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Biomass and Bioenergy 21 (2001) 121–132

A two-phase one-dimensional biomass gasication


kinetics model
Daniele Fiaschi ∗ , Marco Michelini
Dipartimento di Energetica “Sergio Stecco”, University of Florence, Via Santa Marta, 3, 50139 Firenze, Italy

Received 29 May 2000; received in revised form 4 January 2001; accepted 6 April 2001

Abstract
A mathematical model of biomass gasication kinetics in bubbling ,uidized beds has been developed. It is one-dimensional,
as it is capable of predicting temperature and concentration gradients along the reactor axis, and considers two phases, a
bubble and a dense phase. In addition to the reaction kinetics in the dense phase, mass transfer between the two phases
and a quantitative estimation of local bubble and particle properties are included in the model. A theoretical optimization
with respect to ER, pressure, bed height and gas velocity has also been performed. Finally, a comparison with experimental
data from the literature was done, which showed a largely satisfactory agreement, though further validation is still required.
c 2001 Elsevier Science Ltd. All rights reserved.

Keywords: Biomass; Gasication; Kinetics; Fluidized bed

1. Introduction as instantaneous because they are much faster than the


gasication process [1,2]. Then, the related starting
A correct design of the reactor, accounting also for products are set on an experimental basis. The major
the reaction kinetics, is fundamental to achieve an op- problem that arises is to correctly tune the kinetic pa-
timal conversion of the chemical energy present into rameters on experimental–theoretical basis, which are
the biomass feedstock. Several mathematical models able to depict a wide range of operating cases. Un-
have been proposed for biomass gasication kinetics fortunately, very poor detailed experimental data are
[1– 6], with di9erent degrees of compliance, accuracy available on this argument, and then it is diCcult to
and adaptability to the di9erent reactor types. Gener- verify the general validity of the proposed mathemat-
ally, almost the whole of computational models con- ical models.
sider the pyrolysis and sub-stoichiometric combustion The primary goal of this study has been to improve
previous biomass gasication kinetics models [1,7],
introducing the one-dimensionality and other di9usion
phenomena, which are typical of bubbling ,uidized
∗ Corresponding author. Tel.: +39-055-4796-436; fax: +39-055-
beds.
4796-342.
The present kinetic model considers a one-
E-mail address: danif@as.de.uni.it (D. Fiaschi). dimensional (axial) cylindrical ,uidized bed, divided

0961-9534/01/$ - see front matter  c 2001 Elsevier Science Ltd. All rights reserved.
PII: S 0 9 6 1 - 9 5 3 4 ( 0 1 ) 0 0 0 1 8 - 6
122 D. Fiaschi, M. Michelini / Biomass and Bioenergy 21 (2001) 121–132

Nomenclature
T local gasier temperature (K)
A reactor cross sectional area (m2 )
tdis time bound between dominating mass trans-
Ab bubble surface area (m2 )
fer and kinetics e9ects (s)
Cb reactant species molar concentration into the
vb bubble phase velocity (m=s)
bubble phase
Vb bubble volume (m3 )
Cd reactant species molar concentration into the
vikin reaction kinetics speed (mol=s)
dense phase
vit mass transfer speed (mol=s)
D di9usion coeCcient
vmf minimum ,uidization velocity (m=s)
Db bubbles diameter (m)
v0 inlet oxidizer velocity (m=s)
Dg gasier diameter (m)
vg ,uidizing gas velocity (m=s)
dp char particle diameter (mm)
vt solid particles entrainment velocity (m=s)
dp0 initial char particle diameter (mm)
w total moles of H2 O added (biomass wetness
dp0 average particle size after the primary frag-
+ eventual steam=water additions)
mentation (mm)
xdi fraction of solid particles of di size at the
h specic enthalpy of the chemical species
generic time t
(kJ=kg)
xib ith species molar fraction in the bubble phase
H overall reactor height (not including free-
xid ith species molar fraction in the dense phase
board)
y moles of oxidizing O2 per mole of biomass
hf enthalpy of devaluation of the chemical
ztot total moles of N2 added with the oxidizer (air
species (kJ=kg)
+ other)
j particle shrinking rate exponent
kbd bubble—dense phase mass transfer coeC-
Greek letters
cient
 moles of H2 per mole of C in the biomass
kc mass transfer coeCcient
∗ formula
Ki∞ elutriation rate (kg=m2 s)
 moles of O2 per mole of C in the biomass
Mb mass of solid particles in the ,uidized bed
formula
(kg)
 coeCcient accounting the in,uence of Dg on
n1 coeCcient accounting the primary fragmen-
vb
tation at the reactor inlet
b bubble phase fraction
n2 number of char particles coming through the
 initial molar ratio H2 Ovapour =CO2 produced
burn-o9
in the pyrolysis=combustion process
ns number of species involved in reactions
 local char particle density (kg=m3 )
P gasier pressure (bars)
ql local external heat transfer (kJ=kg)
Subscript
r dense phase overall reaction velocity (mol=s)
tot total amount from bubbles and dense phases
t generic instant of the gasication process (s)

into vertical elemental cylinders (with dense and bub- (1) input of the biomass composition and the oxidizer
ble phases) up to the freeboard zone: the reactions type, ER, moisture;
occurring in this volume have been neglected (the frac- (2) input of the general reactor design parameters:
tion of char particles where the surface reactions take length, diameter, thickness and wall materials;
place and the residence time of these particles in this (3) calculation of the bottom temperature;
reactor’s zone are very low). (4) iterative process for each cylindrical element
The main steps of the calculation procedures are into which the ,uidized bed has been divided,
summarized as follows: involving bed hydrodynamics, heat and mass
D. Fiaschi, M. Michelini / Biomass and Bioenergy 21 (2001) 121–132 123

transfer and gasication kinetics, up to the bed The gas ,ow entering the reactor at v0 speed
top; (Fig. 1), is split into two phases: the dense phase,
(5) comparison of the results with experimental data. (characterized by the minimum ,uidization velocity
vmf ), and the bubble phase (the velocity is v0 − vmf ).
The solid particles were supposed to be present only
2. Mathematical one-dimensional model for the in the dense phase; both phases follow a piston mo-
uidized bed reactor tion (compact ,ow without any mass transfer along
the z direction). No heat exchange occurs along the
The mathematical models for ,uidized bed reactors axial direction.
can be divided into three main groups, characterized The mass balance in the starting bubble phase has
by the number of phases accounted in the reactor: the following expression:
single-, double- and three-phase model [8]. dCb
The double-phase model has been the basis for the (v0 − vmf ) = kbd b (Cb − Cd ):
dz
present study, with a dense phase (gas plus solid par-
ticles) and a bubble phase (mainly gaseous with much Similarly, the overall mass balance for bubble and
lower solid matter) [8]. dense phases is
The two-phase reactor (Fig. 1) is modeled as the dCb dCd
sum of several elemental reactors of d z thickness. The (v0 − vmf ) + vmf + r(1 − b ) = 0:
dz dz
related di9erential equations are solved versus the tem-
perature and the syngas composition, along the gasi- The molar concentration of the ith component in the
er axis, for both dense and bubble phases. The model two phases has been expressed in terms of molar
is one-dimensional, and then it is particularly suitable fraction:
for bubble and circulating beds, where a high mixing xid nb xib nb
degree is present. The reactor is supposed to be down- Cid = ; Cib = ;
(1 − b )Vtot b Vtot
draft, both for the oxidant and biomass feeding. At a
model level, the freeboard area has been considered then, the mass balance in the bubble phase referred to
to be chemically inert. one mole of biomass is as follows:
 
vb1 d xib xid xib
= kbd − :
b2 d z (1 − b ) b

The dense phase mass balance, referred to one mole of


biomass, results from the algebraic sum of the chem-
ical kinetic rate and the bubble-dense phase transfer
rate:
d xid bxib
vmf = − vb1 − ri :
dz dz
The boundary conditions at z = 0 assume the same
concentration of each i species for both phases, then,
adding this statement to the mass balance condition:
xid xib
xitot = xib + xid = ;
(1 − b ) b

the only solid species C (carbon) has been set to zero


in the bubble phase (xCtot = xCd ).
The bubble-dense phase mass transfer coeCcient
Fig. 1. Two-phase model reactor. kbd has been estimated by the two-phase theory [8]
124 D. Fiaschi, M. Michelini / Biomass and Bioenergy 21 (2001) 121–132

as the sum of two terms (convective and di9usive) while the equivalent diameter
through the bubble surface Ab :
De = 0:2Hf0:8 P 0:06 (v0 − vmf )0:42
0:5 0:25
(N + Ab kc ) vmf D g
kbd = = 4:5 + 5:85 : exp[ − 0:00014P 2 − 0:25(v0 − vmf )2
Vb Db Db1:25
− 0:1P(v0 − vmf )]:
The bubble volume fraction b is expressed as
b (h) = v0v−v mf
b (h)
[5], where vb (h) is the local rising
particle speed, depending both on bubble and √ bed 3. Abrasion and elutriation phenomena
diameters. In this study, the expression vb = $ gDb
has been adopted [5], where  is a coeCcient re- The abrasion has been modeled considering both
lated to the gasier diameter Dg . The bed sand and primary and secondary fragmentations [12]: a multi-
the ,uidization mean in,uence these parameters (i.e. plying constant n accounts for the particle diameter re-
density and viscosity of the produced syngas). duction in the bed. The bed is supposed to be perfectly
The evaluation of bubbles diameter is one of mixed with uniform particle size, which reduction is
the topics for the proposed kinetic model. Several attributed to the following contributions (fragmenta-
theoretical–experimental investigations [9] lead to tion and spread of solids outside the reactor have been
many kinds of equations: however, they do not com- neglected):
pletely agree with each other, due to the in,uence of
the specic operating conditions on the several kinetic 1. chemical reaction kinetics, accounted by the j fac-
parameters. However, some general behaviors can tor (j is the exponent of the particle shrinking rate
be considered to relate the bubbles size, the reactor expression −d(dp )=dt = kdjp ) is related to the lim-
pressure and the gas velocity: iting reactions mechanisms (for example, j = 0 if
the reactions are kinetically limited);
• at a constant pressure, increasing the gas speed leads 2. abrasion, accounted by two multiplying constants
to an increase in the bubbles size for boiling bed n1 (primary fragmentation e9ect at the reactor inlet)
regime and a decrease at turbulent regime; and n2 (number of char fragments generated by the
• at xed v0 (or v0 − vmf ), the bubble size decreases burn-o9 of one char particle). The real number of
with increasing pressure for both turbulent and char fragments is assumed to be the mean between
boiling regimes (except for extremely low speed n2 and 1).
values).
Then, the following expression of mean Sauter particle
Being the main goal of this work, the evaluation of diameter comes out:
syngas composition versus residence time (i.e. along  −1=3
gasier height), an expression of the bubble size 3−j n1 (n2 + 1)
dp = dp0 :
as a function of the above parameters and the bed 4−j 2
level is required. Starting from the time averaged
For circulating beds, the particles rising from the bot-
bubble diameter at a xed bed height, it is often
tom to the top of the reactor vary their size, with re-
convenient to evaluate the equivalent diameter De
spect to the initial value; the average particle size after
(mean bubble diameter along the whole ,uidized bed,
H the primary fragmentation is related to its initial value
De = H1f 0 f Dbh dH ). The Rowe equation [10] and
by the following expression:
some coeCcients tuned on experimental data, have
been adopted to have an expression Dbh used in the (dp0 )3 = (dp0 )3 =n1 :
model [11]:
The elutriation has been modeled following two dif-
Dbh = 0:38 × H 0:8 P 0:06 (vo − vmf )0:42 ferent approaches [12,13]:
exp[ − 0:00014P 2 − 0:25(vo − vmf )2
• the rst one has been introduced into the existing
− 0:1P(vo − vmf )] model by calculating the instantaneous diameter and
D. Fiaschi, M. Michelini / Biomass and Bioenergy 21 (2001) 121–132 125

porosity of the particles and then the correspond- lated solid (carbon) and volatile products (CO2 , CH4 ,
ing entrainment velocity: if this is lower than the H2 O) are xed as the initial gasication species.
operating reactor speed, the corresponding elutri- Their amount depends on the composition and type of
ated mass at a xed height is subtracted from the biomass considered. The only hydrocarbon accounted
total mass of C. The elutriation rate is evaluated as in the syngas has been CH4 , while the other minor
in [13], for reactor levels higher than the Transport species Cn Hm have been neglected and eventually
Disengaging Height (TDH): included in the CH4 .
∗ With respect to the merely chemical models, the
Ri = d=dt(xbi Mb ) = Ki∞ Axdi ;
mass transfer contribution to the overall reaction speed

Ki∞ = 33(1 − vt =vg )2 has been added:
evaluated with the Colakyan correlation [13]. 6
vit = kc xid :
The main inaccuracy of this procedure is due to the dp
supposed particle’s uniform diameter: this implies
Two serial e9ects then limit the gasication speed:
that, at a certain height, the elutriation phenomena
chemical kinetics and mass transfer. Then, the rate
starts suddenly, which is quite diCcult to observe
of the ith chemical species follows (electrical model
in real cases.
analogy):
• The second one considers abrasion and burn as in-
dependent phenomena, then the elutriation is mainly vit vikin
vi = :
due to the rst one and the elutriated ,ow rate de- vit + vikin
pends on the instantaneous particle diameter (v0 − The char particle diameter at the ith time, is given by
vmf ), by the amount of C present in the bed and, the sum of the chemical reaction and abrasion e9ects
nally, by the friction coeCcient [12]. Following
the elemental reactor approach, the mass of char at dp (ti−1 )(xi (ti )=xi (ti−1 ))1=3
dp (ti ) = :
a given height is obtained by subtracting from the 1 + (nf − 1)p(1 − xi (ti )=xi (ti−1 ))
initial mass of C the amount consummated by the If the chemical reaction kinetic is the slowest process,
chemical reactions and the elutriation. This second the char particle reduces its density by increasing its
calculation scheme leads to a more gradual depic- porosity and leaving its external diameter dp almost
tion of the elutriation phenomena. unchanged. If at tdis time the chemical kinetic becomes
the limiting e9ect, the expression of the density (ac-
counting for the char consumption) when t ¿ tdis is
4. Evaluation of the overall reaction kinetics  
xi (tdis ) − xi (t)
(t) = (tdis ) 1 − :
The general biomass gasication reaction can be xi (tdis )
written as follows, starting from one mole of a generic
The mass transfer e9ects are predominant in the lowest
biomass CH O :
part of the reactor, where high temperature levels are
CH O + yO2 + ztot N2 + wH2 O = x1tot C + x2tot H2 +
present: then, tdis ¿ 0; obviously, tdis is a function of
x3tot CO + x4tot H2 O + x5tot CO2 + x6tot CH4 +
the temperature along the bed height.
ztot N2 = (x1d )C + (x2d + x2b ) H2 + (x3d + x3b )CO +
The temperature has been evaluated by a ther-
(x4d + x4b ) H2 O + (x5d + x5b ) CO2 + (x6d + x6b )
mal balance along each of the elemental reactors
CH4 + (zd + zb )N2 .
into which the ,uidized bed has been divided (time
The chemical gasication reactions considered in the
interval tj+1 − tj ):
present mathematical model are [1,7]:
ns
 ns

C + CO2 = 2CO; C + H2 O = H2 + CO; xitot (tj )hitot + xitot (tj )hfitot
C + 2H2 = CH4 ; H2 O + CH4 = CO + 3H2 : itot =1 itot =1
ns
 ns

The pyrolysis and partial combustion are supposed = xitot (tj+1 )hitot + xitot (tj+1 )hfitot + ql (tj ):
to be much faster than the gasication, then the re- itot =1 itot =1
126 D. Fiaschi, M. Michelini / Biomass and Bioenergy 21 (2001) 121–132

The heat exchange between the gas and the inert lling b (Fig. 4): at high values, (b ¿ 0:3) the inter-phase
material (sand) has been neglected, considering the mass transfer is high, since a great amount of mass is
elemental virtual reactor as a homogeneous ,uid with present in the bubble phase. Successively, the gasi-
uniform temperature [14]. cation products such as H2 and CO are rapidly trans-
However, the model also has the possibility of ferred from the dense phase (where they originate) to
working at a xed value of temperature, constant the bubble phase. Moreover, the mass transfer coeC-
along the whole bed height, like the previous basic cient is high enough to allow a fast stabilization of the
models [1,7]. concentration gradients and the related mass transfer
between the two phases. When both the bubble phase
fraction and the chemical reactions speed are consis-
5. Basic model results tently lowered (approach to the equilibrium), a par-
tial bubble-dense phase transfer can be observed for
The composition of the product gas versus the bed the gasication products. Also, the pyrolysis products,
height in both dense and bubble phases is shown in such as CH4 , CO2 and H2 O, decay in the bubble phase;
Figs. 2(a) and (b); the related basic data are reported the dense phase, after the starting, increased due to
in Table 1. Fig. 3 shows the resulting overall gas com- the increase in its volume, moves toward the stabiliza-
position: the equilibrium composition is practically tion while approaching the equilibrium. Finally, Fig. 4
reached after half of the reactor height. shows the non-linear trend of the minimum ,uidiza-
It is interesting to remark the correlation between tion velocity versus the reactor height: this is due to
the bubble phase composition and the void fraction vmf , which depends on the di9erence between the ll-
ing sand and gas densities as well as on the inverse
of gas viscosity, the latter decreasing with lowering
temperature.
The temperature behavior along the reactor axis is
shown in Fig. 5: a rapid decay can be observed just
after the Flame Pyrolysis (FP) zone, where the en-
dothermic gasication reactions start and a large and
rapid consumption of the combustion heat takes place.
Along the remaining 85% of the reactor height, the
temperature gradient is much lower, with values rang-
◦ ◦
ing between 900 C and 750 C, which are on line
with those from commercial ,uidized bed gasiers.
The above thermal balance can be regarded also as a
rst principle verication of the model along the bed
height.
The temperature at the transition time tdis has been

evaluated to be about 1610 C. Two di9erent char con-
sumption mechanisms can be drawn at model level:
char particle diameter reduction at the starting process,
due to the surface reaction and the abrasion mech-
anisms; subsequently, after tdis , the reaction kinetic
becomes dominant and the reacting char particles in-
crease their porosity, with low reduction of the exter-
nal diameter. It implies high values of dp at the reactor
exit, but the related particles density is strongly re-
Fig. 2. (a) Gas composition versus bed height in dense and bubble
duced, so they are characterized by a great amount of
phases (dense phase); (b) Gas composition versus bed height in voids, accounting for the e9ective char consumption
dense and bubble phases (bubble phase). (see Figs. 4 and 5). This mechanism is rather di9erent
D. Fiaschi, M. Michelini / Biomass and Bioenergy 21 (2001) 121–132 127

Table 1
Basic data for the gasication model run

Biomass composition (sawdust) CH1:41 O0:59  3

Humidity (dry basis) 10% Primary fragmentation factor n1 1.1


ER 0.33 Secondary fragmentation factor n2 1.8
Oxidizer Air Oxidizer inlet speed vo 1 m=s
Bed height 2:1 m Reactor wall thickness 0:25 m
Bed diameter, dg 1:30 m External convection 10 W=m2 K
Initial char particles diameter 5 mm Wall conductivity 0:1 W=m K

Char density 1500 kg=m3 External temperature 30 C
Inert particles diameter 800 m kat (elutriation coeCcient) 5 × 10−6
Inert particles density 2600 kg=m3 Gasier pressure 1:013 bar

Fig. 3. Overall gas composition versus bed height. Fig. 5. Gasication temperature, char particle density and bubble-
dense mass transfer coeCcient versus bed height.

mentation” mechanism; however, this aspect has not


been accounted in the present model.
Finally, Figs. 4 and 5 show also the behavior of the
bubbles diameter Db and the inter-phase mass transfer
coeCcient kbd along the reactor axis: the initial low
values of Db promote the mass transfer between the
two phases, due to the high bubble external specic
surface, then the high kbd values can be observed. This
parameter, however, remains high enough to allow a
fast inter-phase mass transfer along the whole reactor,
regardless of its initial rapid decay.
Fig. 4. Bubble phase fraction, particle diameter, bubbles diameter
and minimum ,uidization velocity versus bed height.
6. Sensitivity analysis: e'ects of the main
from those reported in [1,7], where the char density is operating variables
considered to be constant and the char consumption
is accounted by the reduction of the particle diameter The in,uence of the main parameters (Equivalence
dp . Obviously, particles with such high voids fraction Ratio ER, pressure and surface gas velocity) on the
tend to desegregate, following the “percolation frag- gasication process has been investigated.
128 D. Fiaschi, M. Michelini / Biomass and Bioenergy 21 (2001) 121–132

Fig. 7. A 70% char conversion ratio z(tC0:3 ) and syngas caloric


Fig. 6. Molar fractions of the di9erent species versus ER value at t = tC0:3 versus ER.
(bed height = 0:25 m).

The in,uence of ER is due to two important factors:

1. bottom reactor temperature increases with ER;


2. at xed values of temperature, the gasication re-
actions are predominant with respect to the com-
bustion reactions, up to ER = 0:4.

In this way, the gasication yield initially increases


with ER, and then it starts decreasing when the com-
bustion reactions become predominant. If the bed
height is limited (and the residence time is therefore
low, Fig. 6), relatively high ER values (¿0:4) are
Fig. 8. The tC0:1 bed height versus surface gas velocity with local
required to have a good syngas yield. For ER ¡ 0:2,
and mean overall Db evaluation.
the initial temperature is not suCcient to reach the
90% conversion of the char (C0:1 ). Accounting only
the 70% degree of the char conversion (C0:3 ), the cor- minimum bubbling value (about 0:5 m=s in this case)
responding bed height decreases with increasing ER, the bubble phase fraction is minimum and only the
but the gasication yield shows an opposite behavior dense phase can be accounted for in the reactor. In-
(see Fig. 7). creasing the surface gas velocity b increases: at v0 val-
Then, the ER values giving a suCcient initial tem- ues close to 1:1 m=s, almost 100% of the lower reactor
perature to make the gasication process eCcient for part is on a bubble phase, that undergoes a rapid de-
limited bed heights (approximately 1:5 m) are be- cay along the bed height. However, it remains higher
tween 0.3 and 0.4. This result is well evidenced by a than in the cases with lower v0 . In this way, the reac-
two-phase model, because it emphasizes the impor- tor volume available for the gasication reactions de-
tance of the mass-transfer e9ects for limited reactor creases in the rst part of the gasier and the related
heights, where the temperature is relatively high. gasication yield is lowered. Fig. 8 shows this e9ect
The surface gas velocity does not have a direct in- in terms of char conversion level: the increase in the
,uence on the chemical reaction rates, but only on the bubble phase fraction with v0 leads to an increase in
residence time, on the bubble phase reactor volume the reactants molar fractions for this phase, so they
(b ) and on the inter-phase mass transfer coeCcient cannot directly take part in the gasication until the
kbd (by b and Db ). For surface velocity close to the dense phase transfer has been completed.
D. Fiaschi, M. Michelini / Biomass and Bioenergy 21 (2001) 121–132 129

Fig. 10. Char conversion ratio and temperature discriminating the


dominant mechanism in the gasication process versus gasication
Fig. 9. Inter-phase mass transfer coeCcient versus v0 at di9erent pressure (bed height = 2 m).
bed heights.

ature at the beginning of the gasication process


The inter-phase transfer coeCcient kbd decreases (with reference to the selected biomass, see Table 1)

with increasing v0 , leading to a slower transfer of the is 1648 C, for pressure values over 20 bar, the reac-
reactants to the dense phase and, nally, of the prod- tions are completely limited by the chemical-kinetics.
ucts to the bubble phase (Fig. 9). The char conversion ratio versus the gasier pres-
Adopting the previously reported integral expres- sure shows (for a 2 m height bed) an optimizing value
sion of bubble diameter De [11], an optimizing value of 5 bar (Fig. 10): this is still mainly due to the opti-
of v0 in terms of char conversion z(C0:1 ) has been iden- mization of the Buduard’s reaction, together with the
tied close to 1:1 m=s due to the optimal inter-phase consistent inversion of the methanation reaction. At
mass transfer conditions (part of the reactants and this pressure level, the maximum CO and H2 and the
products are in both phases). In this way, the reactants minimum CO2 and CH4 molar fractions are found (this
of the dense phase allow a high degree of solid–gas result substantially agrees with those reported in [1]).
reactivity and, simultaneously, a consistent part of the
products is transferred to the bubble phase, allowing
the gasication reactions to be shifted toward the syn- 7. Comparison between single phase and double
gas products (Fig. 8). phase models
The gasication pressure in,uences the reaction
kinetics and equilibrium, the bubbles diameter and The two phase and the single-phase (b = 0) ap-
the bed voids fraction b . Generally, an increase in proaches have been tested and compared. The same
pressure leads to a reduction of the bubble diameters basic data have been assumed for both cases; the
and to an initial reduction of residence time: this, surface gas velocity v0 = vmin has been set for the
however, starts increasing at relatively high pressures single-phase runs.
(over 20 bar for the inquired biomass composition). The presence of two phases generally lowers the
The bed temperature increases with pressure: overall reaction kinetics, especially during the rst few
this is substantially due to the Buduard’s re- steps (Fig. 11), while the compositions tend to over-
action (C + CO2 = 2CO), that is shifted to the lap moving toward the equilibrium conditions at the
left-hand side and leads to an overall reduction bed top. This behavior is due to the presence of all the
of the gasication process. Also the limiting mass reactants only in the dense phase, for the single-phase
transfer=chemical kinetics temperature increases with model. For the two-phase model, when the bubble
the gasication pressure (Fig. 10), showing that fraction is suCciently reduced, the kinetic becomes
a more restricted part of the reactor is kinetically similar to that of single-phase cases. The methana-
mass-transfer limited. Since the maximum temper- tion reaction is mostly in,uenced by the presence of
130 D. Fiaschi, M. Michelini / Biomass and Bioenergy 21 (2001) 121–132

gasication (RUN 1, Table 2, Figs. 12 and 13). The


temperature value at the bed top is always underes-
timated: this is due to the overestimation of the ax-
ial energy transfer between the elements into which
the ,uidized bed has been divided at a model level.
As a consequence of these low nal temperatures, the
gasication process stops earlier, leading to an over-
all underestimation of the outlet char conversion ratio.
Accuracy within 12% for the caloric value and the
volumetric fractions of the di9erent gas species were
registered; H2 is highly overestimated.
The second test run was performed using the data
Fig. 11. Comparison between the e9ects of Chemical Kinetics + collection from an agricultural wastes gasication pro-
Mass Transfer (CK + MT) and Chemical Kinetics only (CK). cess [15] (RUN 2, Table 2, Fig. 14). The parameter
accounting the volatile matter at the gasication pro-
cess start up has been reset superimposing the CH4
the bubble phase: in the reference single-phase mod- relative errors to zero. The only experimental avail-
els, hydrogen is not initially present, which leads to able data were the caloric value and H2 ; CO and
a fast inversion of this reaction with an immediate CH4 + Cn Hm volumetric fractions: the agreement of
production of H2 and the subsequent rapid methane the calculations with the available experimental data
consumption. is quite satisfactory, showing an overestimation of H2 ,
Given the relatively high starting temperature, the while the other volumetric fractions have been well
mass transfer e9ects have been found to be important predicted.
up to tdis ; after this time, the results of the two ap- Finally, a test run was performed with RDF (RUN 3,
proaches tend to resemble each other, since the chemi- Table 2): the basic available data are shown in
cal kinetic becomes the slowest process. On the whole, Table 2 [16]. Fig. 15 summarizes the related results,
it can be concluded that only the initial gasication re- for both air and oxygen as oxidizers. In the rst case,
actions steps are substantially in,uenced by the mass the agreement between theoretical and experimental
transfer e9ects, while at the top of the reactor only the data is quite satisfactory, while it is poor in the second
chemical kinetic plays a dominant role on the overall case. It is mainly due to the initial higher temperature,
reaction mechanisms (Fig. 11). which leads to an over estimation of the Buduard
reaction speed (and the related CO production) for
oxygen gasication. A test with constant xed bed
8. Model veri-cation temperature has been performed for the oxygen gasi-
cation, which brought a consistent improvement to
A preliminary test validity of the developed kinetic the predicted data.
model has been carried out using some experimental
data from the literature. These data often missed some
of the needed topic parameters for the simulation: in 9. Conclusions
these cases, they have been reasonably assumed. The
comparison of the numerical results with the experi- The present gasication kinetics model has been de-
mental data, also allowed an improvement in the set- veloped starting from previous zero-dimensional mod-
tings of some reactions’ chemical kinetic parameters, els. It is one-dimensional and biphasic, which allows
such as the activation energy and the frequency fac- the mass transfer e9ects to be accounted on the re-
tor. Three of these test runs have been chosen to be action kinetics mechanisms. The gasier freeboard is
reported in the present work. considered to be inert.
Keeping the same data entry of [5] (Table 2), the The introduction of the two phases allowed to point
rst test was performed with two runs of wood chips out that the mass transfer activity is an increasing
D. Fiaschi, M. Michelini / Biomass and Bioenergy 21 (2001) 121–132 131

Table 2
Basic experimental test data conditions

RUN 1 RUN 2 RUN 3

Wood chips Wood chips Almond Grass straw Corn stalk Pelletized
1.1 3.1 shell RDF

ER 0.298 0.273 0.132 0.157 0.162 0.27– 0.41


Moisture (%) 16.2 17.4 33.0 42.5 43.5 5.8
Biomass composition CH1:41 O0:59 CH1:59 O0:70 CH1:38 O0:65 CH1:53 O0:74 CH1:6 O0:56
Bed height (m) 1 0.75 0.5
Bed diameter (m) 0.3 0.66 0.15
Wall thickness (m) 0.1 0.25 —

Wall conductivity (W=m C) 0.03 0.03 0.03
Ext. ,uid convection 6 6 6
coe9. (W=m2◦ C)

Ext. Temp. ( C) 25 25 25
Sand diameter (mm) 0.5 0.58 7
Sand density (kg=m3 ) 2670 2670 2600
Char initial diameter (mm) 12 7 6 6 9
Char initial apparent density (kg=m3 ) 1500 1500 1500

Fig. 12. Model verication for RUN 1.1. Fig. 14. Model verication for RUN 2.

Fig. 13. Model verication for RUN 3.1. Fig. 15. Model verication for RUN 3.
132 D. Fiaschi, M. Michelini / Biomass and Bioenergy 21 (2001) 121–132

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