and estimating the kinetics. Beneting from
its features of quick heating, minimized diffusion inhibition and
differential isothermal conditions, the measured reaction kinetics in MFBR should be closer to the intrinsic chemical kinetics of
the tested reaction, while the claried reaction characteristics may
reveal the true reaction mechanisms.

5. Conclusions
The so-called micro-uidized bed reactor (MFBR) was used to
investigate the pyrolysis of beer lees. The reactor (20 mm in i.d.)
allowed instantaneous feed of 1050 mg fuel sample in m at a preset temperature to enable the occurrence of the so-called isothermal differential reaction. For comparison the pyrolysis was also
conducted in a micro-xed bed reactor. It was shown that the pyrolysis in the MFBR nished in about 10 s at 800 C, indicating a quicker
pyrolysis than in the literature reports using uidized beds having
diameters of tens of millimeters. The pyrolysis gas yield in the MFBR
was much higher than that in the micro-xed bed reactor. The time
to start and end the release of pyrolysis gas was also distinctively
different in the micro-xed bed and uidized bed. While the time
shared obvious difference for gases H2 , CO, CO2 and CH4 in the xed
bed pyrolysis, there was little difference for the tests in the MFBR.
The pyrolysis kinetics was analyzed on the basis of the pyrolysis
gas releasing characteristics for both individual gas component and
pyrolysis gas mixture. The estimated kinetic parameters included
activation energy, frequency factor and reaction order. These
parameters were different for different gas components, indicative of the different mechanisms involved in forming the different
gas species. The overall pyrolysis kinetics based on formation of
the pyrolysis gas mixture was analyzed in terms of the shrinking
core model, leading to a reaction order of 1.62, an activation energy
of 11.77 kJ/mol and a frequency factor of 1.45 s1 , respectively.
Against the measurements in TG and xed bed reactors, the values
of these kinetic parameters were obviously lower, indicating the
quick pyrolysis reaction in the MFBR. A consequent comparison on
the kinetic data of biomass pyrolysis obtained in different reactors
revealed that the values of activation energy and frequency factor
are subject to the heating rate and the test approach, either isothermal at present temperatures or non-isothermal via programmed
heating. The isothermal test with heating rate of hundreds of K/s
leads to low activation energy and frequency factor in order of tens
to hundreds, whereas the non-isothermal test in TG may result in
activation energy larger by 1030 times and frequency factor high
as 105 1015 . These demonstrate that the MFBR, which minimizes
the gas diffusion inhibition, realizing quick heating and offering
isothermal differential characteristics, enabled the isothermal differential analysis of gassolid reactions, especially the fast reactions
like pyrolysis for investigating the reaction characteristics and estimating the kinetics.
Acknowledgements
Financial support of National Natural Science Foundation
of China (20606034, 20776144), National High-Tech Research

J. Yu et al. / Chemical Engineering Journal 168 (2011) 839847

and Development Program (863 program, No. 2009AA02Z209)

and Chinese Academy of Sciences (Y2005014, GJHZ200824,
0829011198), are greatly appreciated. Acknowledgements would
be also extended to Ms. Jianhong Zhu for their helps in experiments.
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