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Fuel Processing Technology 86 (2005) 1021 – 1053

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Modeling circulating fluidized bed biomass gasifiers.


A pseudo-rigorous model for stationary state
Jose Corella*, Alvaro Sanz
Department of Chemical Engineering, University "Complutense" of Madrid, 28040-Madrid, Spain

Received 11 June 2004; received in revised form 19 November 2004; accepted 19 November 2004

Abstract

A 1-dimensional model for an atmospheric circulating fluidized bed biomass gasifier (CFBBG)
under stationary state is presented in this paper. The model is based on the kinetic equations for the
reaction network solved together with mass and heat balances and with several hydrodynamic
considerations. Kinetics used include both our own kinetic data and published equations with some
corrective factors. The reaction network used involves twelve different reactions. A sub-model for
the tar generation-elimination in the CFBBG is included in the whole model. The model has an
academic structure, but several assumptions were made because of lack of accurate data in some
areas. The overall model has some empirical aspects and can therefore be considered as semi-
rigorous. Hydrodynamics in the model were checked with a survey carried out worldwide among the
existing pilot and commercial CFBBGs. The axial profiles of concentration of ten different species
(H2, CO, CO2, tar, char, . . .) and temperature can be calculated with this model which was conceived
to optimize both design and operation of CFBBGs.
D 2004 Elsevier B.V. All rights reserved.

Keywords: Reaction engineering; Energy; Fluidization; Mathematical modeling; Biomass gasification; Tar

1. Introduction

Thermochemical gasification of biomass generates a useful gas (a mixture of H2, CO,


CO2, CH4, small hydrocarbons,. . .) using a gasifying agent, usually air, also being the only

* Corresponding author. Tel./fax: +34 91 394 4164.


E-mail address: narvaez@quim.ucm.es (J. Corella).

0378-3820/$ - see front matter D 2004 Elsevier B.V. All rights reserved.
doi:10.1016/j.fuproc.2004.11.013
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gasifying agent considered in this paper. Commercial biomass gasifiers are nowadays
facing serious problems, especially their economical feasibility: the energy from the
produced or gasification gas has to be competitive with natural gas which is abundant and
cheap. One biomass gasifier which can have some future is the atmospheric circulating
fluidized bed gasifier (CFBBG) with a few commercial units operating in the Netherlands,
Austria, Sweden, Finland and Germany [1]. The produced gas is bdirtyQ (contains some
tar) and usually it is directly fired in an adjoining combustor. Nevertheless, the most
promising future applications of the thermochemical gasification of biomass will require at
least both (i) generating a bquite cleanQ gas (to be fired in gas engines or turbines, for
example), and (ii) having no troubles in the gasifier (with a continuous non-stop
operation). These two facts require that the gasifier has an optimized design and operation
which does not occur very often. Although most gasifier manufacturers may claim that
their respective gasifiers are already optimized, a good model might help to optimize both
gasifier design and its operation. For this reason this work is devoted to develop a model
bas good as possibleQ for CFBBGs.
There is huge amount of papers on hydrodynamics of CFBs which are very useful for
modeling CFBBGs, as the book edited by Grace et al. [2]. Concerning the modeling of
fluidized bed gasifiers, the field of coal is well ahead of that of biomass. There are a lot of
works (i.e., [3–16]) on modeling CFB coal combustors and gasifiers which contain very
valuable information and help to model CFBBGs. They were used in different parts of the
modeling of CFBBGs presented here. Nevertheless, it is well known and accepted that
thermochemical processing of biomass has some important differences with respect to the
processing of coal. Two of them are important for the CFBBG modeling: (1) biomass is
much more reactive than coals, it pyrolyzes very quickly and its ash content is usually very
low. For these and other reasons, another solid, sometimes called fluidizing, has to be used
in the gasifier. It is usually silica sand. Besides, an additive (dolomite, limestone,
olivine,. . .) is also used in the gasifier for tar cracking, alkali capture, etc., . . . The particle
size of these two solids (silica sand and additive) is an important variable in the process. (2)
Biomass gasification below 1000 8C always produces important amounts of tar whose
content in the flue gas has to be estimated with a good model for it to be it useful. Literature
on biomass is therefore more important for CFBBG modeling than coal, but it is less
abundant and the existing approaches are not yet as rigorous and developed as those for
coal. The literature on modeling biomass gasification in fluidized bed is much more related
to this work than that of coal but it is so scarce that it can be fully cited.
In modeling biomass gasification (with air) in bubbling fluidized beds (BFBBG),
Belleville and Capart [17] developed an empirical but quite interesting model which was
successfully applied to the biomass gasifier of Creusot Loire in Clamecy (France). Fan and
Walawender [18] and Van den Aarsen [19] reported two of the pioneering models, which
are well known today; Corella et al. [20] modeled some non-stationary states of BFBBGs;
Bilodeau et al. [21] considered axial variations of temperature and concentration and
applied their results to a 50 kg/h pilot gasifier; Jiang and Morey [22,23] introduced new
concepts in this modeling, especially related to the freeboard and the fuel feed rate; Hamel
and Krumm [24] provided interesting axial profiles of temperature, although their work was
mainly focussed on gasification of coal and did not give many details of their model;
Mansaray et al. [25,26] presented two models using the ASPEN PLUS process simulator
J. Corella, A. Sanz / Fuel Processing Technology 86 (2005) 1021–1053 1023

but referred to their specific bdual-distributor-typeQ BFBBG, limiting their usefulness.


Concerning modeling of BFBBGs with steam, Corella et al. [27] presented a model based
on the Kato and Wen model for fluidized beds. The main contribution of their model is that
it identifies, amongst the complex gasification reaction network, the four main (for
modeling purposes) chemical reactions. That model fits then the experimental gasification
data with only four parameters (chemical kinetic constants).
If there are only a few papers on modeling BFBBGs, literature on modeling CFBBGs is
even more scarce. The absence of details in the literature on CFBBG modeling is not
surprising because, besides the very few existing commercial CFBBGs, it was mainly
written for marketing purposes. Models claimed to exist can neither be checked nor used
by readers because most of the key information is missing. Most of the manufacturers and
users of CFB biomass gasifiers at commercial and pilot scales claim to operate a good own
model but not much more is said about it. Lurgi, ECN, TPS, IGT, etc.,. . . for instance,
reported to have their own models but they did not provide details of such models. The
UMSICHT Institute in Oberhausen, Germany, [28] and University of Siegen in Germany
too [29,30] provided some data from their own models for CFBBGs, but what is
considered to be the core of such models is again missing from their papers. Kersen et al.
[31] recently provided a model for the pilot CFBBG at ECN but, as the same authors
recognized, it is an interpretation model which cannot be used for design and scale-up
purposes. Finally, the model for CFBBGs recently published by Liu and Gibbs [32], which
were also our partners on the same project that financed the work presented here, is similar
to the model presented in this paper, but theirs is manly addressed to NH3 and HCN
emissions.
A detailed and advanced model for CFBBGs does not exist in the open literature, up to
now. Such a model would be useful to optimize both the design and operation of a
CFBBG. The main aim of this paper is to develop a valuable model for CFBBGs and to
give a description of its main parts or sub-models. Results from the model are being
presented in the next paper [33].

2. Basis of the model

2.1. Topology or description of the considered CFBBG

Atmospheric CFB biomass gasification nowadays is not yet a well established


technology. There are very few commercial gasifiers worldwide and each gasifier
manufacturer (TPS AB, Lurgi, Foster Wheeler Energy, Austrian Energy,. . .) has its own
design. So far there is no consensus on the detailed design of a CFBBG. The selection
of a standard scheme for a CFBBG was therefore not an easy task. After a detailed
analysis of the existing technology, including the small CFBBG owned and handled by
the authors, the selected scheme for a CFBBG is shown in Fig. 1. Some aspects of it are
the following:

i) Although some CFB coal gasifiers do not have a dense bed at the bottom, the
CFBBG considered here has a bottom bed, which is quite important in biomass
1024 J. Corella, A. Sanz / Fuel Processing Technology 86 (2005) 1021–1053

gasification. It increases the heating transfer rate to the particles of biomass, and
decreases the tar yield [34]. Among the CFBBGs analysed by the authors, the ones
with a stationary bottom bed and a biomass feeding into it generate less tar than if
there is not such bottom bed or if the biomass is fed above it. An additive (D), such
as calcined dolomite (OCad OMg), limestone or related materials, is also considered
to be as stationary, permanent or fluidizing material, together with the silica sand (S).
This additive decreases the tar yield at the gasifier exit and prevents bed
agglomerations [35–37].

Gas

ε = 0.99 Dilute Zone


Hdz

2nd Air Mixing 2nd Air H4


HT
H3

Transition Zone
ε = 0.90 Htz
H2nd
ε = 0.77
Bottom Zone
Biomass Feed Pyrolysis H2 Hbt

H1

1st Air
Fig. 1. Scheme for the selected CFBBG to be modeled.
J. Corella, A. Sanz / Fuel Processing Technology 86 (2005) 1021–1053 1025

ii) Biomass feeding point is located at the bottom of the gasifier, the biomass is fed
directly into the bottom bed.
iii) The stationary bed and main circulating material will be a mixture of silica sand and
20–30 wt.% of calcined dolomite [35].
iv) Air flow will be handled as the equivalence ratio, ER [total air flow fed to the
gasifier/stoichiometric (for total combustion)air flow]. The total air fed (to the
gasifier) is split into the primary and secondary air flows shown in Fig. 1. The
secondary air flow is located above the biomass feeding point; together with the
biomass feeding there could also enter some additional sealing air which would be
considered as secondary air. The height of such 2nd air flow inlet is called H2nd, Fig.
1. This secondary air flow is usually used to increase the temperature in the upper
part of the gasifier to decrease, by thermal reactions such as cracking, the tar content
in the gas flows. As a typical or reference case, the 2nd air flow is considered to be
the 20% of the ER value.

2.2. Scales studied for the CFBBG

Not only commercial CFBBGs are of interest. There are other CFBBG of smaller scale,
pilot and demo sizes, which have also been considered and covered by the modeling.
Three scales were therefore considered. They are indicated in Table 1, together with their
representative values.
The gasifiers corresponding to the three scales were considered to have the same area
specific throughput (=1740 kg biomass fed, as received/h m2 of gasifier cross-sectional
area in the dilute zone), weight hourly space velocity for the biomass (WHSV) [=1.9 (kg
biomass fed, as received)/h]/kg solids inventory in the CFBBG] and total height for the
riser (=14.8 m). These values have been selected from a careful analysis and survey of the
existing CFBBGs worldwide. The inner diameters in the dilute zone of the CFBBGs for
these three scales are 7.6 cm, 0.85 m, and 3.3 m, respectively.

2.3. Operation intervals considered

After a careful analysis of biomass gasification itself and of existing bed biomass
gasifiers, the intervals for the main operation variables were selected. These are shown in
Table 2. Most of the existing fluidized biomass gasifiers operate, or should be operated,
between the intervals or limits shown in Table 2.

Table 1
Scales studied for the CFBBG
Scale ṁB Basis/Reference i.d. HT
(kg a.r./h) (m) (m)
Throughput WHSV W sand+dolomite
(kg a.r./h m2) (h1) (kg)
Pilot 8.0 1740 1.9 4.2 0.076 14.8
Demo 1000 1740 1.9 520 0.85 14.8
Commercial 15000 1740 1.9 7760 3.3 14.8
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Table 2
Intervals considered for the main operation variables
Parameters Intervals considered
ER: 0.20–0.45
Biomass moisture (wt.%): 5–30
Biomass flow rate (kg/h): 2–20,000
WHSV (h1): 1.0–3.0
Throughput (kg biomass a.r./h m2): 1000–7000
2nd air flow (%): 0–40
2nd air inlet height (m): 5–10
u o (m/s): 2–10
T bottom bed (8C): 750–980

2.4. Inputs and outputs to/from the modeling

The inputs for the model are indicated in Table 3. They include the biomass to be
gasified, the air (gasifying agent), the gasifier design and the biomass feeding flow which
can be expressed in several ways: as mass flow rate (kg/h), as weight hourly space velocity
[WHSV in (kg biomass/h)/kg solids inventory in the CFBBG] or as throughput (kg
biomass/h m2 cross-sectional area in the dilute zone). Two important input data concerning
the biomass feedstock, particle size distribution and its alkali (K+Na) content (sintering or
agglomeration problems), are not directly handled by the model in its present state of
development. For now, these two parameters will have to be handled in parallel with the
model shown here.
Direct outputs from the model (the only ones presented in this paper) are the gas
composition, the gas yield, the tar content in the produced gas, the carbon (in biomass)
conversion to gas, and the temperatures both at the gasifier exit and inside the gasifier
(axial profiles and bottom bed temperatures). Experts in biomass gasification should be
able to draw some more and important (indirect) outputs from the above direct
outputs. For instance, the model, if understood well, enables an optimized design of a
CFBBG, possible revampings and improvements of existing CFBBGs, detection of
limits of operation and zones in which the gasifier operates badly. All these outputs
can appear quite ambitious but in fact they have already been applied by the authors
to some gasifiers with positive results and, therefore, these outputs are realistic for the
authors.

2.5. Strategy in this modeling

CFBBGs are quite complex reactors and their modeling is difficult. Besides the need to
know biomass gasification technology in depth, there is as yet not enough accurate data for
some aspects. More needs to be known on the kinetics of some reactions under gasification
conditions and on radial and axial profiles in the whole gasifier of the char and of the
charred biomass, which are required to develop a good model [38]. During the modeling
work the authors continuously experienced uncertainties and lack of accurate information.
Besides, a model must be checked with existing CFBBGs but this checking was very
difficult in our case. The manufactures of the few existing pilot and commercial CFBBGs
J. Corella, A. Sanz / Fuel Processing Technology 86 (2005) 1021–1053 1027

Table 3
Inputs and outputs from the model
Inputs. variables considered
Biomass Chemical analysis (C, H, O, N)
Moisture
Ash content
(Particle size. Content in potassium: constraints in operation temperatures
by possible agglomerations)
Air Preheating temperature
Volumetric or mass flow rate
Equivalence ratio primary air
secondary air flow
Moisture
Gasifier Topology. Size, shape and main dimensions
bBedQ composition (solids and particle sizes) inventory
Heights of feeding: 1st air
2nd air
biomass
Biomass feeding Mass flow rate (kg/h)
WHSV (h1), [mass flow rate/mass of solids (inventory) in the gasifier]
Throughput

Outputs
Direct
Gas Composition (H2, CO, CO2, CH4, C2Hn , H2O, O2 contents)
Heating value (LHV, MJ/Nm3, dry basis)
Yield (Nm3/kg biomass daf)
Quality: tar content (g/Nm3)
Exit temperature
Carbon Conversion (%)
Content in exit fly ash
Temperature Longitudinal profiles
Exit
Bottom bbedQ
Indirect Optimized design of a CFBBG
Limits of operation, zones of bad-functioning
Maximize throughput
Possible rewampings of the CFBBGs
Optimized MW/m2

did not publish many details about their gasifiers, and a private worldwide survey carried
out by these authors did not provide enough data as was required.
Due to the complexity of handling all aspects required in a model for a CFBBG, Corella
and co-workers at the Universities of Saragossa and Madrid (Spain), after twelve years of
work on this modeling, have developed two different models for CFBBGs. Each one uses a
different approach. In order to develop a model, given that till now not enough accurate
basic or scientific information exists, several assumptions were made. Depending on where
such assumptions are introduced or localized, a different model can be generated. In this
paper only one model is presented. It is 1-dimensional and for CFBBGs under steady state.
The 2nd model mentioned above is based on an empiric partitioning of the O2 (air) fed to
1028 J. Corella, A. Sanz / Fuel Processing Technology 86 (2005) 1021–1053

the gasifier, it does not consider axial profiles inside the CFBBG and is for non-stationary
states. The 1-dimensional model presented here might seem academic because it is based on
the Chemical Reaction Engineering (CRE) principles: chemical kinetics together with
mass, heat and momentum balances. A rigorous academic approach would contain more
than 20 parameters, some of them being absolutely unknown today [38]. Such unknown
parameters would be some kinetic parameters concerning in-bed tar appearance and
elimination and the ones concerning heterogeneities (plumes and radial gradients) existing
in the biomass and 2nd air flow feeding zones (i.e., [39]). Therefore, several assumptions
had to be made to solve and handle the initially very complex rigorous academic approach.
Making these experience based assumptions, the model became semi-rigorous. The degree
of empirism in it will decrease, hopefully, in the future when new and accurate information
(for CFB biomass gasifiers) is available.
The equations presented and solved here will basically be a set of kinetic equations for
the complex reaction network together with the mass balances for all the species or
reactants considered in such network. To calculate the values of all kinetic constants, axial
profiles of temperature are required. A lot of hydrodynamic considerations and details are
also required. These temperature profiles and hydrodynamic considerations will be
handled as sub-models and/or sub-routines in parallel with the main program.
A model without extensive good verification means nothing for these authors. Although
some experimental verification is usually not enough to demonstrate the validity and
usefulness of a model, it is absolutely required. For this reason, a lot of effort was made to
verify the model presented here. Such validation was carried out in two different ways: (1) a
worldwide survey with all the known commercial gasifiers manufacturers and owners
[AMERGAS, LURGI, TPS, ECN, UMSICHT, LAHTI, FOSTER-WHEELER E. Oy,
VÄRNAMO (Sydkraft), CLAMECY Plant,. . .]. Some of them do not exist nowadays, for
example, the gasification plant in Clamecy (France), but some useful information from such
plants were obtained years ago and were used in this work. Some information obtained from
some manufacturers and owners had a confidential character and cannot be explicitly shown
here. Nevertheless, it was used in several parts and steps of the modeling presented here.
Some data have also been obtained during the IEA Biomass Gasification task meetings.
(2) Some tests were carried out on small pilot plant scale to check this model. For that
objective, a BFB biomass gasifier at University Complutense of Madrid (UCM) was fully
modified by increasing its height and the biomass and air flow rates and connecting a
standpipe and an L-valve, thus generating a CFB. This CFB biomass gasifier was
presented in [37] and is shown in Fig. 2. Its main dimensions are (a) bottom zone: 70 mm
internal diameter (i.d.) and 1.2 m height; (b) a 2nd zone of 120 mm i.d. and 1.4 m height;
(c) upper zone: 150 mm i.d. and 2.2 m height. Temperatures were measured at different
heights with different thermocouples. Some tests were designed and carried out in this
CFBBG to check the model. This verification continues.

2.6. Species considered in the gasification reaction network

i) Concerning biomass, pine wood was selected as reference. The composition (dry,
ash free) was 50.0 wt.% C, 5.8 wt.% H and 44 wt.% O. Its weight formula was
C4.2H5.8O2.8.
J. Corella, A. Sanz / Fuel Processing Technology 86 (2005) 1021–1053 1029

ii) Gases. Air (in primary and secondary flows) and gases formed in the pyrolysis and
gasification reactions: H2, CO, CO2, CH4, C2H4 and H2O. H2O comes from biomass
and air mixtures and as a product in some reactions.

1. Hopper.
2. Feeding system.
3. Primary air inlet.
4. Preheating zone.
5. Secondary air
6. Gasifier
7. Additives inlet
7

H2O
2

PRIMARY AIR
3

Fig. 2. New small CFBBG pilot plant at UCM used to check the model.
1030 J. Corella, A. Sanz / Fuel Processing Technology 86 (2005) 1021–1053

iii) Tar. Although it is in gas phase and could be considered as one more gas, it will be
studied separately due to its importance in biomass gasification.
The first fast pyrolysis or devolatization generates a tar which will be called
tar1. In the bottom bed tar1 very quickly undergoes a lot of thermal
degradation reactions generating a tar called here tar2. It would be the one
detected if the CFB reactor was operated as pyrolizer, with an inert gas. In
a CFB gasifier this tar2 reacts, to some extent, with the primary air
generating a tar called btargasifQ. If, besides, there is a catalyst like calcined
dolomite (as it is the case considered here) in the bottom bed, this btargasifQ
undergoes some steam and dry (CO2) reforming reactions which decreases its
total amount and changes its composition. This new tar generated with in-bed
dolomite will be called btardolQ. The 2nd air flow in the dilute zone
additionally converts and transforms this tar (the btardolQ coming from the
bottom bed) to another tar which will be called btar2ndairQ. Not only the
amount of tar decreases but also its composition changes by the above
reactions [40]. To show the difference between the tars (tar2, targasif, tardol
and tar2ndair), the corresponding tar yields obtained in similar FB biomass
gasifiers using the same feedstock, pine wood chips, are shown in Fig. 3.
This Fig. 3 clearly shows how, at a given gasification temperature, the tar
yield depends very much on the existence of in-bed dolomite and on a 2nd
air flow.
Concerning tar composition, the 6-lump model for tar evolution (generation-
elimination) developed by Corella et al. [40–42] is now being applied to
study the axial profiles of the tar species. These axial profiles can be
handled by a sub-routine with 9 kinetic constants. This sub-routine, not used
in this paper, may be added or incorporated in the model presented here to
predict or calculate the axial profiles (in the riser) of the species present in
the tar.
The different tars existing in a CFBBG will be represented in this model by two
different species only:
– tar2, obtained from the devolatization+thermal reactions at the bottom bed
(see Eq. (1)). Its general formula is Cx Hy Oz , with x=1 and y, z to be determined
from mass balances ( y/x for tar2 is less than 1 in the range of temperature
considered, according to Van den Aarsen [19]).
– tar4, generated by in-bed catalytic steam (and dry) reforming reactions (Eq.
(9)). Its general formula is CxU HyU with xU=yU.
The btotal or overall tar contentQ at the exit of the CFBBG will be the addition
of, first, the tar2 generated in the pyrolysis step (Eq. (1)) minus the tar2 reacted
by reactions (2) and (9), and, second, the tar4 generated by Eq. (9) minus the one
reacted by reaction (2b).
iv) Char. Two different compositions will be considered for the char:
– char2, generated in the devolatization+in-bed thermal reactions (Eq. (1)).
Its general formula is Cx V Hy V Oz V with xV=1 and yV, zV to be determined
from mass balances [(H/C)char2b(H/C)tar2b1, in the range of temperatures
considered].
J. Corella, A. Sanz / Fuel Processing Technology 86 (2005) 1021–1053 1031

160

`
Gonzalez-Saiz [43]
Narvaez et al. [36]
140
Gil et al. [35]
Lammers et al. [46], Kurkela [73]
Tar yield (g/kg biomass, daf)

120

100

80
tar2

20

10 targasif

tardol
tar2ndair
0
700 750 800 850
Bed temperature (°C)
Fig. 3. Tar yields after pyrolysis (tar2) and after atmospheric gasification with air (ER=0.24) without (targasif) and
with (tardol) in-bed dolomite, without and with (tar2ndair) secondary air flow.

– char3, generated in the gasification of char2 with CO2, reaction (11). Its general
formula was determined from analysis of this char obtained during the
experiments at UCM. It can be noticed that (H/C)char3N(H/C)char2.

The bchar concentrationQ inside and at the exit of the CFBBG will be the addition of
two contributions: first, the generated one by reaction (11) and the char3 unreacted in
reaction (3b), and second, the char2 unreacted in reactions (3) and (10).
The compositions of tar2 and char2, according to Van den Aarsen [35], depends on
the gasifier temperature, Table 4, and on the type and composition of the biomass used.
The chemical compositions of tar2, tar4, char2, char3 were calculated for a gasification
temperature of 850 8C, for a given biomass (pine wood was used as reference), and for
the Htar2/Hchar2 and Otar2/Ochar2 ratios (Ctar2/Cchar2 ratio is 1) indicated in Table 4.

Table 4
Composition of tar2 and char2, according to Van den Aarsen [19]
Pyrolysis temperature (8C) tar2 char2
715 CH0.81O0.20 CH0.25O0.14
815 CH0.75O0.13 CH0.21O0.12
915 CH1.00O0.17 CH0.14O0.14
Averaged CH0.85O0.17 CH0.20O0.13
1032 J. Corella, A. Sanz / Fuel Processing Technology 86 (2005) 1021–1053

Table 5
Calculated compositions for tar2, tar4, char2 and char3 (T=850 8C)
Specie Formula H/C
Biomass C4.2H5.8O2.8 1.40
tar2 CH0.85O0. . .17 0.85
tar4 C0.54H0.54 1.0
char2 CH0.20O0.13 0.20
char3 C0.30H0.15O0.46 0.50

Tar2, tar4, char2 and char3 compositions, calculated at 850 8C as reference, are shown
in Table 5.

3. CFBBG modeling

3.1. Reaction network considered

The most suitable reaction network for biomass gasification with air in a CFB was
previously discussed by Corella and Toledo [38]. Such a network contains all the reactions
which were considered relevant and it is shown below (reactions (1)–(12)). Axial profiles
of concentration for all the species considered in this network will be further obtained from
the model.

3.1.1. Reaction network considered for the zone between the biomass feeding point and the
2nd air inlet (zone which covers the bottom zone, the transition zone and part of the dilute
zone, Fig. 1)
Fast Pyrolysis:

(1)
Oxidation with the primary air of the products formed in the pyrolysis step:
tar2½CH0:85 O0:17  þ q2  1st O2 ! e2  CO þ g2  CO2 þ s2  H2 O ð2Þ

char2½CH0:20 O0:13  þ q3  1st O2 ! e3  CO þ g3  CO2 þ s3  H2 O ð3Þ

H2 þ O1st O2 ! H2 O ð4Þ

CO þ O1st O2 ! CO2 ð5Þ

CH4 þ 1:51st O2 ! CO þ 2  H2 O ð6Þ

C2 H4 þ 31st O2 ! 2CO2 þ 2H2 O ð7Þ


J. Corella, A. Sanz / Fuel Processing Technology 86 (2005) 1021–1053 1033

Steam reforming of methane:


CH4 þ H2 OYCO þ 3  H2 ð8Þ
Tar and char reforming reactions:

(9)

char2½CH0:20 O0:13  þ s10  H2 O ! e10 CO þ d10 H2 ð10Þ

char2½CH0:20 O0:13  þ g11  CO2 ! e11 CO þ u11 char3bCxx Hyy Ozz c ð11Þ

3.1.2. Reaction network considered for the zone between the 2nd air inlet and the exit to
cyclone (part of the dilute zone, Fig. 1)
Besides the reactions given by Eqs. (2)–(11),
Oxidation with the secondary air of products coming from first zone of reaction:
tar4tCx00  Hy00 b þ q2b  2ndO2 ! e2b  CO þ g2b  CO2 þ s2b  H2 O ð2bÞ

char3tCxx Hyy Ozz b þ q3b  2nd O2 ! e3b  CO þ g3b  CO2 þ s3b  H2 O ð3bÞ
Shift reaction:

(12)
The non fixed stoichiometric coefficients in these reactions were calculated by mass
balances for each of the components (C, H, O) in each chemical reaction. These
coefficients, for a temperature of 850 8C, are shown in Table 6.

3.2. Kinetic equations used for the chemical reactions involved in the reaction network

The set of kinetic equations for the reaction network given by Eqs. (1)–(12), used to
calculate the product distribution, is shown in Table 7. These equations originate both from
our own findings/research and from some published papers.

Table 6
Stoichiometric coefficients for T=850 8C
Eq. Stoichiometric coefficients
(1) b 1=0.87; c 1=0.45; d 1=1.3; e 1=1.5; g 1=0.51, h 1=0.47; p 1=0.18
(2) q 2=0.68; s 2=0.31; e 2=0.75; g 2=0.25
(2b) q 2b=0.60; s 2b=0.26; e 2b=0.093; g 2b=0.42
(3) q 3=0.58; s 3=0.073; e 3=0.75; g 3=0.25
(3b) q 3b=0.032; s 3b=0 ; e 3b=0.037; g 3b=0.17
(9) d 9=0.13; e 9=0.35; s 9=0.15 v 9=1.2
(10) d 10=0.45; e 10=0.54; s 10=0.38
(11) g 11=1; e 11=1.7; u 11=1
1034 J. Corella, A. Sanz / Fuel Processing Technology 86 (2005) 1021–1053

Table 7
Reaction rates for the reaction network
Reaction Reaction rate (mol/m3 s) Parameters Reference
(1) y i=m o,i+m 1,i ST+m 2,iST 2 Jiang and Morey [22,23],
Gonzalez-Saiz [43]
Zanzi et al. [66], Dai et al.
[67], Di Blasi et al. [68,69]
(2) r2=k2SCtar2SCO2 k2=ftar2S(1-cv)1.58S 1010S Dryer and Glassman [44,45]
exp(-24200/T) Lammers et al. [46]
(2b) r2b=k2S(ftar4/ftar2)SCtar4SCO2 The same of (2) with Dryer and Glassman [44,45]
different value for the Lammers et al. [46]
kinetic constant
(3) r3=k3ScvSUsSCchar2SCO2 k3V=5.3S105Sexp(-15000/T) Janse et al. [47]
0.53
or r3=k3VSpO 2
S(1-Xchar)0.49 Fushimi et al. [50]
Kulasekaran et al. [71]
(3b) r3b=k3ScvSUsSCchar3SCO2 The same of (3) with Janse et al. [47]
different value for the Fushimi et al. [50]
kinetic constant Kulasekaran et al. [71]
(2), (3), e2 e3 e2b e3b Belleville and Capart [17]
(2b), g2 ¼ g3 ¼ g2b ¼ g3b
(3b) ¼ 4:30expð  3390=T Þ
Kulasekaran et al. [62]
Hayhurst and Parmar [70]
Cozzani et al. [72]
2
(4) r 4=k4SCH 2
SCO2/CCO k4=3.09S1011Sexp(-12000/T) Kim et al. [11]
(5) r 5=k5SCCO SCO2 k4=8.83S1011Sexp(-12000/T) Kim et al. [11]
-0.5 1.5
(6) r 6=k6SyCH 4
SyO2 k6=7.0S1011Sexp(-30200/T)ST Srinivasan et al. [7]
De Souza-Santos [63]
(7) r 7=k7SCC0.72H4 SCO0.82 k7=fC2H4S(1-cv)1.58S1010S Dryer and Glassman [44,45]
exp(-24200/T) Philippek et al. [64]
(8) r8=k8SCCH4SCH2O k8=3S1005exp(-15000/T) Thérien et al. [48]
Liu and Gibbs [32],
from Fletcher et al. [49]
0.25 1.75
(9) r9=k9SCtar2 SCH2O k9=f9S70.0Sexp(-2000/T) Gonzalez–Saiz [43]
(10) r10=k10SCchar2SCH2O k10=2.0S105Sexp(-6000/T) Gonzalez–Saiz [43]
Fushimi et al. [50]
(11) r11=SSr11
W V =7.2SCCO0.83
r11 2
exp(-20000/T) Van den Aarsen [19]
Van den Aarsen et al. [51]
  Tang et al. [65]
(12) CCO2 CH2 a) T N 1123 8C (equilibrium) Gonzalez–Saiz [43]
r12 ¼ k12 S CCO SCH2 O  S
KW k12 Xu and Froment [52]
KW ¼
CH2 SCCO2 k12V Simell et al. [53]
KW ¼
CCO SCH2 O ¼ 0:0027expð  3960=T Þ
b) Tb1123 8C (no-equilibrium)
KW ¼ kk12V
12
¼ 520expð  7230=T Þ
k12 ¼ 106 expð  6370=T Þ

Some comments on these kinetic equations:

1st) For reaction number 1 (fast pyrolysis in fluidized bed) a product distribution,
instead of a btypicalQ kinetic equation, was preferred because such product
J. Corella, A. Sanz / Fuel Processing Technology 86 (2005) 1021–1053 1035

distribution was obtained with the same type of biomass as the one considered
in this paper (small pine wood chips) and in a fluidized bed working under
experimental conditions similar to those used in a CFBBG. The values for the
parameters m 0, m 1, and m 2 appearing in Table 7 are given in Table 8 for all
species. The units for y i , in equation for reaction 1, when calculating tar yield
and yield to char were [kg/kg daf] and when calculating H2, CO, CO2, CH4 and
C2H4 contents were [mol i/total mol, dry basis]. The authors are confident of
the validity of this equation and those m-values for this application. Never-
theless, it has to be pointed out how this product distribution may be quite
different for some other types of biomass, because the word bbiomassQ covers a
big spectrum of fuels which can be very different between themselves.
2nd) The selection of the rate expressions for reactions (2)–(12) was made after a deep
analysis of the abundant bibliography on most of these reactions. Their respective
reference or origin are given in Table 7. Since for some reactions there were
different possible kinetic equations in the literature and since there was no
discrimination method among those rival kinetic models, different references are
given in Table 7 for some reactions. When there were several possible kinetic
equations for a given reaction, the easiest or simplest one (1st order, for instance)
was preferred although several other kinetic equations could also be used for that
reaction.
3rd) Since some reaction rates originally had different units (the ones provided by the
corresponding authors) an important effort was made to adopt the same units in
all kinetic expressions. For this propose, a change of units which takes into
account variables such as pressure and temperature in the riser, voidage, density or
dolomite content in the considered zone, . . . had to be made in several kinetic
equations.
4th) Since most of the kinetic equations shown in Table 7 were obtained under gas
atmospheres and environment, such as the existence of calcined dolomite
(OCad OMg) which may have some catalytic effects for several reactions, different
to the ones existing in a CFB biomass gasifier, most of the rate equations shown in

Table 8
Values of parameters m 0, m 1, and m 2 for the fast pyrolysis of small pine wood chips in a bubbling fluidized bed
(from Gonzalez-Saiz [43] and Jiang and Morey [22,23])
i (species) m0 m1 m2
H2 0.255 4.47 104 4.54 107
CO 0.255 5.44 104 3.88 107
CO2 2.14 3.53 103 1.55 106
CH4 0.45 1.12 103 5.47 107
C2H4 1.32 2.51 103 1.15 106
N2 0.118 1.99 104 8.64 108
Tar 0.382 2.16 104 0
Char 2.09 3.47 103 1.48 106
H2O the corresponding to the initial biomass moisture
1036 J. Corella, A. Sanz / Fuel Processing Technology 86 (2005) 1021–1053

Table 9
Corrective factors used in the kinetic equations
Corrective factors Intervals considered
f2 0.6–1.7
f 2b 1
f3 1.6
f4 0.5
f5 0.1–0.9
f6 0.1–1
f7 1
f8 2
f9 1.6
f 10 0.4–0.7
f 11 0.2–2
f 12 0.3–0.7

Table 7 have to be understood as approximate, not exact ones. For this reason, and to
fit some experimental data from existing commercial CFBBGs, some corrective
factors ( f n ) were introduced in the kinetic equations above. These corrective factors
are shown in Table 9. The value of 1 in Table 9 means that the corresponding kinetic
equation remains without modification.

3.2.1. Overall volumetric rate equations


Each i-th species (H2, CO, . . . , tar2, char2, . . . ) existing in the reaction network
indicated by Eqs. (1)–(12) appears in several reactions, sometimes as reactant, sometimes
as product. The overall or net rate of appearance (indicated by R i ) of the i-th species will
be the badequateQ addition, by the well known rules of Chemical Reaction Engineering, of
the rates for all the reactions in which such species appears.
The two main zones considered in the CFBBG (till the 2nd air feeding point and from
this point to the exit) were considered separately. Some examples of the calculation of these
overall reactions rate, for the zone between the biomass feeding point to 2nd air inlet, are
Rtar2 ¼ eq:1  r2  r9 ð13Þ
Rchar2 ¼ eq:1  r3  r9  r10  r11 ð14Þ
RH2 ¼ eq:1 þ d8  r8 þ d9  r9 þ d10  r10  r4 : ð15Þ
RCO ¼ eq:1 þ e2  r2 þ e3  r3 þ e6  r6 þ e8  r8 þ e9  r9 þ e10  r10 þ e11

 r11  r5 ð16Þ
and from the 2nd air inlet to the gasifier exit.
Rtar2 ¼  r2  r9 ð17Þ
Rtar4 ¼ v9  r9  r2b ð18Þ
RH2 ¼ d8  r8 þ d9  r9 þ d10  r10 þ r12  r4 ð19Þ
RCO ¼ e2  r2 þ e2b  r2b þ e3  r3 þ e3b  r3b þ e6  r6 þ e8  r8 þ e9  r9 þ e10  r10
þ e11  r11  r5  r12 ð20Þ
J. Corella, A. Sanz / Fuel Processing Technology 86 (2005) 1021–1053 1037

3.3. Mass balances for all species

Two main assumptions were made:


1st) One-dimensional model. Piston or plug flow considered in the CFBBG for all the
species.
2nd) Steady-state operation.
Three different scales for the CFBBG were considered: pilot, demo and commercial
scales (see Section 2.2). The temperatures used, to calculate the values for all the kinetic
constants, come from the heat balances shown below. Pressure drop considered in the riser
is 0.10–0.20 atm (10.1–20.2 kPa) and the percentage of the 2nd air flow between 0% and
40% (standard: 20%). Two different units for the space time (s) were used in the mass
balances depending on the i-th species under consideration (gases, tars and chars). These
units for s are indicated in the notation.

3.4. Heat balances

Axial profiles of temperature (T) in the riser of a CFBBG are very important because all
kinetic constants in the set depend on temperature. To calculate a given kinetic constant at a
given height in the riser, the temperature at such height has to be known and to know such
axial temperature profiles several heat balances have to be made. The contours for such heat
balances are indicated in Fig. 4. For a given heat balance, the fuel gas composition has to be
known at the inlet and exit of this contour which, in turn, depends on the temperature in
such points. An iterative process therefore has to be used in each contour.
For a CFBBG under steady state the contours under consideration are shown in Fig. 4:
the bottom zone (contour 1, with the biomass feeding point in it), the 2nd air feeding zone
(contour 2), the zones of the riser with no feeding points (contours 3a and 3b) and the
whole riser (contour 4).
Once fixed the process conditions the axial profiles of T are calculated but, since the
heat released by each reaction in the network (Eqs. (1)–(12)) depends on its conversion
and this conversion depends on T, an iterative calculus has to be made in each contour. The
heat losses considered in each contour are the 2% of the overall heat released.
For a CFBBG under a non steady state (starting up period, changing in biomass feeding
flow, etc., . . .) the only contour considered was the whole gasifier (contour 4 in Fig. 4). In
this case all the gasifier was considered isotherm. The evolution of the only one bgasifier
temperatureQ then with time-on-stream, until a steady state was reached, was also calculated.

3.5. Hydrodynamic considerations and constrains

The hydrodynamics in a CFBBG are extremely complex because at least there are the
following four types of different solids in a CFBBG:

– Silica sand (S), as fluidizing material.


– Raw dolomite [(CO3)2CaMg] as additive for in-bed tar cracking and to prevent
agglomerations. At gasifier temperature the raw dolomite quickly calcinates to
1038 J. Corella, A. Sanz / Fuel Processing Technology 86 (2005) 1021–1053

Gas

4th

3rd b Heat losses

2nd Air
2nd

3rd a

Biomass

1st
Bottom
ashes

1st Air air conditions


Tamb = 15 °C
rel. moisture = 30%

Fig. 4. Zones or contours where heat balances have been made.

OCad OMg. Calcined dolomite (D) has a density half of that of the raw dolomite and a
softness three times higher than the raw material dolomite. So, in fact, raw dolomite and
calcined dolomite should be considered, both chemically and physically, as two
different solids for hydrodynamics studies.
J. Corella, A. Sanz / Fuel Processing Technology 86 (2005) 1021–1053 1039

– Biomass, which usually contains very different types of particles (from different
origins) each having different shape factors.
– Char, charred biomass and ash from biomass, with a very low density and high
softness. They very easily erode at the bottom bed by the effect of the abrasive silica
sand. When gasifying, the particle sizes of the biomass, charred biomass, char and ash
change very much and very quickly [54].

The hydrodynamics of this mixture of solids in a CFBBG is very complex [58] and will
not be well known until a lot of the remaining work is done in future. Some hydrodynamic
aspects taken into account in the modeling of CFBBGs are the following:

1st) The zone between the inlet of the primary air and the biomass feeding point (height
H1, see Fig. 1) is difficult to model: the axial profiles of biomass and chars (char1,
char2 and char3) are not yet well known. Since there is a stationary fluidized bed in
that zone [61], it might be supposed that there would be back-mixing for all species
in solid phase, as biomass and chars. Nevertheless, chars, and also biomass, have
such a low density compared with the one of the bfluidizing materialQ (silica sand
and additive) that there is a near instantaneous segregation of the chars once
generated in the pyrolysis zone, just above the biomass feeding point. Aznar et al.
[55] studied this fast segregation and published a lot of axial profiles of the char and
of some types of biomass in binary, ternary and quaternary mixtures. Until other
even more accurate axial profiles for char and biomass are published, the axial
profiles for char and biomass published by Aznar et al. [55] will be the ones used to
calculate the extent of the reactions and the resulting profiles of the gases in that
zone.
2nd) The comminution and carry over of the calcined dolomite in a CFBBG occurs by
different simultaneous mechanisms, as studied by Aznar and co-workers [56]. They
found the reason why 1 to 3 wt.% (respect to the biomass fed) of dolomite has to be
continuously fed to the gasifier to replace the dolomite lost by elutriation. They also
established why an enough good behaviour of a CFBBG occurs when there is a 20–
30 wt.% of dolomite in its bottom bed. The remaining 70–80 wt.% is silica sand. The
char and ash content in the bottom bed is usually very low (1–4 wt.%) and can be
omitted when calculating the weight hourly space velocity (WHSV) of the biomass
[(kg biomass fed/h)/kg solids inventory (S+D)] in the CFBBG.
3rd) To get realistic data on hydrodynamics in commercial and in big (pilot, demo)
biomass gasifiers, a worldwide survey was carried out among all the existing
CFBBG manufacturers and owners. Most of them provided to the authors some
important values, sometimes confidentially, about the following parameters in which
their gasifiers operate:
– WHSV [weight hourly space velocity, (kg/h)/kg inventory] from 1 to 3 h1.
– Throughputs (kg/h m2 cross-sectional area): between 1000 and 7000 kg/h m2.
– Superficial gas velocities: 2–10 m/s.
– Mean residence times for the gas in the bottom and in the dilute zones: 1 and 3 s,
respectively, on average.
– etc . . . (gas compositions, for instance).
1040 J. Corella, A. Sanz / Fuel Processing Technology 86 (2005) 1021–1053

In the solution of the model shown here, all this information was taken into
account. This information defined the limits of operation or constrains of the whole
model. It was one of the main verifications (in the calculations carried out in the
model) shown in Fig. 8.

4. Model development

The simultaneous solution of the mass and heat balances with the kinetics and the
hydrodynamic aspects was very complex. Although certain details are omitted some
important results are given below:

4.1. Heat balances and the axial profiles of temperature

Some results concerning the axial profiles of temperature are

1) Axial temperature profiles obtained from the model are of the same type as the few
already existing in the literature for CFBBGs [28,57]. They were also confirmed by
the measurements made in the small CFBBG shown in Fig. 2.
2) From the bottom of the gasifier until the 2nd air flow inlet point
(H 1+H bt +H tz +H 3 in Fig. 1) the temperature decreases because the endothermal
reactions in this zone consume more heat than that provided by the simultaneous
exothermal ones. Nevertheless, one simplifying assumption can be made, at a
first attempt, to facilitate further calculations in that zone: an average temperature
can be considered in this zone. This average temperature is calculated supposing
that all devolatilization occurs there and that all the 1st air reacts in this zone. To
give one example, the temperatures in the bottom zone for different ER values
are shown in Table 10 for a 2nd air flow of 20% of the total air flow, a biomass
moisture of 15 wt.% and a 1st air flow preheated to 250 8C before feeding it to
the CFBBG. These temperatures are the ones at the lowest part of Fig. 5.
Temperatures at the bottom zone for several other process conditions will be
shown in our next paper [33].
3) One very important fact concerning the axial profiles of temperature (in the riser) is
the increase of T (DT) because of the secondary air flow in the upper (dilute) zone.
Such increase of temperature may also appear when the particle size of the biomass
fed is very low. In that case it is carried out from the bottom bed by the flue gas and
partially combusted, if there is still some O2 left there, in the upper (dilute) zone, as
van der Drift and van Doorn [57] demonstrated at the ECN (The Netherlands) pilot

Table 10
Standard bottom zone temperature depending on the ER value (secondary flow=20% of ER; biomass
moisture=15%; preheated air temperature=250 8C)
ER 0.20 0.25 0.30 0.35 0.40 0.45
T b. bed (8C) 824 837 850 863 877 890
J. Corella, A. Sanz / Fuel Processing Technology 86 (2005) 1021–1053 1041

16

Total ER
14
0.20
0.25
12
0.30
0.35
0.40
10 0.45
Riser Height (m)

0
800 850 900 950 1000 1050

Fig. 5. Longitudinal profiles of temperature for different total ER values with a 2nd air flow of 20% of total air.

plant. The reference (or average) DT by the 2nd air addition calculated for several
percentages of this 2nd air is shown in Fig. 6.
4th) In the upper part of the riser, from the 2nd air inlet point till the gas exit point,
there is a continuous decrease of the temperature. The heat consumed by the
endothermal reactions there, together with the heat lost by the walls, is usually
not compensated by the heat released by the exothermal reactions occurring with
the O2 fed in the 2nd air flow. Again it can be assumed, as a first attempt and to
facilitate some further calculations, that the upper zone of the riser is isothermal,
with an average temperature in it. The simplified axial profiles of temperature in
the riser of the CFBBG for the case of a 2nd air flow of 20% of the total air,
and for a 2nd air inlet height of 6 m are shown in Fig. 5. These simplified
profiles can be used in the whole model when more precise or accurate profiles
1042 J. Corella, A. Sanz / Fuel Processing Technology 86 (2005) 1021–1053

200

150
∆T (= T exit-Tb.bed )

100

50

0
0 10 20 30 40

2nd air flow (%)


Fig. 6. Difference of temperature (DT) used as reference between the averaged in the upper zone and in the
bottom zone of the CFBBG, for different percentages of 2nd air flow.

cannot be calculated. In fact, in the present state of development of this model


and with the existing data, the axial profiles of T cannot be calculated with
accuracy for some experimental conditions (i.e., for some types of feedstocks or
for some particle size distributions of the biomass). In such circumstances a
simplified two-zone temperature profile, as the ones shown in Fig. 5, can be
used. In such cases, the temperature is considered constant from the biomass
feeding point until the 2nd air feeding point. Then, there is an increase of T (DT)
by the 2nd air addition (which depends on the percentage of 2nd air used) and
then, from the 2nd air feeding point to the exit of the riser, the temperature is
considered constant. Only two calculations (not easy sometimes) are needed in
this simplified approach: the temperature in the bottom zone and the DT value by
the secondary air flow.

4.2. Hydrodynamics of the CFBBG

Some noticeable comments about modeling the hydrodynamics in the CFBBG are:
1) Although it is well known how in CFBs there is a continuous, along their axis or
height, variation of voidage (e) or solids fraction, the gasifier was considered as composed
by the following three zones (see Fig. 1):

– bottom zone, with a height of H bt . The reference porosity in this zone is 0.77.
– transition or splash zone, with a height of H tz and e=0.90.
– dilute zone, with H dz of height and e=0.99. Secondary air is fed into this zone.
J. Corella, A. Sanz / Fuel Processing Technology 86 (2005) 1021–1053 1043

An exit zone may also be considered, if required. Other values for the porosities might
also be used but these ones were considered as acceptable or representative; they are the
averaged values from the published porosities for similar CFB reactors.
2) Clouds and strands of particles which may lead to a different velocity-behaviour of
the gas and of the solids were not considered. Besides, the behavior of the solids is
different in very slim reactors compared with wide commercial reactors. These facts,
which have been very well studied in coal combustors for instance, have not yet been
studied enough in biomass gasifiers. These phenomena are therefore recognized, but a
piston flow (1-dimensional model) has always been used in the model. Some errors are
recognized at this point in the model but this situation is acceptable until more useful data
concerning CFBBGs are available.
3) Biomass devolatization once biomass enters into the bottom bed in the CFBBG,
although it is very fast, it is not instantaneous. There is some evidence that a plume or
something like a small jet of gas is formed (i.e., [39]). The flow in such feeding zone is not
an academic piston or plug flow [39] and today there is not enough information published
for a good sub-model for this zone. It will remain as one of the main unknowns or weak
points of this model.
Something similar occurs with the 2nd air flow and its mixing with the upwards flow. It
is not instantaneous and generates a lot of effects (i.e., [74]). The authors think, from their
own experience, that the bmixing zonesQ above both the biomass and 2nd air feeding
points should be at least 1 m height each. Nevertheless, to facilitate handling the
mathematics in the present model, it was considered that such feeding of biomass and 2nd
air occurs at just bone point or heightQ, as Fig. 1 indicates. In real CFBBGs, however, the
space above these points has a lot of heterogeneities. For instance, the pipe(s) for the
biomass feeding has sometimes 0.50 m diameter, it is therefore not just a point. When
examining longitudinal profiles for this model, it will have to be remembered that such
two bpointsQ (biomass and 2nd air injection) are not bpointsQ but zones of around 1 m
height.
4) The heights of the different zones are indicated in Fig. 1. From the works of
Schlichthaerle and Werther [75], Malcus et al. [76], etc., . . . the standard values considered
in this paper for these zones are H 1=1.5 m; H 2=1.0 m; H 4=0.5 m; H T =14.8 m. Although
H bz and H tz (see Fig. 1) vary with the air flow rate or ER value, these heights were
considered constant, 1.4 m each one, for all ER values. Nevertheless, all these heights are
variables in the model and can be varied to adapt it to a existing gasifier.
5) The terminal velocity (u t) of the solids was calculated by well established and known
methods, recently refined and applied by Hartman et al. [59] to the raw and calcined
dolomites. u t for the four main solids (in the riser of the gasifier there could be another
ones as big stones and irons too) existing in a CFBBG are shown in Fig. 7. The flue gas
considered for such calculation was air at 850 8C and 1.1 atm of total pressure. The particle
density and shape factor (very difficult to know for biomass char in a CFBBG under
operation) of the solids considered are shown in Fig. 7. Since the biomass, the charred
biomass and the char (and ash) usually have a broad spectrum of shape factors and of
densities, a zone, instead of a line, was considered for the reacting biomass in this figure.
If the superficial gas velocity at the exit of the riser of the CFBBG is 4 m/s, for instance,
Fig. 7 indicates how a silica sand of 0.5–1.0 mm would remain at the bottom bed, not
1044 J. Corella, A. Sanz / Fuel Processing Technology 86 (2005) 1021–1053

SILICA RAW
SAND DOLOMITE
5

CALCINED
DOLOMITE

WOOD
Terminal velocity (m/s)

CHIPS

CHAR FROM THE


3 WOOD CHIPS

LEAFS

2
Silica sand, 2.6g/cm3, φ=0.9
Raw dolomite, 2.4g/cm3, φ=0.8
Calcined dolomite, 1.3g/cm3, φ=0.9
1 Wood chips, 0.85g/cm3, φ=0.4
Leafs, 0.5g/cm3, φ=0.1
Ash from wood, 0.2g/cm3

0
0 1 2 3 4 5 6 7 8 9 10
dp (mm)
Fig. 7. Terminal velocity of the main solids existing in a CFB biomass gasifier (calculated for air, at 850 8C and at
a total pressure of 1.1 atm).

transported (its u t is higher than 4 m/s). A raw dolomite of 0.6–1.0 mm would


initially remain in the bed as well, but once and quickly calcined it would be
elutriated out. Biomass, char and charred biomass particles below 1.0 cm
approximately (depending on its initial shape, density and degree of charring) would
be transported out from the bottom bed first and then out of the riser. Fig. 7 is
interesting for the CFBBG modeling. For instance, the very important mean residence
time of both gasification gas and biomass in the bottom bed can be varied by
changing the bottom bed height which (for a given ER or superficial gas velocity)
depends not only on the inventory of solids (kg of S+D) but mainly on their particle
size distributions. Depending on their particle sizes they will generate a bed at the
bottom of the CFBBG or carried out. Since the particle densities of the silica sand and
of the raw dolomite are fixed, their particle sizes remain as the main variable which
can be varied (between some intervals only) to increase or decrease the mean gas
residence time in the bottom bed. This will modify, in turn, the composition, yield and
quality (tar content) of the gas exiting the bottom zone. So, a good choice of the
particle size distributions of both sand and dolomite is of paramount importance in the
J. Corella, A. Sanz / Fuel Processing Technology 86 (2005) 1021–1053 1045

CFBBG design and operation. Consequently, these particle sizes are very important in
this modeling.
6) The main or first cyclone as well as a second and in-series high efficiency cyclone,
usually required for some applications of the produced gasification gas, were taken into
account but are not reported in this paper. The content of particles in the produced gas
mainly refers to the top of the riser and not of the flue gas hence leaving the whole
gasification unit. The calculus of the particle content in the fuel gas after the whole
CFBBG still has a considerable error. In fact, the overall particle content is due to different
solids (char, ash, calcined dolomite, etc. . .) and some of these contributions (to the whole
content in particles) have not been deeply studied yet [56].
7) Char recirculation: the total conversion of the char produced in a CFFBG is not
produced in one pass of the solid through the riser [60]. The char is recycled in the
CFBBG until the (highest) final conversion is obtained.
The internal recycling of solids causes a spread in the residence time of the particles;
some pass only once through the riser while others are recycled several times [60]. Some
assumptions in the calculus of the char conversion include:

– The inlet to the riser of the recycled char stream is made at the same height as the
biomass feeding point.
– The char composition in the recycled stream is the same as that at the outlet of the riser.
– The conversion of the total char, the one generated in the pyrolysis step and the
recycled stream of char, in each passage in the riser is the same in each passing.

Several other hydrodynamic considerations were also used, but are not included here to
keep this paper within limits.

4.3. Calculation procedure

The overall model is protected and for reference purposes it will be called Al-CoreR.
The flow diagram for the overall solution of the Al-CoreR program is shown in Fig. 8. For
its solution, the following inputs must be given:

– Biomass (B): flow rate, moisture and ash content, and its ultimate analysis daf (C,H,O
wt.%).
– Operational conditions: pressure, inventory or weight of bed material (assumed 30
wt.% dolomite and 70 wt.% silica sand), and temperature at inlet of bottom bed.
– Inlet Air: ER, temperature of preheating, ambient temperature, relative moisture and
2nd/1st air flows.
– Gasifier topology: main dimensions, wall thickness or weight of the gasifier (which is
needed in a heat balance), etc . . .

The flow diagram for the solution of the Al-CoreR program is shown in Fig. 9 with
some more detail. Some procedural steps are given below.
It is necessary to make a first assumption for the axial profile of voidage (e) and for the
volumetric flow rate of the flue gas along the gasifier height ( Q 1).
1046 J. Corella, A. Sanz / Fuel Processing Technology 86 (2005) 1021–1053

INPUTS

B, E R ( ... )

Resolution of kinetics +
mass balance eqns. (for
each specie)

[1 ] Heat balances
[2 ] Temperature at inlet of bottom
[3 ] bed T1 (°C) - depending of ER
.. .

[ 12 ]
Hydrodynamics:
ε and char axial profiles
WHSV
Total gas flow in the riser (Q).
Sup. gas velocities, profiles
Mean gas residence times
T
Xta r OUTPUTS
C ch a r
.. . Axial profiles of
Xo 2 T (°C)
at exit of the gasifier
Gas comp. (% vol.)

P · V1 LHV of gas (MJ /N m3)


ni = · Xi
Rg · T
NO T Gas yield
NO GOOD (Nm3/kg daf,dry basis)

YE S OK Tar content (g /Nm3)


Rg ·T Checking with
·Σ n
Q2 = Q
Q2 = i
1 exp. data
P Char concentration (g/kg S+D )

Fig. 8. Simplified flow diagram of calculation for the overall solution of the 1st, 1-dimensional pseudo-rigorous
model.

It is also assumed that the inlet air is heated at the bottom bed from the preheated air
temperature, of around 250–350 8C, to the temperature at which the gasifier operates in the
bottom bed.
When the mass balance for all the species is solved, the composition (vol.%) of the gas
species, char concentration and volumetric flow rate of gas ( Q 2) are obtained. Two zones
of resolution have been considered (1st: bottom zone–transition zone–part of dilute zone;
2nd: rest of the dilute zone).
In the 1st zone of resolution, two steps in series have been considered: the first
one is the fast pyrolysis; with Eq. (1) the product distribution are obtained (see
Section 3.2., kinetic equations used). The results from the fast pyrolysis are used in
J. Corella, A. Sanz / Fuel Processing Technology 86 (2005) 1021–1053 1047

START

INPUTS INPUTS: B, ER, ...


(As a function of the riser height)
Supposed Q 1 Supposed gas temperature
Supposed riser voidage, total gas flow
MODULE 1
Bottom Zone-Pyrolysis
OUTPUTS: X1, Cchar, total gas flow
SOLUTION: Subroutine 1 LHV, C content in fly ash
gas field
Xio, Cchar0
Xi0: initial molar fraction of the components after the
pyrolysis, for H2, CO, CO2, CH4, C2H4, H2O, N2, tar
MODULE 2
Transition, bottom zone
1st O2 and part of dilute zone XiA: molar fraction of the components before 2nd air
(air) inlet, for H2, CO, CO2, CH4, C2H4, H2O, N2, tar
SOLUTION: Subroutine 2
Subroutine 3
Xi: final molar fraction of the components, for H2, CO,
CO2, CH4, C2H4, H2O, N2, tar
XiA, CcharA, Q1'
NO CChar,0: char concentration after the pyrolysis
Q1 = Q1' Q1 = Q1' in g char / (kg sand + dolomite)
CChar,A: char concentration before 2nd inlet
YES
in g char / (kg sand + dolomite)
XiA, CcharA, Q1'
CChar: char concentration at riser exit
in g char / (kg sand + dolomite)
MODULE 3
Dilute zone
2nd O2
(air) SOLUTION: Subroutine 4 Subroutine 1: Pyrolysis reactions
Subroutine 5
Subroutine 6
Subroutine 2: Oxidation of products from pyrolysis

Xi, Cchar,Q2 Subroutine 3: Tar - char reactions and steam reforming of methane
NO
Q1'=Q2 Q2 = Q1' Subroutine 4: Oxidation of products from the bottom bed

YES Subroutine 5: Tar - char reactions and steam reforming of methane

OUTPUTS
Subroutine 6: Shift reaction

STOP

Fig. 9. Flow diagram for the solution of the mass balances.

second step as initial conditions for the resolution of mass balances for oxidation, tar
and char steam reforming and methane reactions. The values obtained at the exit of the
first zone are used as initial conditions for the resolution of the mass balances in the 2nd
zone. A fourth–fifth order Runge–Kutta method has been used to solve the mathematical
problem.
1048 J. Corella, A. Sanz / Fuel Processing Technology 86 (2005) 1021–1053

The volumetric flow rate of gas was considered constant along each zone. A
volumetric flow rate of gas is assumed for the entry point of each zone and it is used to
calculate the gas composition, tar content and char concentration at the end of that zone.
The volumetric flow rate of gas is calculated then for the end of the zone. If the
calculated volumetric flow rate of gas is not the same as the first value, Q 1pQ 1V, the
mass balance is repeated until the two values agree. The volumetric flow rate of gas
finally calculated for the first zone is used as the flow rate entering into the second one,
then repeating the same calculation.
The solution of the heat balance is carried out simultaneously with the kinetics and the
mass balances.
The char concentration in the flue gas was calculated in a two-step process:

– Char concentration is calculated along the gasifier height without considering its
recycling to the riser (first step).
– Once fixed the efficiency (99% for instance) of the (first) cyclone, the char recycled to
the bottom of the riser is known. The recycled (to the riser) char is taken into account in
a second step for an improved calculation.

When the kinetics and the mass and heat balances are solved, the axial profiles for
tar content, char concentration, gas composition and LHV are obtained as model
outputs. Besides, tar and char contents, C content in fly ash, gas composition, gas yield
and LHV at the gasifier exit are obtained at very different operating conditions. Results
from the model for very different operating conditions are shown in our next paper
[33].

Notation
b,d Reaction orders for the species i and w.
B Biomass flow rate, kg daf/h.
cv Volumetric fraction of solids, dimensionless.
Ci Concentration of the i-th species in the gas phase, mol/m3.
daf Dry, ash free.
ER Equivalence ratio, air fed/stoichiometric air, dimensionless.
fn Corrective factor in some kinetic equations.
i (from (1)–(10)): H2,CO, CO2, CH4, C2H4, H2O, O2, tar, char.
j Air, if the specie i considered is a gas; B daf, if the specie i is tar or char.
kn Kinetic constant of the n-th reaction, units depending on the considered reaction.
ṁ B Biomass flow rate (kg a.r./h).
ni Total moles of all the species in the flue gas, mol.
P Pressure in the riser, atm.
Q Volumetric gas flow rate, m3/h.
R Ideal gas constant, J/mol K (and also atm l/mol 8C in R appearing in Fig. 8).
Ri Overall reaction rate of the i-th species, units depend on the species considered.
rj Rate of the j-th reaction, units (given by the authors who provided each rate)
depend on the reaction and species considered.
J. Corella, A. Sanz / Fuel Processing Technology 86 (2005) 1021–1053 1049

T Temperature, K.
tg Mean residence time of the gas, s.
uo Superficial gas velocity at the bottom of the gasifier (gas inlet), m/s.
ut Terminal velocity of the particle, m/s.
W Mass of sand and dolomite in the gasifier (kg).
WHSV Weight hourly space velocity for the biomass [(kg biomass fed a.r.)/h]/kg solids
inventory in the CFBBG.
xi Molar fraction of the i-th species. For char, it is char concentration [kg char/kg
(sand+dolomite)].
xw Molar fraction of w, botherQ gas species which affect to the kinetics of the i-th
species. For char, it is char concentration [kg char/kg (sand+dolomite)].
yi Yield to the i-th species. For the gas species [H2,CO,CO2,CH4,C2H4,H2O, O2] its
units are (mol i/mair in3). For tar and char its units are (mol i/kg B daf).

Greek symbols
e Voidage in each zone of the riser, dimensionless.
s Space-time, based on m3 of riser (mR3) when the i-th species considered is a gas
component [units then: mR3/(mair,in3/h)], or based on mass of sand and dolomite
(S+D) in the whole gasifier(W S+D) when the i-th species considered is tar or char
[units then: kgS+D/(kg B daf/h)].

Acknowledgment

This work was carried out under the EC-financed project no. JOR3-CT98-0306. A.
Sanz thanks J.I. Civicos for his personal help in performing this modelling. Scientific
discussions with Dr. Hao Liu from University of Leeds (Chem. Eng. Dept.) have been very
stimulating for the development of this model.

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