Renewable and Sustainable Energy Reviews 134 (2020) 110380

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Renewable and Sustainable Energy Reviews

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Modelling soot formation during biomass gasification

A.I. Ferreiro *, R. Segurado , M. Costa
IDMEC, Mechanical Engineering Department, Instituto Superior Técnico, Universidade de Lisboa, Lisboa, Portugal

A R T I C L E I N F O A B S T R A C T

Keywords: Biomass gasification offers a significant potential to close the loop of agriculture and many other activities that
Non-woody residues produce biomass residues. However, the presence of tars and impurities, such as soot, in the gasification products
Gasification is still a major bottleneck causing operational problems, particularly blocking or fouling of equipment and low
Modelling
syngas quality. Numerical modelling is a very attractive solution to enhance the understanding of the physical
Soot formation
and chemical phenomena occurring in gasifiers and thereby to overcome these barriers. In addition, under­
standing the biomass gasification fundamentals in laboratory-scale devices, such as drop tube furnaces (DTF), is
crucial to evaluate its relevance for industrial applications. The main objective of this study is to develop a model
able to predict soot formation during the gasification of biomass in a DTF. The model developed is based on a
kinetic-diffusion approach and was implemented in Python using the Cantera reaction kinetics library. The
model is validated against experimental data that assessed the effect of the temperature and steam to biomass (S/
B) ratio on char and soot yields and syngas composition during the gasification of wheat straw in the DTF.
Overall, the model developed captures with a rather good accuracy the evolution of the char yields, but with a
less accuracy the evolution of the soot yields and syngas composition with the temperature and S/B ratio.

1. Introduction conversion processes like combustion, pyrolysis and gasification. In

Most of the environmental indicators prove that the rhythm of the
current economic growth is far from being sustainable and from
strengthen social and economic concerns, such as equality and well­
being. In fact, there is still electricity deprivation in several communities
around the world, which represents a failure in providing basic human
needs. These concerns associated with a worldwide increase of pollution
levels and irresponsible waste disposable and treatment have led to
serious difficulties in finding the environment natural equilibrium.
Thus, it is imperative to address these barriers by increasing the number
of green energy infrastructures [1–3]. On this matter, biomass is very
appealing due to its ease storage and transport, low price, flexibility and
availability in different forms [4–6]. Among the numerous types of
biomass, non-woody agricultural wastes are worthy of focusing due to
their high abundancy, fast growth, promptly availability and low cost.
However, these residues are characterized by low density, low quality
solid fuel, whose disposal can entail significant costs, due to its lignin
and high ash content [7–9]. Hence, improving the energy conversion
efficiency of the non-woody agricultural wastes remains a necessity and
a significant challenge.
Energy production from biomass involves thermochemical
particular, gasification allows the conversion of a wide variety of
biomass feedstock into chemical products and gaseous fuels (syngas)
that can be used for the production of value-added chemicals or burned
to produce heat and power, respectively [10,11]. Gasification occurs at
high temperatures and in the presence of an oxidizing atmosphere as
oxygen, air, steam, carbon dioxide or a proper mixture of these and its
primary objective is to convert the biomass feedstock into syngas with a
higher hydrogen-to-carbon (H/C) ratio. Even with low concentration,
condensable liquids and tars, such as polycyclic aromatic hydrocarbons
(PAH), are also released as gas product and represent one of the utmost
challenges on the development of biomass gasification infrastructures,
since these components are very heavy and stable at high temperatures,
being often converted into impurities, as soot, rather than the desired
combustible gases. The remaining solid product is termed char, which is
a mixture of a very high fraction of unconverted carbon with impurities
as ash and, as mentioned, a small fraction of soot [12–15]. Soot particles
are formed through 1) nucleation/inception by physical interactions
(collision) between PAH molecules that originate the primary soot
particles, 2) surface growth by the adhesion of CnHm or PAH components
on the particles surface, and 3) coagulation of the primary soot particles
[16]. These particles are known to endanger human well-being and to

* Corresponding author.
E-mail address: ana.ferreiro@tecnico.ulisboa.pt (A.I. Ferreiro).

https://doi.org/10.1016/j.rser.2020.110380
Received 30 April 2020; Received in revised form 19 June 2020; Accepted 15 September 2020
Available online 29 September 2020
1364-0321/© 2020 Elsevier Ltd. All rights reserved.
A.I. Ferreiro et al. Renewable and Sustainable Energy Reviews 134 (2020) 110380

have direct and indirect effects on the atmospheric climate [14]. processes is quite limited. As discussed earlier, the gasification process
Moreover, soot particles are very rich in carbon and can cause technical represents a reliable solution to increase the use of this type of resource.
difficulties in process operations, such as blocking or fouling of equip­ However, it is still a challenge to operate gasifiers with this type of
ment, and its formation must be inhibited. An efficient way to mitigate feedstock and often suboptimal results are delivered. In this sense, nu­
the formation of soot is enhancing the gasification processes, where the merical modelling is a very attractive solution to overcome these bar­
tars produced during pyrolysis can be reformed under the presence of an riers and it has shown itself to be crucial for research since it enlightens
oxidizing atmosphere [16,17]. physical and chemical phenomena that occur in gasifiers [11]. The
Biomass gasification occurs through different and complex steps, complexity involved in modelling the biomass gasification behavior,
which, depending on the type of gasifier, are often overlapped, making it especially in the formation of soot, has drawn the attention of several
difficult to establish a clear order of the different gasification stages. researchers in addressing this topic using different modelling ap­
Despite the difficulties, Sansaniwal et al. [5] proposed a sequence for the proaches [10,11,14–17,20,22,26,28–41]. The most common approaches
thermochemical reactions, namely, drying, pyrolysis, partial oxidation are thermodynamic equilibrium models, kinetic and kinetic
or combustion and reduction. The drying stage is an endothermic re­ diffusion-controlled models, and phenomenological and artificial neural
action that represents the evaporation of the moisture from the biomass. network models. It is unquestionable that modelling entangles a high
As more moisture is released, more energy is lost and the quality of the effectiveness in optimizing the gasification process and accuracy in
end product suffers accordingly. The pyrolysis stage occurs in the testing its limits. Other important advantage of performing simulations
absence of oxygen, between 280 ◦ C and 500 ◦ C, and corresponds to the relies on the low-cost exploration of the potential benefits, costs, and
primary decomposition of the hemicellulose, cellulose and lignin into risks associated when selecting the feedstock, operating conditions and
light and heavy condensable and permanent gases and solid residues. atmosphere environment in order to achieve the required syngas
The oxidation stage plays an important role in the type and quality of the composition [11,32]. Hence, in order to support the industry of com­
end product. In this stage, heterogeneous exothermic reactions occur mercial biomass gasification is of utmost importance to have simple and
between the remaining solid fuel and oxygen to produce a significant fast numerical tools that are able to evaluate the influence of biomass
amount of heat at temperatures between 1000 ◦ C and 1500 ◦ C. Finally, characteristics and operating conditions on the formation of soot during
the reduction stage can occur in absence of oxygen or under gasification to prevent costly operational problems. The selected
sub-stoichiometric conditions, where both homogenous and heteroge­ approach often depends on the type of gasifier, but for soot predictions
neous reactions, of which mostly endothermic, take place at tempera­ kinetic models are proven to give better results in comparison to other
tures between 800 ◦ C and 1000 ◦ C. This is the critical stage where tars models [14–16,35,40]. However, the kinetic parameters for these
are reformed to release light permanent and combustible gases [12,15, mechanisms are very case dependent and often derived from coal gasi­
18–21]. Table 1 summarizes the gasification processes and corre­ fication [42–44], which is comprehensive as a first step since similar
sponding main reactions [22–24]. chemical reactions are inherent for both biomass and coal thermal
Many recent studies focused on the mitigation of the formation of conversion processes. For instance, Wijayanta et al. [35,45] studied the
tars and, consequently, soot through secondary measures, such as cat­ formation of soot on both biomass and coal volatiles combustion using a
alytic thermal cracking [12,15,18,19,25]. It is known that the type of detailed soot formation kinetic reaction mechanism. The authors carried
gasifier and its operating conditions strongly affect the yields and out a comparative study on the released combustion products (including
composition of the syngas, tars and char products. Thus, the selection of PAH and soot) from both samples. They concluded that due to the
the type of gasifier, feedstock and its control strategy are essential to significantly higher oxygen content of the biomass sample, more
attain the most efficient and clean energy production [7,26]. Each type oxygenated radicals are released during the secondary gas-phase py­
of reactor is used accordingly with the type of feedstock, availability, rolysis reactions that can effectively oxidize PAH compounds preventing
physical properties, pre-treatment and composition [5,12,20,27]. the formation of soot, contrary to what is observed in coal. These studies
Currently, the use of non-woody biomass in energy conversion highlight the benefits of using biomass instead of coal in thermal con­
version processes.
The understanding of soot formation during gasification at a labo­
Table 1 ratory scale is a preliminary step to develop numerical models that can
Gasification processes and corresponding main reactions [22–24].
evaluate its relevance in industrial applications, for which drop tube
Process Reaction furnaces (DTF) and entrained flow reactors (EFR) can provide extremely
Drying Biomasswet →Biomassdry + H2 Ovapor ⋅ (R1) useful information [12]. The main objective of this study is to develop a
(endothermic) model able to predict soot formation during the gasification of a biomass
Pyrolysis Biomassdry →Char + Gases + Tars (R2) particle in a DTF considering products speciation and assess the effect of
Tar reforming Tar + H2 O→CO + H2 ⋅(endothermic) (R3) temperature and different gasifying agents on the products final yields
Tar cracking Tar + O2 →CO + H2 O⋅(endothermic) (R4) and composition. Initially, the present manuscript reviews the relevant
Tar + CO→CO2 + H2 + CH4 ⋅(endothermic) (R5) studies on the formation of soot during the gasification of biomass res­
Soot formation PAH→H2 + Soot⋅(endothermic) (R6) idues in DTFs and EFRs. Particular emphasis is given to numerical
Char complete oxidation C + O2 →CO2 , ΔH = –394kJ/mol (R7) studies that discuss the effect of operating parameters under the current
Char partial oxidation C + 0.5O2 →CO, ΔH = − 111kJ/mol (R8) used modelling approaches in order to clarify and enlighten existing
Boudouard reaction C + CO2 ↔ 2CO, ΔH = 172kJ/mol (R9) gaps. Subsequently, the manuscript presents a case study that assesses
Char steam reforming C + H2 O ↔ CO + H2 , ΔH = 131kJ/mol (R10) the effect of the temperature and of the steam to biomass ratio (S/B) on
C + 2H2 ↔ CH4 , ΔH = − 75kJ/mol (R11) the char and soot yields and syngas composition during the gasification
H2 + 0.5O2 ↔ H2 O, ΔH = − 242kJ/mol (R12) of wheat straw in a DTF. The approach used to develop the numerical
Water shift gas (WSG) CO + H2 O ↔ CO2 + H2 ,ΔH = − 41.2kJ/mol (R13) model is based on a pure kinetic regime-controlled model and was
reaction implemented in Python using the Cantera reaction kinetics library [46,
Dry reforming (DR) 2CO + 2H2 ↔ CH4 + CO2 , ΔH = − 247kJ/ (R14) 47]. Python is a high-level, scripted object-oriented programing lan­
reaction mol
guage, that is well known in the scientific community for data analysis
CO + 0.5O2 ↔ CO2 , ΔH = − 284kJ/mol (R15)
with several appliances in mathematics, general science and engineering
CH4 + 1.5O2 ↔ CO + 2 H2 O, ΔH = 36kJ/ (R16)
[48]. The modelling approach considers the biomass particle motion
mol
along the DTF and the different stages of the gasification, including the
CH4 + H2 O ↔ CO + 3 H2 , ΔH = 206kJ/mol (R17)
formation of soot. The experimental data used here to validate the

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A.I. Ferreiro et al. Renewable and Sustainable Energy Reviews 134 (2020) 110380

numerical model was obtained in our previous works [49,50]. numerical study, the authors used the GASPAR software. The model
includes drying, one step pyrolysis reaction, gas-phase and gasification
2. Modelling of soot formation reactions. The authors also proposed a kinetic mechanism for soot for­
mation, where the kinetic parameters were estimated using a classic
The soot formation process requires high energy, since it is governed method. All the reactions and mass species conservation were resolved
by endothermic reactions, and it needs a sustained dehydrogenation and through CHEMKIN subroutines using a detailed mechanism. Overall, the
polymerization of aromatic radicals to form larger PAH radicals, which GASPAR model gave satisfactory results in predicting products’ yields,
are promoted with temperature. These PAHs can then undergo through but the influence of the steam was not well captured for temperatures of
a series of complex secondary reforming, cracking and polymerization 1000 ◦ C and 1200 ◦ C, which was attributed to the reduced tar reforming
reactions originating light CnHm hydrocarbons, which can also be model used. Additionally, the GASPAR model was able to predict the
decomposed by the effect of heat and originate soot [14–17,51,52]. reduction of soot through the reforming of soot precursors and gasifi­
Several studies have focused on modelling the formation of soot [14–17, cation reactions. Li et al. [14] studied the effect of the temperature and
34–40]. The level of complexity of the model requires some dexterity, biomass composition on soot formation during fast pyrolysis in an EFR.
and the answer is not straight forward. A detailed model can provide Woody and non-woody samples were selected to perform measurements
very meticulous information about the chemical and physical processes, within a temperature range between 900 ◦ C and 1400 ◦ C. The authors
such as kinetics [14,16,34,35,38–40], rate of collision [37,39], surface modelled the formation of soot using the combination of KM2 (a detailed
growth [37,39], effect of catalysts [15,36] and even soot particles soot formation mechanism that contains 202 species and 1351 re­
number density [17,39] to obtain its final yield and composition. actions) with an improved CPD sub-mechanism (17 reactions associated
The three most common routes used to predict the soot formation to the formation of large aromatics compounds), included in CHEMKIN
during thermal conversion processes are through 1) hydrogen abstrac­ software. Both KM2 with and without CPD route were tested. The KM2
tion and carbon addition (HACA), a conventional hydrocarbon mecha­ was able to predict soot formation from biomass pyrolysis, which means
nism; 2) dimerization of two resonance stabilized cyclopentadienyl that in this case HACA was the dominant route for the soot formation,
(CPD) radicals to produce aromatic rings; and 3) transformation and whereas the CPD contribution was neglected. Moreover, these authors
condensation of PAHs. However, further investigations are needed to also concluded that lignin is the main source of soot formation in
comprehend the route that most influences the formation of soot [14, biomass, followed by cellulose, hence, woody biomass samples, which
42]. generally have higher lignin content, and produce two times more soot
As mentioned, several studies have focused on modelling the for­ than agricultural residues, as also observed by Qin et al. [53]. Umeki
mation of soot, but to follow the purpose of this study, focus is here given et al. [15] studied the effect of potassium in the reduction of tar and soot
to studies performed in DTFs and EFRs [14–16,35,36,40]. Table 2 formation during the gasification of woody biomass in an EFR, under a
summarizes the principal existing soot kinetic mechanisms. Septien N2/CO2 atmosphere at temperatures between 900 ◦ C and 1400 ◦ C. The
et al. [16] studied the effect of temperature, residence time and particle authors concluded that K2CO3 salt acts efficiently as a heterogeneous
size on soot formation during the gasification of woody biomass sam­ catalyst in the promotion of char reactions and in the reduction of tar
ples. Gasification tests were performed under a steam atmosphere at and soot during the gasification process, especially at temperatures
temperatures between 1000 ◦ C and 1400 ◦ C, using two distinct ranges of higher than 1100 ◦ C. In addition, the authors used a thermochemical
particle sizes (313–400 μm and 730–900 μm). The increase of residence equilibrium model to conclude that potassium remains in the
time at 1400 ◦ C led to a complete char gasification, but no significant solid-phase, in contrast with the experimental observations. Chhiti et al.
variation of the soot yields was observed. The particle size ranges used in [36] studied the effects of temperature and atmosphere on the formation
the experiments did not affect the products’ yields, which led the au­ of soot during the gasification of bio-oil, produced from woody samples.
thors to conclude that particles small than 1 mm could be gasified in an Experiments were carried out in an inert atmosphere and in mixtures of
EFR with similar characteristics of the one used in their study. For the N2/steam and N2/O2 for temperatures between 1000 ◦ C and 1400 ◦ C.
The authors adapted the conventional GASPAR model to predict the
formation of soot. A single reaction model was used, being C2H2 the only
Table 2
Summary of the principal existing soot kinetic mechanisms.
soot precursor, along with three heterogeneous reactions able to
consider soot oxidation and reduction. Overall, the model was able to
Reference Mechanism Process Kinetic parameters
capture the soot formation trends in a satisfactory way, but the best
A E (kJ/ β n results were obtained between 1000 ◦ C and 1200 ◦ C. Above this tem­
(s− 1) mol) (− )
perature, the single step model was unable to predict the final soot
[16] C2 H2 →2Soot + H2 Inception 1.0 × 167 0 1 yields. The authors also concluded that the main contributor for the soot
m Inception 106
Cn Hm →nSoot + H2 reduction was H2O, being the CO2 contribution very small and the O2
2 5.0 ×
consumed prior to this event and hence with no effect on soot oxidation.
106
[14] m Inception Billaud et al. [41] studied the influence of steam, CO2 and O2 addition
Cn Hm →nSoot + H2 – – – –
(2 Reforming during the gasification of sawdust in an EFR. Experiments were per­
Cn Hm + H2 O→ n + Reduction formed for temperatures between 800 ◦ C to 1400 ◦ C. The authors used
m) the GASPAR software and CHEMKIN subroutines to solve the mass
H2 + nCO
2
species conservation. A very detailed gas-phase model was used (176
Cn Hm + nCO2 →
(m) species and 5988 reactions) following the work of Ranzi et al. [54]. For
2
H2 + 2nCO soot formation, the authors included two chemical reactions that are
[35] C2 H2 →2Soot + H2 Inception – – – – able to capture the inception effects and a third of the soot growth ef­
Soot + 0.5O2 →CO Oxidation
fects. The authors concluded that the model is able to predict the final
Soot + H2 O→CO + H2 Reforming
Soot + CO2 →2CO Reduction
yields of char, gas, tars and soot evolution. This confirms that the use of a
[40] C20 H16 →20 Soot + Inception 5.0 × 167 0 1
detailed model to predict with good accuracy the tar cracking and
8H2 Inception 106 167 reforming processes is crucial to have reliable predictions of the for­
C20 H10 →20 Soot + Growth 5.0 × 41.8 mation of soot. Finally, the addition of H2O and CO2 lowered the for­
5H2 106 mation of soot, but also decreased the energy of the released gas.
C2 H2 + Soot→3 Soot + 2.5 ×
H2 108

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A.I. Ferreiro et al. Renewable and Sustainable Energy Reviews 134 (2020) 110380

3. Case study

3.1. Experimental

The experimental data used in this study was taken from our previ­
ous work [49,50]. Wheat straw (WS) was used as feedstock, due to its
high availability as agricultural residue and low cost. The WS was pul­
verized and sieved to sizes between 90 μm and 150 μm with the aid of a
SS-15 Gilson Economy 203 mm Sieve Shaker. Before the experiments,
the biomass was dried in an oven at 105 ◦ C overnight. Table 3 shows the
ultimate, proximate and ash analysis of the WS. The ultimate analysis
was determined following the procedures specified in the standards
CEN/TS 15104 and CEN/TS 15408 and the proximate analysis following
the procedures specified in the standards CEN/TS 15414:2006, CEN/TS
15402: 2006 and CEN/TS 15403:2006. The heating values of the
biomass were determined following the procedures specified in the
standard CEN/TS 14918:2015, and the chemical composition of the
ashes was determined using x-ray fluorescence spectroscopy.
The amounts of hydrophilic and hydrophobic extractives, hemicel­
lulose, cellulose and lignin present in the WS were determined experi­
mentally, as discussed elsewhere [55]. In order to use the pyrolysis
Bio-PoliMi model [56], the composition of the three structural lignins
(LIG-C, LIG-H e LIG-O) was estimated using a two-step fitting procedure
algorithm developed and applied in our previous works [55,57]. Fig. 1
shows the chemical composition of the biomass.
Fig. 1 shows a schematic of the experimental setup used for the
gasification experiments [49,50]. It comprises a biomass feeder, a gas
supply system, for O2, CO2 and N2, a vertical electrically heated
nonporous mullite tube, a particle collection system and a gas sampling
and analysis system. The biomass feeder consists of a twin-screw volu­
metric feed where the biomass is poured. The biomass particles are
carried to a water-cooled injector with the aid of a carrier gas, N2 in this
case. This injector feeds the particles (and the carrier gas) into the ver­
tical mullite tube. The mullite tube has a total length of 1750 mm and an
inner diameter of 40 mm, and its wall temperatures are continuously
monitored by three type-K thermocouples uniformly distributed along
the tube. The wall temperature can be varied up to 1300 ◦ C and particles
injected from the top of the DTF typically experience heating rates of
~105 K/s and residence times of around 2 s. A concentric passage be­
tween the mullite tube and the injector ensures the introduction of the
gasifying agent stream, a mixture of N2, O2 and steam, into the tube of
Table 3
WS chemical properties.
Proximate analysis (wt.%., as received)
Fig. 1. Chemical composition of the WS.
the DTF. The steam is generated by an evaporator at a pressure of 2 bar.
The remaining gases are supplied from pressurized bottles. At the bot­
tom of the reactor is located the particle collection system. This system is
composed of two cyclones, an in-house made cyclone and a commercial
cyclone (Dekati®), and a low pressure 13-stage cascade impactor (DLPI,
Dekati® Ltd.). To avoid gas condensation during the experiments, the
particle collection system was maintained at temperatures above 150 ◦ C
using heating blankets. The two cyclones were able to capture particles
(char) with sizes above 10 μm, while the 13-stage cascade impactor was
able to capture particles (soot and char) with sizes below 10 μm. The
particles retained in the 13-stage cascade impactor were identified as
soot and char using two methods: scanning electron microscopy/energy
dispersive X-ray spectroscopy (SEM/EDS) and ultimate analysis of the
samples. The syngas composition was measured using a paramagnetic
pressure analyzer for O2, a non-dispersive infrared analyzer for CO2 and
CO and a gas chromatograph Clarus 500 for the remaining gases.
In the previous works [49,50], we evaluated the influence of the
temperature and gasifying agent on the WS gasification, including soot
formation. Table 4 summarizes the experimental conditions used in
these earlier studies. The temperature during the gasification experi­
ments was varied between 900 ◦ C and 1200 ◦ C. Two distinct gasification
atmospheres were used: O2/N2 and O2/H2O/N2. The oxygen ratio, λ,
defined as the ratio between the oxygen fed and the stoichiometric ox­
ygen for the biomass combustion, was kept constant for all experiments
and equal to 0.4.

Moisture 8.0 3.2. Modelling

Volatile matter 64.9
Ash 14.7
Fixed carbon (by dif.) 12.4 In the present work, a kinetic-diffusion controlled model was
Heating value (MJ/kg) developed and implemented in Python using the Cantera reaction ki­
Low 13.0 netics library [46,47]. The model aims to predict the gasification
High 14.1
behavior of a biomass particle, considering products speciation. Since
Ultimate analysis (wt.%, dry ash free)
Carbon 41.1
pyrolysis is the utmost important step in gasification, the Bio-PoliMi
Hydrogen 5.3 pyrolysis mechanism [56] and a very detailed secondary gas-phase
Nitrogen 0.7
Sulphur
Table 4
<0.02
Oxygen (by dif.) 52.6
Ash composition (wt.%, dry basis)
Experimental conditions used in our previous works [49,50].
Al2O3 8.7 T (◦ C) ṁbio (kg/h) S/B V̇O2 (L/min) V̇air (L/min) V̇N2 (L/min)
CaO 28.0
Cl 0.6 900 23 0 0 0.5 10
Fe2O3 5.0 1000
K2O 6.9 1100
MgO 3.7 1200
Na2O 0.6 1000 30 0 0.11 0 9.89
P2O5 2.6 0.5 9.35
SO3 1.0 0.8 8.99
Others 0.9 1.7 8.09

4
A.I. Ferreiro et al.
reaction model [58], including the formation of soot [14,16,40], were
incorporated in the model. As for the gasification stage, distinct het­
erogeneous chemical reactions were considered to account for the ef­
fects of each gasifying agent. To solve the species conservation and
calculate the reaction rates, a stiff ordinary differential equation solver
(CVODE) [47] in Python was used. The measured temperatures profiles
of the gas and reactor walls, biomass composition, reactor and mass flow
characteristics were used as models’ inputs. The approach adopted in
this study aims to enlighten existing gaps in the literature kinetic
mechanisms; focus was therefore given mainly to the kinetic-diffusion
controlled model, while a simple approach for the particle movement
and mass transfer was kept.
3.2.1. Model assumptions
A single biomass particle and the carrier gas enter in a pre-heated
environment (DTF) and are heated up through radiation and convec­
tion. The volatiles release rate from the particle and the heat transfer
between the particle and its surroundings are calculated along the axial
direction of the DTF. The biomass and gas flow inlets in the DTF are
treated as a single biomass particle and as a surrounding gas volume,
respectively. Both mass and heat transfer between the particle and its
surroundings are treated as a function of the particle position along the
axial direction of the DTF; hence for each position, a 0-D modelling
approach is considered.
Fig. 2. Schematic of the experimental setup used for the gasification experiments.
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Renewable and Sustainable Energy Reviews 134 (2020) 110380
Several characteristic times, related to physical and chemical phe­
nomena, are estimated to evaluate the influence of mass and heat
transfer in the biomass gasification conditions. As a result, this model is
based on a pure kinetic-controlled regime. In addition, the internal heat
transfer within the particle is neglected. More details are given in Ap­
pendix A. The model assumptions are as follows.
1. The fuel particle has a one-dimensional, spherical geometry, and is
considered isothermal.
2. Particle shrinkage is considered during gasification.
3. External mass transfer is instantaneous.
4. Radiative external heat transfer occurs only through the reactor
walls.
5. Heat transfer to the particle surface occurs through convection and
radiation.
6. Interactions between organic and inorganic components of the
biomass are neglected.
3.2.2. Particle movement
In this study, the initial particle velocity (vp,0 ) was taken as that at the
exit of the water-cooled injector (cf. Fig. 2), and was calculated using the
following equation [59]:
A.I. Ferreiro et al. Renewable and Sustainable Energy Reviews 134 (2020) 110380

( )
dp2 g ρp − ρg ( ) ( )
vp,0 = , Re < 2 (Eq. 1) kpyr (T) = ATpβ exp −
E
, kgas (T, P) = ATpβ Png exp −
E
(Eq. 14)
18μg RTp RTp
The governing equation of the particle trajectory is derived from the √̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅
gravity, drag and buoyancy forces acting on the particle, which can be f (X)char = (1 − X) 1 − ln(1 − X), f (X)soot = (1 − X) (Eq. 15)
written as [60]: Note that f(X)soot considers a homogenous reaction throughout the
( )
dvp vg − vp particle and a linearly decreasing reaction surface area with conversion,
= 2 +g (Eq. 2) and f(X)char assumes the overlapping of pore surfaces, reducing the
dt 4 ρp dp
3 CD Reμg available surface area for reaction [62].
Expressions for the Reynolds number and drag coefficient (CD ) are
given in Appendix A. 3.2.5. Pyrolysis and gasification kinetic mechanisms
The kinetic mechanisms used for the pyrolysis and the secondary gas-
3.2.3. Particle mass phase, where tar cracking reactions are considered, can be found in the
The mass species conservation is solved through the SUNDIALS works of Ranzi et al. [56] and Debiagi et al. [58], respectively. The
solvers (CVODE) included in the Cantera Reactor Class [47,61]. It reads evaporation reaction and its kinetic parameters are considered in the
as [61]: pyrolysis mechanism and were taken from Refs. [68]. Global kinetic
parameters for these reactions are inexistent and, hence, are very case
dYsp ∑ ( ) dependent. Additionally, most of these studies apply kinetics derived
mp = ṁbio,in Ysp,in − Ysp + ṁsp,gen (Eq. 3)
dt sp from coal gasification. Table 5 shows the kinetic parameters of the
heterogeneous and homogeneous chemical reactions used to describe
with: the gasification behavior in the present work.
/
ṁsp,gen = ω̇ × Mw,sp ρg (Eq. 4)
3.2.6. Soot kinetic mechanism
As already mentioned, soot particles are formed in the secondary gas-
Consequently, the total particle mass at each position (x) along the
phase reactions through the cracking and reforming of PAHs and CnHm
DTF is given by:
hydrocarbons [14–17,51,52]. Additionally, like gasification, global ki­
∑
mp = mp,0 × Ysp (Eq. 5) netic parameters for the soot reactions are inexistent, and often soot is
sp thermodynamically treated as a pure carbon particle. For these reasons,
in this work, soot gasification was treated using the same approach as
The particle diameter and density along the DTF are updated using
char, including the use of the same thermodynamic properties. CnHm
the following equations [62,63]. The exponent in Eq. (6) is based on the
species were selected from the secondary gas-phase kinetic mechanism
experimental results.
[56] and their contribution to soot formation was accessed through the
( )0.4
mp mass species conservation calculations (Eq. (3) and Eq. (12)). Table 6
dp = dp,0 × (Eq. 6) shows the kinetic parameters of the soot inception and reduction re­
mp,0
actions considered in the present work. Note that the kinetics for reac­
ρp =
mp
=
mp
(Eq. 7) tion R23 were assumed similar to those for reaction R22.
Vp πdp3/6

3.3. Results and discussion

3.2.4. Energy conservation
The unsteady energy equation for the heat released from a particle
Fig. 3 shows the measured and predicted char and soot yields as a
under gasification conditions can be expressed as the elementary sum of
function of the gasification temperature and of the S/B ratio. Overall, it
all energy contributions that are absorbed or released from the particle
is observed that the predictions agree reasonably well with the experi­
[59,63–67]:
mental results, revealing that as the gasification temperature or the S/B
dT ratio increase both the char and the soot yields decrease.
cp,p mp = Q̇in − Q̇out = Q̇convection + Q̇radiation − Q̇pyrolysis − Q̇soot − Q̇gasification
dt Actually, the predictions capture with a rather good accuracy the
(Eq. 8) evolution of the char yields, but with a less accuracy the evolution of the
soot yields. As already mentioned, the formation and reduction of soot is
with: directly connected to the formation and thermal cracking of tars. The
λg ( ) predictions in Fig. 3c indicate a maximum in soot formation for a gasi­
Q̇convection = Nu Ap Tg − Tp (Eq. 9) fication temperature of 1000 ◦ C – it is interesting to observe that this
dp
maximum also exists in the experimental data. For temperatures below
( ) 1000 ◦ C, the rate of thermal cracking of the tars is low and the inception
4
Q̇radiation = Ap εσ Twall − Tp4 (Eq. 10)
reactions are promoted (R18 and R19), increasing the formation of soot
rxpyr
∑ ( )
Q̇pyrolysis = kpyr,j (T)ΔHj dmp (Eq. 11) Table 5
j=1 Kinetic parameters of the heterogeneous and homogeneous chemical reactions
used to describe the gasification behavior in the present work.
∑
rxsoot
( ) Reaction A (s− 1) E (cal/ n Reference
Q̇soot = kgas,j (T, P)ΔHj f (X)soot dmp (Eq. 12) β
mol)
j=1

R7 C + O2 →CO2 9.35 × 104 19.8 0 1 [42]

rxgas
∑ ( ) R8 C + 0.5O2 →CO 9.35 × 104 19.8 0 1 [42]
Q̇gasification = kgas,j (T, P)ΔHj f (X)char dmp (Eq. 13)
j=1 R9 C + CO2 ↔ 2 ​ CO 3.4 × 107 42.9 0 1 [42]
R10 C + H2 O ↔ CO + H2 1.4 × 108 42.9 0 1 [42]
and: R13 CO + H2 O ↔ CO2 + H2 2.0 × 1011 38.0 0 1 [56]

6
A.I. Ferreiro et al. Renewable and Sustainable Energy Reviews 134 (2020) 110380

Table 6
Kinetic parameters of the soot inception and reduction reactions considered in the present work.
Reaction Route A (s− 1) E (cal/mol) β n Reference

R18 C2 H2 →2 Soot + H2 Inception 1.0 × 106 39,910 0 1 [16]

R19 m Inception 5.0 × 106 39,910 0 1 [16]
Cn Hm →n Soot + H2
2
R20 Soot + 0.5O2 →CO Oxidation 1.2 × 1010 38,200 0 [Soot] [O2]0.78 [56]
R21 Soot + O2 →CO2 Oxidation 2.5 × 1011 32,300 0 [Soot] [O2]0.78 [56]
R22 Soot + H2 O→CO + H2 Reforming 2.5 × 109 52,000 0 [Soot]0.5 [O2]0.78 [56]
R23 Soot + CO2 →2 ​ CO Reduction 2.5 × 109 52,000 0 [Soot]0.5 [O2]0.78 –

Fig. 3. Measured and predicted char and soot yields as a function of the gasification temperature (a, c), and of the S/B ratio (b, d).

Fig. 4. Measured and predicted syngas composition as a function of the gasification temperature (a, c), and of the S/B ratio (b, d).

7
A.I. Ferreiro et al.
up to 1000 ◦ C. For temperatures higher than 1000 ◦ C, the rate of thermal
cracking of the tars increases substantially, inhibiting the soot inception
reactions and, at the same time, promoting the oxidation and reduction
reactions (R20 to R23), and thereby decreasing the soot yields. These
results are in line with literature findings [16,35,40,69–71]. The pre­
dictions in Fig. 3d reveal that the increase of the steam in the gasifying
agent promotes both the reforming of the tars (R3) and the soot
reforming reaction R22, both inhibiting the formation of soot, as
observed by Septien et al. [16] and Billaud et al. [41].
In conclusion, the present model is able to capture the evolution of
the soot yields as a function of the gasification temperature and of the S/
B ratio, but improvements are obviously possible. For example, the
global kinetic parameters for the reactions used were derived from coal
gasification experiments [42–44], with the quality of the predictions
suffering accordingly.
Fig. 4 shows the measured and predicted syngas composition (H2,
CO2, CO and CH4) as a function of the gasification temperature and of
the S/B ratio. Le Chatelier’s principle states that higher temperatures
(≥1000 ◦ C) promote the formation of reactants and products for
exothermic and endothermic reactions, respectively. This means that in
Fig. 4a and c, the heterogeneous and endothermic reactions R9 and R10
take a preferred path enhancing the formation of CO and H2. Simulta­
neously, the exothermic reactions R13 and R14 shift the equilibrium
towards the left side further increasing the formation of CO and H2,
while inhibiting the formation of CO2 and CH4. This is attributed to the
tars thermal cracking (R3 to R5) that promote the release of H2 and CO,
as also observed in related works [43,44,71–75]. For this set of experi­
ments, the model predicts unwell the evolution of the syngas composi­
tion with the temperature. This is ascribed both to the kinetics of the
homogenous reactions used and to the absence of the kinetics for the dry
reforming reaction (R14), which path is preferred in gasification pro­
cesses that occur in air/N2 environments [19,71,74].
Fig. 4b and d show opposite evolution trends in the production of CO
and H2 and of CO2 and CH4 as a function of the S/B ratio, respectively.
An increase in this ratio leads to the boost of H2 production and a slight
increase of CH4 formation, while the production of CO and CO2 is
inhibited, which agrees with the Le Chatelier’s principle. Reactions
where the water has a reactant role, i.e., R10, R13 and R17, lead to the
enhancement of the char conversion and H2 production, when the H2O/
C ratio increases. Similar outcomes were found in other works for
different types of biomass [16,19,53,71,76,77]. For this set of experi­
ments, the model is also unable to predict the evolution of the syngas
composition with the S/B ratio. This is ascribed to the kinetics of the
homogenous reactions used here being derived from coal gasification
experiments.
4. Conclusions
In this work, a kinetic-diffusion controlled model was developed and
implemented in Python using the Cantera reaction kinetics library to
Appendix A
A.1 Wheat straw and carrier gas properties
Tables A.1 and A.2. show the wheat straw and carrier gas properties considered in this study.
Table A.1
WS properties.
Description
Emissivity
Raw particle density
Pore diameter
8
Renewable and Sustainable Energy Reviews 134 (2020) 110380
predict the gasification behavior of biomass particles, considering
products speciation. The model was validated against experimental data
that assessed the effect of temperature and S/B ratio on char and soot
yields and syngas composition during the gasification of wheat straw in
a DTF.
The experimental results show that high gasification temperatures
and S/B ratios enhance the char conversion, being the impact more
accentuated for the temperature. The model developed captures with a
rather good accuracy the evolution of the char yields, but with a less
accuracy the evolution of the soot yields and syngas composition with
the temperature and S/B ratio.
The implemented model presented in this study is very flexible, since
it is able to provide information about the chemical and physical
properties of a biomass particle and surrounding flow characteristics in
any stage of an EFR/DTF reactor and in different operating conditions
(temperature, gasifying agent, feedstock, mass flow). This is of extreme
importance for scaling up an experimental facility since it reduces time
and costs in the selection of the proper feedstock and reactor operating
conditions, according to the desired end product, and also to prevent
operational and environmental problems related to the formation and
deposition of soot.
The present model provided encouraging results for the soot yields
from biomass gasification, but improvements are obviously needed.
Model improvements require kinetics derived from biomass gasification
experiments. In this context, the use of optimization processes, such as
genetic algorithms and least squares procedures, that are able to esti­
mate kinetic parameters with a high degree of precision should be
considered.
CRediT authorship contribution statement
A.I. Ferreiro: Conceptualization, Methodology, Formal analysis,
Writing - original draft. R. Segurado: Conceptualization, Supervision,
Writing - review & editing. M. Costa: Conceptualization, Supervision,
Writing - review & editing.
Declaration of competing interest
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influence
the work reported in this paper.
Acknowledgements
This work is dedicated to the memory of Professor Mário Costa, our
mentor, a great scientist and person that will be missed. This work was
supported by the Fundação para a Ciência e a Tecnologia (FCT), through
IDMEC, under LAETA, projects PTDC/EME-EME/30,300/2017 and
UID/EMS/50,022/2019. A.I. Ferreiro acknowledges FCT for the provi­
sion of the scholarship SFRH/BD/129693/2017.
Symbol (units) Value
ε (− ) 0.70 [78]
ρp (kg/m3) 121 [79]
6
dpore (m) 3.2 × 10− [71]
(continued on next page)
A.I. Ferreiro et al. Renewable and Sustainable Energy Reviews 134 (2020) 110380

Table A.1 (continued )

Description Symbol (units) Value

Raw biomass specific heat capacity cp,p (J/kg.K) 1500 + Tp [71]

Raw biomass thermal conductivity λp (W/m.K) 0.21 [79]

Table A.2
Carrier gas properties [59].

Description Symbol (units) Value

Specific heat cp,g (J /kg.K) 770 + 2.09.Tg + 1.90 × 10− 4

× Tg2
Thermal conductivity λg (W /m.K) 0.026
Dynamic viscosity [80] μg (Pa.s), (kg /m.s) 4.847 × 10− 7 × Tg0.64487
Gas density 3
ρg (kg /m ) 362.65 × Tg− 1

The Reynolds (Re), Prandtl (Pr), Nusselt (Nu), Sherwood (Sh) and Schmidt (Sc) numbers, and drag coeffi­
cient (CD ) are defined as [81].

A.2 Fluid dynamics non-dimensional numbers

⃒ ⃒
dp ⃒vp − vg ⃒ρg
Re = (Eq. A1)
μg

cp,g μg
Pr = (Eq. A2)
λg

Nu = 2.0 + 0.6Re1/2 Pr1/3 (Eq. A3)

hm dp
Sh = (Eq. A4)
D
μg
Sc = (Eq. A5)
ρg D 0
[ ]
24 ( ) 0.413
CD = 1.5 1 + 0.173Re0.657 + 1.09
(Eq. A6)
Re 1 + 16300Re−

A.3 Physical and chemical characteristic times

The characteristic times for the physical phenomena associated with a spherical particle are defined as follows:

• External mass and convective heat transfers [52]:

ρp cp,p dp λg
tconvection = , hconvection = Nu ​ (Eq. A7)
hconvection dp

ρp RTdp
texternal mass = (Eq. A8)
6hmass Pgas MWCO

• External radiative heat transfer [52]:

ρp cp,p dp2
tradiation = ( )( ) (Eq. A9)
6εp σ Tg + Tp Tg2 + Tp2

• Heat conduction inside the particle [52]:

ρp cp,p dp2
tconduction = (Eq. A10)
6λp

• Internal mass diffusion [52]:

dp2
tinternal mass = (Eq. A11)
36Deff

9
A.I. Ferreiro et al. Renewable and Sustainable Energy Reviews 134 (2020) 110380

( )
εp
Deff = D (Eq. A12)
τp
( )− 1
1 1
D= + (Eq. A13)
D0 Dknudsen

The binary diffusion coefficient D0 is given by Ref. [82]:

[( )/ ]1.75
10− 3 Tgas + Tp,k 2 MWO0.52
D0,O2 = [∑ ∑ ]2 (Eq. A14)
P ( υ)1/3
O2 + ( υ)1/3
N2

3
[( )/ ]1.5 0.5
2.628 × 10− Tgas + Tp,k 2 MWi,N
D0,i = 2
(i = CO2 , H2 O) (Eq. A15)
Pσ 2i,N2 ΩD

with [80]:
MN2 + Mi
MWi,N2 = , (i = ​ CO2 , H2 O) (Eq. A16)
2MN2 Mi

σ N2 + σ i
σN2 ,i = , σ = 0.841Vc1/3 (Eq. A17)
2
( )
ΩD = 44.54⋅T •− 4.909
+ 1.911⋅T •− 1.575 0.10
(Eq. A18)
( )
Tm Tgas + Tp,k
T• = ( )0.5 , Tm = , (i = CO2 , H2 O) (Eq. A19)
0.75 Tc,N2 ⋅Tc,i 2

The only unknowns in the Eq. (A17) and A19 are Vc and Tc, the critical volume (m3/mol) and temperature (K), respectively, that can be taken
from NIST website [83], or through the Cantera’s library [47]. Table A3 shows the parameters needed to determine the diffusion coefficient (D0,i )
for mixtures of N2/CO2, N2/H2O and N2/O2.
Table A.3Parameters needed to determine the diffusion coefficient D0,i .

Parameter Unit N2 CO2 H2O O2

Tc K 126.2 304.1 647.1 154.6

ρc kg/m3 313.3 467.6 322.0 436.1
Mi kg/mol 28.0 × 10− 3 44.0 × 10− 3 18.0 × 10− 3 16.0 × 10− 3
Vca) m3/mol 89.4 × 10− 6 94.1 × 10− 6 55.9 × 10− 6 73.910–6
σi M 3.8 × 10− 10 3.8 × 10− 10 3.2 × 10− 10 3.5 × 10− 10
a)Vc
= (Mi/ρc) (m3/mol).
The characteristic times for the chemical phenomena associated with a spherical particle are defined as follows:
• Pyrolysis time [52]:
1
tpyr = (Eq. A20)
kpyr

1
tgas = (Eq. A21)
kgas

Table A.4 shows the non-dimensional numbers related to biomass gasification estimated in this study [52].

Table A.4
Biomass gasification non-dimensional numbers.

Non-dimensional number Expression

Biot number (Bi) tconduction /tconvection

Damkholer number (Da) tpyr /tconvection
Pyrolysis number tpyr /tconduction
External radiation/Convection ratio tradiation /tconvection
Mass Biot number (Bim) tinternal mass /texternal mass
Gasification/External mass transfer ratio tgas /texternal ​ mass
Gasification/Internal mass transfer ratio tgas /tinternal ​ mass
Gasification/pyrolysis ratio tgas /tpyr

10
A.I. Ferreiro et al. Renewable and Sustainable Energy Reviews 134 (2020) 110380

Table A.5 shows the gasification regime identification associated with each range of the non-dimensional number [52].

Table A.5
Gasification regime identification.

Bi « 1 Bi » 1
Bim « 1 Bim » 1

Da « 1 Da » 1 Py » 1 Da » 1
tgas /texternal ​ mass «1 tgas /texternal ​ mass » 1 tgas /tinternal ​ mass » 1 tgas /texternal ​ mass » 1
Limited by heat external transfer Pure kinetic regime Limited by heat internal transfer

Nomenclature

Parameter Units Designation

A s-1 Pre-exponential factor
Ap m2 Particle area
Bi - Biot number
CFD - Computational fluid dynamics
CPD - Resonance stabilized cyclopentadienyl
CCE % Carbon conversion efficiency
CGE % Cold gas efficiency
CD - Drag coefficient
cp J/kg.K Specific heat
D0 m2/s Binary diffusivity
D m2/s Global diffusion coefficient
Da - Damkholer number
Deff m2/s Effective diffusion coefficient
Di m2/s Diffusional reaction coefficient
Dknudsen m2/s Effective diffusion coefficient
dp m Particle diameter
E cal/mol Activation energy
g m2/s Gravity acceleration (g = 9.8 m2/s)
ΔH kJ/kmol Heat of reaction (kJ/kmol)
hm m/s mass exchange coefficient
hconvection W/m2.K heat of convection coefficient
k s-1 Reaction rate
LHV MJ/Nm3 Lower heating value
m kg Mass
ṁ kg/s Mass flow rate
Mw kg/kmol Molecular weight
n - Reaction order
Nu - Nusselt number
P Pa Total gas pressure
Pg Pa Partial pressure of reactant in the bulk gas at the particle surface
Pr - Prandlt number
Q̇ W Heat generated
Qsyngas Nm3/h Syngas flow rate
rx - Reaction number
R J/mol.K Ideal gas constant (8.314 J/mol.K)
Re - Reynolds number
t s Time
T K Temperature
v m/s Velocity
V m3 Volume
V̇ L/min Volume flow
X wt.% Char conversion
x - Molar fraction
Y - Mass fraction

Greek symbols
Parameter Units Designation
β - Temperature exponent in the Arrhenius law
ε - Emissivity
εp - Particle porosity (εp = 10− 9 )
λ W/m.K Thermal conductivity
μ kg/m.s Dynamic viscosity

11
A.I. Ferreiro et al. Renewable and Sustainable Energy Reviews 134 (2020) 110380

υ cm3/mol Diffusion volume for simple molecules

ρ kg/m3 Density
σ J/s.m2.K4 Stefan-Boltzmann constant (σ = 5.67 × 10− 8 )
σL Å Characteristic length
σ i,N2 Å Binary pair characteristic length
τp - Particle tortuosity (τp = 6)
ω̇ kmol/m3.s Net production rates
Φ - Mechanical factor
ΩD - Diffusion collision integral

Subscripts
Parameter Meaning
0 initial
b backward
bio biomass
c critical
f forward
g gas
gas gasification
gen generated
in inlet
m mass
p particle
pyr pyrolysis
sp specie
wall reactor wall

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