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Drag Coef
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Article history: The pyrolysis of a freely moving cellulosic particle inside a 41:7 mg s1 continuously fed
Received 16 August 2007 fluid bed reactor subjected to convective heat transfer is modelled. The Lagrangian
Received in revised form approach is adopted for the particle tracking inside the reactor, while the flow of the inert
23 April 2008 gas is treated with the standard Eulerian method for gases. The model incorporates the
Accepted 24 April 2008 thermal degradation of cellulose to char with simultaneous evolution of gases and vapours
Available online 20 June 2008 from discrete cellulosic particles. The reaction kinetics is represented according to the
Broido–Shafizadeh scheme. The convective heat transfer to the surface of the particle is
Keywords:
solved by two means, namely the Ranz–Marshall correlation and the limit case of infinitely
CFD
fast external heat transfer rates. The results from both approaches are compared and
Fast pyrolysis
discussed. The effect of the different heat transfer rates on the discrete phase trajectory is
Cellulose
also considered.
Particle modeling
& 2008 Elsevier Ltd. All rights reserved.
Fluidised bed
1. Introduction Fluidised beds are the most widely used type of reactor for
fast pyrolysis, as they offer a number of advantages, such as
Pyrolysis is thermal degradation of organic materials in high heat transfer rates and good temperature control. The
absence of oxygen. The primary pyrolysis products of hydrodynamics of fluidised beds have been widely investi-
cellulosic particles are usually referred to as condensable gated, both experimentally and numerically, to allow valida-
and noncondensable volatiles and char. The condensable tion of the model results. To date most of the computational
volatiles are also often classified as liquids, and the non- research interest has been focused on the simulation of the
condensable volatiles as gases [1]. The liquids are frequently fluidised bed hydrodynamics, using either the Eulerian
subdivided into water and organics. Secondary reactions of (continuum) [7] or the Lagrangian (discrete element) [8,9]
the vapours produced result in the formation of secondary model, as well as novel models like that developed by Bokkers
degradation products, and generally reduced organics yields. et al. [10] which is based on the modelling of the larger
The extent of secondary cracking depends in particular on the bubbles as discrete elements that are tracked individually
hot vapour residence time. The reaction kinetics of cellulose during their rise through the emulsion phase, which is
was originally based on the Broido Shafizadeh scheme [2]. considered as a continuum. Due to the significant increase
Many researchers question the validity of the classic scheme in computing power of recent years, these models have now
[3–6] especially on the initiation of the decomposition with made computational modelling of multiphase granular flows
the formation of ‘‘active cellulose’’. However, researchers possible, though it is still very challenging, particularly so for
have not yet concluded to a global pyrolysis mechanism industrial scale reactor units.
for cellulose and considerable amount of research is still Little attention has been paid to the computational model-
going on. ling of biomass particles tracked through a fluidised bed
Nomenclature T temperature, K
Ti stress tensor of phase i
Ai pre-exponential factor, s1 Tp particle temperature, K
Ap particle surface area, m2 T1 local temperature of the continuous phase, K
CD drag coefficient u continuous phase velocity, m s1
Cp specific heat capacity, J kg1 K1 up particle velocity, m s1
dp particle diameter, m Ui internal energy of phase i per unit mass, J kg1
E activation energy, J mol1 vi velocity vector of phase i ðui ; vi ; wi Þ, m s1
f drag function V volume, m3
fi force acting on phase i
FD drag force per unit particle mass Greek symbols
gx gravitational acceleration, m s2
h convective heat transfer coefficient, W m1 K1 ei volume fraction of phase i
hni enthalpy of phase i at non-equilibrium, J kg1 li bulk viscosity of phase i
k thermal conductivity, W m1 K1 m viscosity, kg m1 s1
Kij interphase momentum exchange coefficient r density, kg m3
mi mass of phase i, kg ri density of phase i, kg m3
m0i volumetric mass source of phase i, kg m3 s1 rp droplet density, kg m3
mp particle mass, kg ti particulate relaxation time
Nu Nusselt number t̄¯ i viscous stresses tensor for phase i
pij interaction forces between phases, kg m2 s2 f shape factor
Pi pressure of phase i, N m2
Pr Prandtl number Subscripts
qi net rate of heat outflow of phase i, kW m3
R universal gas constant, J mol1 K1 D drag
Re relative Reynolds number i; j phase subscripts
Red particle Reynolds number p particle
s path of particle wo wood
S source term
t time, s
reactor during fast pyrolysis, as well as the impact of the gases are simulated, based on the Broido–Shafizadeh scheme
production of vapours and gases on the fluidised bed for cellulose pyrolysis (up to 40–50% of wood composition),
hydrodynamics. Although it is not possible to track a large with simultaneous particle tracking into the reactor. In
number of biomass particles discretely in a reactor, a single this way the residence time of the cellulosic particle can
particle model could provide some representative informa- be determined as well as the flow pattern of the released
tion not available in a general Eulerian flow model. Several gases and vapours. The heat transfer from the fluidising
heat transfer models have been developed to predict the heat gases to the surface of the cellulosic particle is modelled
transfer coefficient for a sphere moving in fluidised beds using (i) the Ranz-Marshall [15,16] correlation (RMC) and (ii)
[11–13] but none of these has been fully incorporated into a the limit case of infinitely fast external heat transfer rates
CFD code, so that the effect of the heat transfer from the (IFEHTR).
bubbling fluidised bed to the surface of a single biomass
particle can be quantified. The innovative work of Brown et al.
[14] was to apply CFD in a laminal entrained flow reactor, to 2. Model description
predict an accurate time–temperature profile of the reactants
and to understand the internal processes of the reactor. For a The 41:7 mg s1 fast pyrolysis reactor of Aston University is
fluidised bed this is a difficult task, since there are many illustrated in Fig. 1. Nitrogen flows through a porous plate at
parameters to be considered, such as the momentum the bottom of the reactor at a velocity of U0 ¼ 1:2 m s1 and
transport from the fluidising gases and the bubbling sand, temperature 773 K. The superficial velocity is more than an
the time fractions of contact with the particulate phase as order of magnitude larger than the minimum fluidising
well as the reaction kinetics of biomass degradation to velocity Umf of the reactor, which is typically around
vapours, gases and char. 0:08 m s1 using a sand bed with average particle diameter
As a first stage of model development, the present study of 440 mm Geldart B Group [17]. As has been stated previously,
focuses on the simulation of a single cellulosic particle, the presence of the sand bed is not taken into account
injected into a 41:7 mg s1 reactor, neglecting the presence of at this stage of model development and the cellulosic
the sand and exposed only to convective heat transfer. The particle is only exposed to convective heat transfer by the
reactor geometry is based on an existing lab scale 41:7 mg s1 fluidising gas. The gas velocity chosen for the work here
unit in Aston University. The evolution of vapours and reported is closer to that of an entrained bed reactor rather
ARTICLE IN PRESS
BIOMASS AND BIOENERGY 33 (2009) 97 – 107 99
Conservation of mass requires that the sum of the volumetric The a coefficients are given by
mass sources ðm0i Þ over i phases be zero, therefore 8
>
> 0; 24; 0 0oReo0:1
>
>
>
> 3:690; 22:73; 0:0903 0:1oReo1
X
n >
>
mni ¼ 0 (4) >
>
>
> 1:222; 29:1667; 3:8889 1oReo10
i¼1 >
>
< 0:6167; 46:50; 116:67 10oReo100
a1 ; a2 ; a3 ¼ (14)
>
> 0:3644; 98:33; 2778 100oReo1000
>
>
>
> 0:357; 148:62; 47 500 1000oReo5000
>
>
>
>
2.2.1.2. Momentum balance. The momentum balance for >
> 0:46; 490:546; 578 700 5000oReo10 000
>
>
: 0:5191; 1662:5; 5 416 700 ReX10 000
phase i is given by
qðei ri vi Þ
þ r ðei ri vi vi Þ ¼ r Ti þ ei ri f i þ pij þ m0i vi (5)
qt
where Ti defines the stress tensor, which is expressed through 2.2.1.3. Energy balance. The energy balance for phase i is
the definition of phase pressure and viscous stresses via the given by
identity matrix I. qðei ri Ui Þ
þ r ðei ri vi Ui Þ
Ti ¼ Pi I þ t̄¯ i (6) qt
qe
¼ r ei qi Pi i Pi r ei vi þ hni m0i þ ui (15)
The viscous stresses tensor t̄¯ i for phase i is given by qt
where Ui is the internal energy of phase i per unit mass, qi is
t̄¯ i ¼ ei mi ðrvi þ rvTi Þ þ ei ðli 23mi Þr vi T̄¯ (7)
the net rate of heat outflow of phase i and hni the enthalpy
The product ei ri f i defines the body forces, pij the inter- entering system i at possibly non-equilibrium conditions.
action forces between the phases and m0i vi the momentum
changes due to phase change. The quantity vi defines 2.2.2. Particle motion equations
the velocity vector ðui ; vi ; wi Þ. The interaction pij term is The equation of motion for particles is given by a force
defined as balance which equates the droplet inertia with the forces
X
n X
n acting on the droplet
pij ¼ Kij ðvi vj Þ (8)
dup gx ðrp rÞ
i¼1 i¼1 ¼ FD ðu up Þ þ (16)
dt rp
where Kij is the interphase momentum exchange coefficient
defined as where FD is the drag force per unit particle mass defined as
18m CD Re
ei ej ri f FD ¼ (17)
Kij ¼ (9) rp d2p 24
ti
The particulate relaxation time ti is defined as The drag coefficient CD given by [19] is defined as
24 b3 Red
ri d2i CD ¼ ð1 þ b1 Rebd2 Þ þ (18)
ti ¼ (10) Red b4 þ Red
18mj
where
and the drag function f is given by [19] as
b1 ¼ expð2:3288 6:4581f þ 2:4486f2 Þ (19)
CD Re
f¼ (11)
24 b2 ¼ 0:0964 þ 0:5565f (20)
where
b3 ¼ expð4:905 13:8944f þ 18:4222f2 10:2599f3 Þ (21)
a2 a3
CD ¼ a1 þ þ (12)
Re Re2
b3 ¼ expð1:4681 þ 12:2584f 20:7322f2 þ 15:8855f3 Þ (22)
and
The shape factor f is given by [21] as
rdjup uj s
Re ¼ (13) f¼ (23)
m S
In the limit case of IFEHTR, the particle temperature (initially 3.1.1. Reaction kinetics
at 303 K) rises instantaneously to the reactor temperature The rapid heating causes the cellulose to be activated
(773 K). The reaction mechanism, which is extremely tem- extremely fast as shown in Fig. 7, which in turn is converted
perature dependent, is instantaneously initiated and the to the pyrolysis products char, gases and vapours. As the
particle is instantaneously heated to 773 K, only 0.0022 s are
needed for the cellulose to be activated. The production
of vapours, gas and char is almost instantaneously initiated.
Table 1 – Simulation parameters Fig. 8 shows the rate of production of the vapours, gases and
char in respect to the residence time of the cellulosic particle
rwo ¼ 700 kg m3 into the reactor. The total amount of the produced vapours
dp ¼ 500 mm ( 92% of cellulose mass) has been generated in 0.235 s, which
U0 ¼ 1:2 m s1 corresponds to the residence time of the cellulosic particle in
T ¼ 773 K the reactor. The amount of gases produced reach 4% of the
r ¼ 0:457 kg m3 cellulose mass, and the produced char is 2% of the cellulose
m ¼ 3:55 105 kg m1 s1 mass.
E1 ¼ 242:8 106 J kmol1 The Broido–Shafizadeh mechanism is based on cellulose
E2 ¼ 150:7 106 J kmol1 and does not take account of char formation due to the
E3 ¼ 196:8 106 J kmol1 degradation of the lignin component of biomass. This results
E4 ¼ 108:0 106 J kmol1 in the high vapours yields and low char and gas yields. The
A1 ¼ 2:8 1019 s1 final quantity of the produced vapours is highly affected by
A2 ¼ 1:3 1010 s1 their residence time in the reactor. The reason is that
A3 ¼ 3:2 1014 s1 secondary reactions (extra-particle vapour cracking catalysed
A4 ¼ 2:6 106 s1 by char/ash) take place as it is illustrated in the reaction
x ¼ 0:35
kinetics schematic (Fig. 2). Consequently, the higher the
y ¼ 0:65
residence time of the vapours is, the higher the amount of
gas produced. In this case, the vapour residence time is
ARTICLE IN PRESS
102 BIOMASS AND BIOENERGY 33 (2009) 97– 107
Fig. 4 – Vapours evolution (volume fraction) in the reactor as particle moves to the outlet (IFEHTR).
700 2.5
x − velocity
600 Particle Density 2
y − velocity
1.5
500
1
400
0.5
300
0
200 −0.5
100 −1
−1.5
0
0 0.05 0.1 0.15 0.2 0.25
0 0.05 0.1 0.15 0.2
Particle Time (s)
Particle Time (s)
Fig. 9 – Particle x–y velocity change inside the reactor
Fig. 6 – Particle density change with time (IFEHTR).
(IFEHTR).
0.9 Vapours
Char
0.8 Gases sufficiently small to have a large impact on the relative yields
of vapours and gas.
0.7
Mass Fraction
Fig. 11 – Vapours evolution (volume fraction) in the reactor as particle moves to the outlet (RMC).
This easily explains the fast increase in the y-velocity of the Figs. 10–12, respectively. In contrast to the IFEHTR case, the
particle, since it is heavily dependent on the particle density. inclusion of convective heat transfer to its surface gives rise
to slower heating. According to Eq. (25), the temperature rise
3.2. Heat transfer using the RMC on the particle is a function of the particle mass. This means
that the sooner the reaction mechanism is initiated and the
3.2.1. Particle heating mass of the particle drops, the faster the heating of the
The particle position at different times as well as the volume particle is going to be. Fig. 13 shows that the particle
fraction contour plots and velocity vectors are illustrated in temperature smoothly rises up to 700 K in 1.2 s, while, in the
ARTICLE IN PRESS
BIOMASS AND BIOENERGY 33 (2009) 97 – 107 105
800 next 0.3 s the particle is rapidly heated up to 773 K. This effect
750 is caused by the rapid density drop of the particle when the
Particle Temperature
reaction takes effect, and due to the fact that only external
700
heat transfer resistance is considered. If conduction inside
650 the particle is taken into account, the average heating would
Temperature (K)
500 Fig. 16 illustrates the x–y velocities of the particle during its
motion in the reactor. Unlike the case of infinitely fast heat
400 transfer rates, the case of convective heat transfer to the
Particle Density particle results in a fall down to the bottom of the reactor,
300 since its density remains unchanged for almost 1.2 s. The
initial cellulose density of 700 kg m3 is high enough for
200 gravity to overcome drag. The boundary condition on the inlet
of the reactor is set to ‘‘reflect’’, which means that the particle
100
was assumed to elastically collide with the perforated plate at
the bottom of the reactor, using a restitution coefficient of 0.9.
0
0 0.2 0.4 0.6 0.8 1 1.2 1.4 1.6 This is the reason why a slight bouncing of the particle,
represented like a saw function, is visible for a period of 1.2 s
Particle Time (s)
in Fig. 16. After the rapid effect of the reaction mechanism on
Fig. 14 – Particle density change with time (RMC). the density of the particle, the latter starts its flight in the
reactor until it reaches the reactor outlet. Again the particle
accelerates in the y-velocity direction, since the decrease of
particle density allows the drag force to overcome its gravity.
As the particle is directed to the outlet of the reactor, the x-
velocity of the fluidising gas again starts to dominate, thus
the particle is easily driven out of the reactor in 1.575 s.
4. Conclusions
2
x − velocity
0.5
−0.5
−1
0 0.2 0.4 0.6 0.8 1 1.2 1.4 1.6
Particle Time (s)
2
y − velocity
Particle y velocity (m/s)
−1
−2
0 0.2 0.4 0.6 0.8 1 1.2 1.4 1.6
Particle Time (s)
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