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Fuel
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a r t i c l e
i n f o
Article history:
Received 13 January 2015
Received in revised form 12 May 2015
Accepted 18 May 2015
Available online 28 May 2015
Keywords:
Kinetic parameters
Reaction rate
Fluidized bed
Char particles
Boudouard
FTIR
a b s t r a c t
A novel method is presented for experimental study of gas-particle reactions, based on realizing a
well-stirred reactor as a small scale uidized bed. This reactor is evaluated against the drop tube reactor
and the thermo-gravimetric analyser. It shows to enable high heat up rates (104 K/s), long timescale
observation (up to several hours), operation with small fuel particles (100 lm) and accurate control
of reaction conditions. Char reaction rates are established from real-time gas product analysis by FTIR
spectroscopy, through a detailed data-analysis procedure. This procedure employs a particle
surface-evolution model and accounts for sampling system signal attenuation. The validity of the
well-stirred conditions is established, and the method is employed for char combustion and gasication.
Highly consistent results for char gasication over a wide range of conditions (T = 8001100 C,
C CO2 = 1976%), are used to demonstrate the establishment of kinetic parameters for an n-th order
approach. Activation energy and order of reaction are found and compare well with the literature.
2015 Elsevier Ltd. All rights reserved.
1. Introduction
A well-stirred reactor provides spatially homogenous, controlled conditions for process and reaction analysis. Therefore, it
might serve as a basis for model development and validation
[1,2]. For example, it can be used to experimentally establish inherent reaction rates of char combustion, required for reliable
reactive-ow CFD simulation [3]. However, practical realization
of such an ideal system is difcult. The present study attempts to
do this using a small-scale Fluidized Bed Reactor (FBR), with focus
on the establishment of kinetic parameters of gas-particle reaction,
under controlled conditions.
An FBR is a commonly used type of reactor, though generally
operated on a larger scale and in continuous-feed mode, for processes such as gasication, bio-oil production or coal and char
combustion (e.g., [46]). Here, this reactor type was chosen and
adapted for kinetic studies, due to the possibility of conducting
long timescale measurements up to reaction completion.
Additionally, it is shown that the signicant mixing of the reactor,
as well as its operation with small fuel batches, promotes
264
2. Experimental method
The experimental setup consists of a small-scale bed of inert
particles, which is uidized by a rate and composition controlled
gas-mixture. Into this, small batches of well-characterized fuel
are introduced, while the products are continuously analyzed from
the exhaust gas. The analysis procedure accounts for the evolution
of the char particle surface during the reaction and the dispersion
caused by the sampling system, to calculate a characteristic reaction rate from measurement data.
2.1. Experimental setup
The experimental system employed here is the same that has
previously been used by the authors and is only briey described
at this point [15,16]. The FBR is located inside a controlled electric
oven, allowing temperatures up to 1280 C to be imposed with high
stability (e.g.: 1000 2 C). The desired composition of the gas mixture can be set from a base gas (air, CO2, N2 or Ar), which can be
enriched with a reactant (O2 or CO2) by independent
temperature-corrected mass ow controllers (MFC), in order to set
ow rate at reactor conditions. This gas mixture heats up as it ows
down the annular gap to the gas distributor (sintered silica glass,
pore diameter range 40100 lm) which uniformly distributes the
ow to uidize an inert bed of round sand-like alumina (Al2O3 diameter dp = 112 30 lm and sphericity /s = 0.80 0.18, established by
laser diffraction analysis and microscopy). A small portion of this gas
mixture is used to purge and mildly pressurize the char injection
(fuel feed) system. For each run a small batch (<25 mg) of pulverized
fuel is dropped onto the bed, where it heats up and reacts with the
uidizing gas. The heating rate has been approximated analytically
taking radiative and convective heat transfer into account. The emissivity of the bed has been calculated adapting the model of Palconok
[17]. The approximation gives values on the order of 104 K/s similar
to the values found by Yu et al. [18]. After complete reaction of the
char, the remaining ash becomes an inert part of the bed material
which is periodically exchanged. The pressure loss over the distributor and uidized bed is measured by differential pressure gauge,
while the bed temperature is measured with an immersed
ceramic-shielded type S thermocouple. The bed has a diameter of
D = 34 mm, with a non-uidized bed height of Hd = 30 mm, and a
typical uidized height uctuating around Hf = 70 mm. The gaseous
reaction products are captured just above the uidized bed. Driven
by a slight reactor overpressure (typically 10 mbar) the exhaust
gas is fed into the gas analyzer through a sampling line and a lter;
afterwards it exits out to a safety venting system. The entire sampling system is heated to 180 C to prevent unwanted tar condensation. A Gasmet DX-2000 FTIR spectrometer, measuring in the mid-IR
range (wave numbers of 6004200 cm1) was employed for
real-time gas analysis, sampling at 0.5 Hz with an accuracy of 2%
of the measurement range after initial calibration.
For additional validation experiments (Section 3.1), some of the
tubes in the FBR were exchanged to measure the temperature and
gas composition at various heights within the bed (details in
Fig. 1). An identically scaled, transparent cold uidized bed was
used for observation of bed uid-dynamics. Therein the pressure
drop across the distributor and bed height was measured as a function of ow rate, under standard air conditions. This system
demonstrated that the char particles are thoroughly mixed into
the bed in less than 2 s.
2.2. Data analysis
The char reactions examined here can be well-described by the
carbon conversion curve, or burnout (the mass fraction of solid
carbon that has reacted). While obtaining the curve from analysis
of exhaust gas-analysis is straightforward, establishing a characteristic reaction rate for the entire conversion requires a more complex analysis procedure: In general, an appropriate char surface
evolution model is used to generate a predicted curve and the reaction rate (control parameter) is found by iterative comparison to
the experimental one.
As the particle is consumed its surface is constantly changing,
and eventually decreases towards complete burnout. By using a
265
Purging gas
Fuel feed
(1)Thermocouple
(2) Sampled gas
Sealings
Fluidizing gas
Fluidized
bed
Distributor
El. heating
Fig. 1. Interior of the uidized bed reactor.
suitable model for particle surface evolution, a characteristic reaction rate covering the entire process can be determined. Several
surface evolution models exist in literature: the uniform reaction
model (URM), stated to be appropriate for Regime I/II conditions
and highly porous chars [11]; the shrinking core model (SCM),
which has recently been shown to be suitable for high-ash/
low-porosity char [19], its offspring the grain model for agglomerated char [20] or the more complex random-pore model [21]. In
this work, due to examination of a highly-porous fuel the URM
was considered and tested for validity. This model (given in Eqs.
(1)) represents a limiting case reaction throughout the volume
of the particle with constant size).
_ O2
_i m
@X
MC m
C CO t DC CO2 t
@t mC;0 M i M O2
1 C CO t=2
1
a 2bt
a 2bt
p
p
exp2abErfc
Erfc
2
2 t
2 t
0.1
0.8
0.08
0.6
0.06
0.4
0.04
X (URM)
X (URM, conv.)
X
dX/dt
0.2
0
0
10
20
30
40
50
60
dX/dt [1/s]
URM : Xt 1 ert
Ft
concentration, i.e. the molar fraction of a gas species instantaneously measured by FTIR, and D indicates the difference between
outlet and inlet value.
As a mass balance based on the samples weight did usually not
obtain closure 50% to 80% of the introduced carbon was captured
in the exhaust gas the data was normalized to obtain complete
burnout (X = 1). This is equivalent to the assumption that a percentage of the char does not undergo a reaction in the uidized
bed. This loss may occur by particles sticking to the fuel feed
system or by elutriation of ne particles in the early stages of the
reaction. In any case, complete conversion of the char in the bed
was veried by continued measurement until recovery of steady
levels of CO2 and CO (<50 ppm). This procedure of normalizing
the calculated burnout curves to the detected carbon in the
exhaust has been done by other research groups, (e.g. Lou et al.
[4], who recovered similar fractions) and doesnt affect the measured reaction rate.
The analysis method is demonstrated for the case of a rapid
reaction (combustion at 800 C in air) in Fig. 2. This gure shows
the carbon conversion rate dX/dt, which is determined by means
of Eq. (2). The resulting carbon conversion X is obtained as the integral over time thereof. Before tting a chosen surface evolution
model (e.g. Eq. (1)) to this experimentally found carbon conversion
curve, it is necessary to take dispersion along the sampling line
into account. These effects are related to the long piping (2 m)
and the ne ltration (<2 lm) required by the gas analyzer. To
allow for these issues the carbon conversion, predicted by the surface evolution model, is convoluted by a transfer function F(t) (Eq.
(3)), which is derived from the TaylorAris convectiondiffusion
transport equation. The procedure of (de)convoluting data is
described in detail by Abad et al. and is outlined briey in the following [22]:
0.02
0
70
Time t [s]
Fig. 2. Experimental rapid char reaction in air T = 800 C, CO2 = 21%. Carbon
conversion rate as calculated from Eq. (2) using FTIR measurements and corresponding carbon conversion and its comparison to URM prediction with and
without convolution. Circles stand for the experimentally found carbon conversion
rates dX/dt. Its integral over time, the carbon conversion, is represented by triangles.
The dashed line gives the carbon conversion prediction of the uniform reaction
model, whereas the continuous line expresses its convolution.
1
0.8
0.6
0.4
unit-step
step-response
fitted step-response
0
0
10
20
30
40
3. Results
50
Time t [s]
Fig. 3. Response of the FBR-System to a sudden increase of CO2 concentration from
0 to 20 Vol.-% in the feed-gas.
Rt S Ft
Considering the predicted carbon conversion curve X(t) as a series of unit-step perturbations at discrete values of t, convolution of
this curve can be carried out by using a linear combination of Eq.
(4):
Rt k St1 Ft k
k1
X
Sti1 t i Ftk ti
i1
By substituting S in Eq. (5) with the predicted carbon conversion X, R(tk) gives its convolution at the specic time tk.
After the convolution has been performed, the resulting burnout curve is iteratively t with a least-square regression to the
measured data by changing the parameter r until convergence
has been achieved. The tting was done to the 1080% part of
the carbon conversion curve, to avoid the inuence of reaction
startup and delayed completion. Reaction rates found according
to this procedure, are representative of the majority of the conversion, and not just of a single part of the reaction, as is often the case
in kinetic studies.
The need for the above described convolution procedure is
especially apparent at short timescales on the order of the typical
system delay. By including the convolution procedure, the working
range of this method is extended.
Fig. 2 shows the different curves obtained by the above
described analysis procedure.
2.3. Fuel characterization
For the detailed kinetic-parameter establishment it is imperative to characterize the fuel used. The fuel chosen was a
well-pyrolyzed wood-based char (biomass). The pyrolyzation has
been carried out in the uidized bed reactor under pure nitrogen
atmosphere with a residence time of 30 min at 900 C. Fuel particles were ground and sieved to a typical diameter of
Table 1
Fuel composition of wood char WC1173 (biomass pyrolyzed at 1173 K for 30 min).
Water
Ash (dry)
Volatiles (dry)
3.88
3.70
To verify operation under well-stirred conditions the uidization regimes of the bed must be identied, as well as homogeneity
of temperature and composition inside the uidized bed.
3.1.1. Qualication of the uidization regimes
To examine the uidization regimes, observations were conducted in a transparent (cold) uidized bed with identical dimensions. From analysis of high-speed video (HSV) and pressure
measurements the regimes of uidization were identied. Bed
height was deduced from time-averaged images, were it was
dened arbitrarily as the location of a 50% decrease in brightness.
Fig. 4a) shows the results. With the onset of ow there is a slight
increase in bed height, though no bubbling can be observed just
gas ow between the particles. The rst bubbles appear 60 Nl/h,
accompanied by a clear increase in bed height, after which bed
height increases almost linearly with ow (Fig. 4a) & leftmost
inset).
An additional interesting observation made is the signicant
inuence of system over pressure (due to back-pressure in the
sampling line). This is represented by the curves in Fig. 4a. As the
gure shows, even a low backpressure of 20 mbar extends the
pre-bubbling and bubbling range. Most importantly it shifts the
transition to full-uidization to somewhat higher ow rates. This
aspect must be considered when operating the bed under higher
pressures.
50
(a)
40
0.2
30
20
10
No back pressure
20 mbar back pressure
0
5
266
(b)
4
3
2
Total
Distributor
Particle Bed
1
0
0
0.44
0.01
2.95
100
200
300
400
500
600
267
As the pressure readings show (Fig. 4b), subtraction of the distributor pressure drop (measured without a bed) from the total
(measured with a bed) gives the additional drop due to the bed
particles. This bed ow resistance shows a constant increase past
the point of bubbling (60 Nl/h), with a clear drop-off from this
trend (saturation of the pressure drop) when full uidization is
attained (100 Nl/h). The fully uidized state can be seen in the
rightmost inset in Fig. 4a at an extreme ow-rate of 500 Nl/h). At
such high ow rates a large amount of particles can be carried
away by the ow obstructing the ow in the sampling line and
leading to an intermittent type ow (periodic eruption).
Therefore, optimal operation of a uidized bed of these size particles is in the lower fully uidized range (well stirring) at 200
250 Nl/h, the range used in subsequent experiments. The ranges
obtained from the cold ow observations were converted to the
much hotter bed conditions under the assumption that the density
follows the ideal gas temperature dependence and viscositys
dependence is described by the kinetic theory of gases.
r k0 eRT C nCO2
where R represents the universal gas constant and T the temperature. In this equation the pre-exponential factor k0, activation
energy E and reaction order n are the kinetic constants that have
to be determined.
First, the activation energy and pre-exponential factor are found
by variation of the temperature, at constant CO2 concentration.
Next, the order of reaction is deduced by variation of the
reactant-gas concentration at constant temperature, as shown in
Figs. 8 and 9, accordingly. The applied reaction rate for the determination of these parameters is the characteristic rate found by
1100
Temperature [K]
1050
1000
950
900
T(t )
1
850
T(t +24 h)
1
800
50
100
150
200
250
300
350
400
1.0
0.8
30 mm
40 mm
50 mm
70 mm
80 mm
0.6
0.4
0.2
0
30 mm
50 mm
60 mm
70 mm
30 mm
50 mm
60 mm
80 mm
R = 0.039 s -1
R 0.006 s -1
0
50
100
150
Time t [s]
Fig. 6. Carbon conversion vs. time in air (21% O2) at 800 C. Different symbols
indicate gas-sampling at different heights above the distributor, and comparison to
average URM prediction.
268
2
50
1.5
1
ln(r) [-]
75
2.5
CO2 [Vol. %]
CO [ppm]
3.6
100
CO2
CO
4.5
25
0.5
0
0
10
15
20
25
30
35
0
40
5
2
Time t [min]
-3
-3.5
0.5
dp
/
6
s
E
ko eRT C n1
CO2
DCO2 e2
1
1
1
/ tan h3/ 3/
-4
ln(r) [-]
ln(CCO ) [-]
-4.5
-5
-5.5
-6
-6.5
7.2
1.5
7.4
7.6
7.8
1/T [1/K]
8.2
8.4
8.6
-4
10
With homogeneity and reliability established, kinetic parameters were obtained for char gasication with high certainty and
in agreement with the literature. Char burnout rates were obtained
in batch-experiments by repeated FTIR spectroscopy of the product
gas. Data analysis procedures and establishment of kinetic parameters were exemplied by gasication of a pyrolyzed wood char.
The presented method having well-controlled conditions and
repeatable results, delivers competitive performance that allows
the development of a reaction kinetics database for support and
validation of simulation. Based on the understanding and results
gained from this study, the FBR can be evaluated as a
well-stirred reactor and by comparison to the mentioned methods.
The presented method also entails shortcomings which are discussed in the following.
The fuel delivery has uncertainty related to it as not all the carbon delivered is recovered in the gas analyzer. Additionally long
timescale operation (>3 h) has proven to be problematic: Lower
fractions of carbon are recovered, possibly because of weak gas
leakage, system noise or continuous particle elutriation from the
bed. Dead volume, piping length in the sampling system and dispersion of the signal limit reliable measurement of reactions
shorter than 15 s. Another limitation is the inherent coupling of
bed uid-dynamics to reactant-gas delivery. At higher ow rates
excessive entrainment occurs, yet sufcient reactant-gas may not
be available. This limit depends primarily on particle size, e.g. in
this study rates were limited to a reaction rate of about 0.07 s1.
Acknowledgements
The authors would like to thank the Helmholtz association for
funding Dr. Herman Haustein and Thobias Kreitzberg within the
frame-work of the Helmholtz Virtual Institute for Gasication
Technology (HVIGasTech). Therein, funding has been provided via
the Initiative and Networking Fund of Helmholtz Association.
Also, the authors would like to express their gratitude to DFG for
funding Benjamin Gvert and Dr. Anna Massmeyer via the
SFB/Transregio 129 Oxyame.
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[3] Geier M, Shaddix CR. Kinetic rate parameters for an extended single-lm char
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