Biomass and Bioenergy 106 (2017) 104e114

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Biomass and Bioenergy

journal homepage: http://www.elsevier.com/locate/biombioe

Research paper

Enhancements in Biomass-to-Liquid processes: Gasication aiming at

high hydrogen/carbon monoxide ratios for direct Fischer-Tropsch
synthesis applications
Andrea Chiodini a, *, Letizia Bua a, Lino Carnelli a, Robin Zwart b, Berend Vreugdenhil c,
Marco Vocciante d
a
Renewable Energies & Environmental R&D Center - Istituto Guido Donegani, Eni S. p. A., Via Fauser 4, 28100 Novara, Italy
b
Dahlman Renewable Technology B.V., Scheldeweg 10, 3144ES Maassluis, The Netherlands
c
Energy Research Centre of the Netherlands (ECN), Westerduinweg 3, 1755LE Petten, The Netherlands
d
DCCI, Department of Chemistry and Industrial Chemistry, University of Genova, Via Dodecaneso 31, 16146 Genova, Italy

a r t i c l e i n f o a b s t r a c t

Article history: The Fischer-Tropsch process is one of the possible routes to produce synthetic liquid fuels and chemicals
Received 6 March 2017 employed on large scale in Gas-to-Liquid and Coal-to-Liquid processes, after appropriate transformation
Received in revised form of respective fossil sources into syngas. However, syngas can be produced by biomass gasication as well.
13 August 2017
One of the main problems is the need to ensure high H2/CO ratio to allow the Fischer-Tropsch reaction to
Accepted 15 August 2017
occur, operation commonly achieved by resorting to a Water-gas shift step. The present work reports an
experimental study on biomass gasication. The aim was to set up a more efcient Biomass-to-Liquid
process, which ensures a high H2/CO ratio syngas suitable for Fischer-Tropsch synthesis directly from
Keywords:
Gasication
biomass gasication. In this way, it is possible to remove the Water-gas shift section and consequently
H2/CO ratio make biofuels production more attractive, reducing costs and plant complexity. Two types of biomass
Biomass-to-Liquid (BtL) have been tested: softwood from forest residues and fast growing crops. Moreover, a bubbling uidized
Biofuels bed reactor and an indirect gasier with internal circulating uidized bed have been used. Gasication
Fischer-Tropsch synthesis tests have been conducted by running gasiers with both inert and catalytic bed materials. The results
Syngas have shown that, using the direct gasier with catalytic bed and a proper conguration, H2/CO molar
ratio of 2 can been obtained even at low temperature and low steam/biomass ratio, whereas this is not
the case in the indirect one. However, tests suggest that an inverted conguration would make it possible
to obtain values near two also with indirect gasiers, resulting in a new interesting approach.
2017 Elsevier Ltd. All rights reserved.

1. Introduction
Nowadays, renewable energy sources (e.g. solar, wind and
biomass) are playing a growing role in the international energy
framework, due to their reduced environmental impact and the
opportunity to reduce dependence on traditional fossil fuels. In this
context, particularly promising is the possibility to obtain energy
from biomass, due to its wide spread availability and potential
neutrality in relation to global warming [1]. In addition to wood and
other traditional forms of biomass, including energy crops [2,3] or
* Corresponding author.
E-mail addresses: andrea.chiodini@eni.com (A. Chiodini), letizia.bua@eni.com
(L. Bua), lino.carnelli@eni.com (L. Carnelli), r.zwart@dahlman.nl (R. Zwart),
vreugdenhil@ecn.nl (B. Vreugdenhil), marco.vocciante@gmail.com (M. Vocciante).
agricultural and forestry wastes, also Municipal Solid Waste (MSW)
(depending on their biogenic fraction) can be considered as a
resource. This possibility makes biomass, and residues in general,
the energy source with the highest potential to contribute to the
needs of modern society, as they are extremely versatile and can be
converted to different forms of energy (power, heat, mechanical
energy, fuels, chemicals) via biological, physical and thermal pro-
cesses in particular [4].
The potential saving in global CO2 emissions using alternative
fuels rather than traditional fossil fuels [5] makes biomass very
attractive, especially in the transportation sector. This is possible
mainly thanks to Franz Fischer and Hans Tropsch, who patented the
synthesis of linear hydrocarbons from a mixture of hydrogen and
carbon monoxide called synthetic gas or syngas [6]. This approach
has provided the opportunity to produce fuels from a variety of

http://dx.doi.org/10.1016/j.biombioe.2017.08.022
0961-9534/ 2017 Elsevier Ltd. All rights reserved.
 A. Chiodini et al. / Biomass and Bioenergy 106 (2017) 104e114
feedstock; for this reason, nowadays, the synthesis of hydrocarbons
through a Fischer-Tropsch (FT) approach is generally referred to as
XtL, where X denotes the fuel used as feedstock: C (coal) [7], G
(natural gas) [8], B (biomass) [9,10] or W (waste) [11]. However, the
conversion of coal, methane or biomass to liquid fuels and chem-
icals via a FT process requires producing syngas to feed the FT
section [12].
Gasication is the technique used to convert solid fuels (coal,
biomass, plastic or waste) into a gaseous fuel. It is achieved by
reacting the material at high temperature (>950 K), in presence of a
controlled amount of a gasication agent [13]. Unlike a combustion
process, where oxidation is substantially complete since the
oxidizing agent is added at least in stoichiometric amount with
respect to the fuel, in gasication processes the oxidant is sub-
stoichiometric and a part of the fuel chemical energy remains in
the ue gas in form of combustible gas. In gasication processes, it
is of little importance the biological composition of the fuel (e.g.
content of cellulose, hemicellulose and lignin, which is central for
biological processes like digestion and fermentation), whereas is of
primary importance knowing its chemical composition. For
example, the composition of the inorganic fraction (ash) is relevant,
since the melting of ashes is not desired and should be avoided. The
average chemical composition of a large number of fuels can be
found e.g. in Ref. [14].
Given the additional possibility to standardize its nal quality,
gasication makes the produced source even easier and more
versatile to use than the original biomass itself e.g. the gas could be
employed to power gas engines and gas turbines, or used as a
feedstock to produce liquid fuels or chemicals as methanol,
methane, ammonia, hydrogen [15].
In this work, as will be claried later, we sought to achieve a
double result: (1) to thoroughly investigate the potential of the
MILENA [16] gasier (a recent and very promising equipment
consisting of an indirect Circulating Fluidized Bed (CFB) gasier) in
comparison with a traditional Bubbling Fluidized Bed (BFB), and (2)
to optimize the operating conditions that allow high hydrogen
yields while limiting temperature and excess of steam, so that plant
simplication and the use of a wider biomasses variety are also
possible.
In our tests, we considered two different biomass types as
feedstock (forest residue and energy crops) and investigated
several congurations, changing operative conditions (temperature
and steam to biomass ratio) and bed material (olivine, sand, mag-
nesium oxide and Sorbacal).
In particular, obtaining a syngas with a high H2/CO ratio just
after the gasier e by stimulating the Water-gas shift (WGS) re-
action without a dedicated section e allows removing the WGS
section in a Biomass-to-Liquid (BtL) process, so that syngas needs
only to be softened (CO2 capture) before the Fischer-Tropsch pro-
cess. If considered alone, the latter possibility permits reducing
slightly both plant complexity and capital costs; however, when
applied to MILENA, further benets can be obtained, making the
gas treatment section downstream of the gasication process even
easier, and thus the production of biofuels denitely more
attractive.
2. Theory
2.1. Types of gasier
There are three main types of gasiers: entrained bed, xed or
moving bed, and uidized bed gasiers [17,18]. Entrained-ow
systems gasify pulverized fuel particles suspended in a stream of
oxygen (or air) and steam; their use for biomass gasication is
rather limited because they require the fuel particles to be very ne
105
(80e100 mm).
Fixed or moving bed gasiers have a simple design: the gasi-
cation medium is passed through a bed of solid fuel particles. They
are reliable and can be used to gasify very wet biomass economi-
cally on a small scale [18]. Depending upon the ow direction of the
gasifying medium, different congurations exist; the downdraft
gasiers are very popular [19]. However, both xed and moving bed
gasiers produce syngas with a large amount of by-products, due to
the low and non-uniform heat and mass transfer between the solid
biomass and the gasifying agent [20].
Finally, in the case of a uidized bed gasier, the fuel (1e3%) is
gasied in a hot bed of small particles made of inert or active ma-
terial uidized by a suitable gasication medium such as air or
steam. Since they can achieve a high and uniform heating rate, high
productivity [21], and higher efciency than other solutions [22],
they are progressively replacing xed bed gasiers [18]. Bubbling
Fluidized Bed (BFB) and Circulating Fluidized Bed (CFB) are the two
major types of uidized bed gasiers; further details and a thor-
ough comparison between them can be found in Ref. [18], yet one of
the main differences is related to the velocity of the gas passing
through the reactor (Ug) compared to the value of minimum
uidization (Umf). The latter, which depends on both the gas and
bed material, is a critical value dening the uidization regime of
the bed: below this value, the bed can be considered xed, while as
the uid speed increases, the bed acts as a liquid at boiling point
until it is dragged for even greater values.
In a BFB, the ratio between the real gas velocity and the Umf is
low (3e4) and extensive entrainment of bed material is thus
avoided. The gas creates bubbles within the bed, generating a
system similar to a liquid at boiling point. This is often combined
with a tapered design where the diameter increases downstream to
further reduce gas velocity and consequently reduce bed material
entrainment. On the contrary, a CFB is deliberately operated at a
velocity high enough (ratios even > 10) to entrain bed material and
a high throughput cyclone is generally needed to recycle the bed
material back to the gasication reactor.
The low gas velocities of a BFB make it relatively large, making it
as the preferred choice for smaller scale applications, whereas a CFB
is generally used for larger scale gasication plants. In any case, the
composition of the gas produced by these two technologies is
generally quite similar.
The indirect Circulating Fluidized Bed technology is a different
approach, which aims at separating the phases of char combustion
and biomass gasication to avoid mixing the ue gas with syngas,
resulting in a non-diluted syngas production with very low N2
content and thus high energy density [23,24]. An industrial appli-
cation of this concept can be found in BATTELLE [25]: two separate
CFBs e one acting as combustor and the other as gasier e are
employed to gasify the biomass indirectly, producing a medium
heating value gas. The circulation of solids between the two CFBs is
a major challenge of this technology [18].
An evolution of the above scheme is represented by MILENA
[16]: it employs a special kind of equipment consisting of two
coupled uidized bed reactors (one CFB and one BFB) within the
same apparatus, and the bed material is continuously recirculated
between them. This enables the above-mentioned physical sepa-
ration of the phases of pyrolysis/gasication (which in a standard
conguration takes place in the CFB located in the inner part of the
equipment) and combustion (occurring in the outermost BFB) and
avoids mixing the ue gas with the syngas. It also ensures the
complete combustion of any fuel that is not converted into syngas,
increasing the total efciency of the plant and minimizing puri-
cation, waste, safety, and energy problems.
106 A. Chiodini et al. / Biomass and Bioenergy 106 (2017) 104e114
2.2. Gasication agent
The gasication agent can be oxygen, air, steam [26], carbon
dioxide [27] or a mixture of them; in addition, an oxidant is
required to support the endothermic reaction of gasication,
partially burning feedstock and its by-products (char, tar and gas).
Among the possible alternatives, the use of air allows removing
the air separation unit (ASU), thus simplifying the process, while
pure oxygen produces syngas with a higher caloric value thanks to
the absence of any nitrogen dilution. Indirect gasication, by
separating the combustion from the gasication reaction, allows
joining the two aforementioned positive aspects by using air while
limiting dilution of the syngas with nitrogen [28].
The role of steam is to promote the gasication reactions,
increasing the gas production and the hydrogen concentration and
reducing the amount of by-products at the price of reducing the
overall efciency of the process due to the energy required to
produce it. Obviously, an excess of steam is not recommended as
the gain in terms of hydrogen yield and by-product removal is
progressively reduced.
2.3. Syngas
Hydrogen, carbon monoxide, carbon dioxide and methane, are
the main constituents of the gas phase produced by a gasication
process; other impurities, liquid (tar) and solid (char) by-products
(generally less than 1%) remain in suspension in the gaseous
stream and tend to settle in cold or low-speed spots. This syngas
can be used to generate heat and power [29], synthesize other
chemicals [30] and liquid fuels [31,32], or produce H2 [33]; obvi-
ously, depending on the case, undesired impurities have to be
removed. In particular, the applicability of a biomass gasication
technology strongly depends on syngas quality control technolo-
gies [34], since the syngas to be used in a Fischer-Tropsch synthesis
has to be free from impurities like tar, char, and catalyst poisons
(H2S, COS, thiophenes, etc.). Furthermore, the total amount of inert
gasses (CO2, N2 as well as CH4) is preferably low, in order to increase
the partial pressure of hydrogen and carbon monoxide, thus
reducing the volumetric ow and the operative pressure.
One of the most important parameter in Fischer-Tropsch syn-
thesis is the H2/CO ratio. Looking at the reaction [35]:
2n H2 n CO / CnH2n n H2O (1)
It is easy to see that the stoichiometric molar ratio between
hydrogen and carbon monoxide has to be near to 2: lower values
reduce the yield reaction and cause risk of carbon deposition while,
if hydrogen is in excess, methane and small-chain hydrocarbons
become the main products of the FT reaction.
Unfortunately, the syngas obtained through a biomass gasi-
cation has a quite low hydrogen yield: the composition and the
level of contamination depend on feedstock, reactor type and
operating parameters, but the obtained H2/CO ratio is generally
close to one or lower [17]. In addition, the Steam reforming reaction
(2), which generally strongly pushes the yield in hydrogen, ends up
affecting only marginally the nal syngas composition and the H2/
CO ratio, since methane is present only in small quantities (about
10% or less) in the reacting system.
CH4 H2O / CO 3 H2 (2)
To overcome the problem, the gas composition has to be
adjusted to have a H2/CO ratio closer to two by means of a Water-
gas shift reactor, where the following reaction (3) occurs:
CO H2O / CO2 H2 (3)
Another possible solution to increase the amount of hydrogen is
its production by water electrolysis, possibly using (excess) elec-
trical energy produced from renewable energies as solar or wind
[36]; however, this solution, which can be considered as a form of
power-to-fuels, is not very common.
2.4. Bed materials and catalysts
The quality of the gas required in a FT synthesis depends on the
catalyst used [37]; in general, iron and cobalt are widely exploited
[38] and comparative studies on the two catalysts in slurry phase
have been carried out [39].
While iron-based catalysts are less sensitive to this aspect, when
using cobalt-based catalysts, if the H2/CO syngas ratio from the
gasier is less than two, a Water-gas shift reactor is recommended,
in order to correct the ratio before FT synthesis; nevertheless, other
possibilities exist. Indeed, dolomite and olivine are two natural
compounds that have shown to possess a considerable catalytic
activity in the gasication process: using a combination of both
catalysts as bed material in a uidized bed gasier with a specic
conguration, a H2/CO ratio even higher than 2 has been observed
in the produced gas [40]. Devi et al. [41] discussed the olivine ac-
tivity as tar removal, showing that the catalytic activity increases if
the olivine is pre-calcinated at 1200 K for 10 h: under these con-
ditions, iron and silicon concentration on the mineral surface in-
creases at the expense of magnesium. On the other hand, other
studies have compared the activity of different types of olivine
showing that not all of them are active in gasication, and that an
active form is more predisposed to attrition and thus to bed losses
[42].
An interesting activity has also been observed by using an
alumina-supported nickel catalyst in a uidized bed reactor: nickel
is a good reforming catalyst and reduces the amount of tar,
methane and light hydrocarbons (mainly unsaturated) compared to
olivine and dolomite [43]. However, nickel-based catalysts in such a
conguration suffer serious problems related to the contamination
of the ashes by attrition of nickel [44].
3. Materials and methods
3.1. Biomass selection and characteristics
In order to widen the scope of the investigation, two biomass
fuels representing different categories of primary interest have
been selected as feedstock: softwood from forest residues (Lignocel
9) and fast growing crop (Triticale).
Lignocel 9 (supplied by JRS Group) comprises residues from
pine, spruce, conifer, etc.; it can be regarded as clean (low on ash)
and is gasied at normal conditions (gasication temperature
~1100 K). Regarding the second fuel, Triticale (supplied by Acciona/
CENER) was selected: this fuel contains problematic ash compo-
nents (Na, K), for which a lower gasication temperature (<1000 K)
has to be chosen. The properties of the two feedstock selected are
reported in Table 1, while details about the experimental procedure
and subsequent analysis are reported in Sections 3.4e3.7.
Looking at the macro elements (C, H and O), the composition of
the two feedstock looks quite similar, yet the ash content is seven
times higher than in Lignocel 9 and even the ash composition is
completely different (potassium and silicon are the main compo-
nents for Triticale while calcium is prevalent in Lignocel 9). Cor-
relations exist between the chemical composition and the initial
sintering melting point of ash [45], with the latter increasing with
calcium mass fraction and decreasing with potassium [46] and
 A. Chiodini et al. / Biomass and Bioenergy 106 (2017) 104e114
silicon content. This information has to be taken into account, since
if ash melts at gasication temperature, bed material particles start
to agglomerate and the bed de-uidizes.
3.2. Experimental facility
In the present study, a direct BFB and indirect (MILENA) gasiers
[16] have been selected for experimental tests (a conceptual
scheme is shown in Fig. 1 and details are reported in Table 2).
As anticipated, the direct gasier (Fig. 1a) consists of an atmo-
spheric Bubbling Fluidized Bed (BFB), in which gasication and
combustion reactions take place within the same reactor [47]. In
this case, the uidizing agent can be air, oxygen, steam or a mixture
of them depending on the quality of the produced gas, which is set
by downstream processes. For this work, an oxygen/steam mixture
was used as the uidizing agent. The bed material, which in normal
operating mode is sand or olivine, is heated at 1100e1200 K
through the partial combustion of the biomass. The reaction gen-
erates the heat required for the endothermic gasication reactions
that convert the residual biomass particles into gas, tar and char.
The gas produced within the gasier increases the gas ow in the
reactor and consequently the vertical velocity, which has to be kept
low in order to guarantee the bubbling effect and reduce bed par-
ticles entrainment.
In regards to the indirect gasier, pyrolysis/gasication and
combustion reactions take place in two separate zones; a schematic
layout of the technology in its standard conguration, using an
internal Circulating Fluidized Bed gasier, is given in Fig. 1b. The
gasication section that forms the internal Circulating Fluidized
Bed consists of three parts: a riser (1), a settling chamber (2) and a
down comer (3). The combustion section also contains three parts,
namely a bubbling uidized bed (4), a freeboard (5) and a sand
transport zone (6).
Considering the standard conguration used in the present
experimental campaign, in the gasication section biomass is fed
into the riser while a small amount of steam or other carrier gas is
added from below. When hot bed material enters into the riser,
biomass is heated up and converted into gas, tar and char (endo-
thermic reaction). The gas production creates turbulence and
carries over the bed material and degasied biomass particle (char).
After the gasier, the gas is sent to the cooling and cleaning section:
the gas velocity decreases within the settling chamber, while the
larger solids fall down into the down comer from which they are
transferred back to the bubbling uidized bed. Here, char and tar
are burned with air (exothermic reactions) to heat the bed material.
Flue gas leaves the reactor to be cooled, de-dusted and emitted. The
heated bed material leaves the bottom of the combustor through an
exit into the riser.
Table 1
Elemental analysis of biomass selected as feedstock. Note: a.r. as received (all moisture counted); d.a.f. on dry and ash free basis.
Biomass
Bulk density kg m3
Particle size mm
LHV MJ kg1 (a.r.)
Ash %dry
Water % 11.0
Carbon (C) % d.a.f.
Hydrogen (H) % d.a.f.
Oxygen (O) % d.a.f.
Sodium (Na) ppm
Potassium (K) ppm
Calcium (Ca) ppm
Magnesium (Mg) ppm
Silicon (Si) ppm
107
In the inversed conguration [48], gasication takes place in the
bubbling uidized bed and combustion occurs in the riser. As
explained below, this conguration can be an attractive approach
because in this way the contact time between gas and bed material
in the gasication zone can be regulated by the ow of the carrier
used.
3.3. Gasier bed material selection
The experimental campaign has been conducted with different
bed materials (Table 3). At the beginning, silica-based bed materials
have been employed, namely sand and Austrian olivine: while sand
does not have any catalytic activity, olivine contains 9% of iron
oxide, a Water-gas shift catalyst. Subsequently, in order to increase
the H2/CO ratio, hydrated lime (Ca(OH)2 converted to CaO at gasi-
cation temperature) has been added to the olivine bed material; in
addition, also magnesium oxide (MgO) has been tested as bed
material. All the beds were prepared to get a granulometry be-
tween 250 and 320 mm (Group B of the Geldart classication [49]).
3.4. Operating conditions
The operating conditions for the different gasication tests are
reported in Table 4. In both gasiers, measurements are completely
automated: several thermocouples (type k) detect the temperature
at different locations and, in particular, the thermocouple located in
the settling chamber of the indirect gasier has been taken as a
general reference for the gas outlet temperature. Heat loss from the
process is compensated by high temperature electrical trace heat-
ing and external insulation. The pressure measurements are made
through PTX 1400 pressure transmitters.
3.5. Analysis procedure
A certied ECN laboratory was instructed to carry out all the
analyses needed to perform this study. The properties of the two
selected biomass feedstock (Table 1) were obtained through a
proximate and ultimate analysis, whereas the bed compositions
(Table 3) were analyzed through ICP analysis. The analytical
methods applied for the analysis of biomass and bed materials are
summarized in Table 5.
Specic gas analyzers (ABB Uras14NDIR, ABB Magnos16, ABB
Caldos17, ABB Limas11, Maihak Paramagnetic sensor, and Ratsch
FID analyzer) continuously monitored the concentration of
hydrogen, carbon monoxide, carbon dioxide and methane in the
produced syngas, and the concentration of CO2, O2 and other con-
taminants in the ue gas. Complementary, a micro gas chromato-
graph (Varian, CP4900 microGC) allowed online measurement of
Lignocel 9 Triticale
175 100
800e1100 900e1100
16.3 16.9
0.6 4.2
<0.1
50.3 47.0
6.4 6.4
43.0 44.2
71 2497
388 10913
1397 3978
354 1528
193 5075
108 A. Chiodini et al. / Biomass and Bioenergy 106 (2017) 104e114

Fig. 1. (a) Direct gasier with bubbling uidized bed, BFB; (b) indirect MILENA gasier [16] with circulating uidized bed, CFB.

Table 2 sensors (online gas analyzers supplied by ABB, Uras14 and Caldos17
Main geometrical and operational parameters of the gasiers employed. above all) continuously detected its composition. Data obtained
Gasier Direct BFB Indirect CFB were normalized on the sole basis of its main components, i.e.
hydrogen, carbon monoxide, carbon dioxide and methane content;
Section 1e2 3 Riser Combustor
Height [mm] 500 600 925 1600 low hydrocarbon, steam, nitrogen, helium and other impurities
Internal Diameter [mm] 74 108 36 250 were not taken into account.
Thermal Input [kWh] 5 30
Productivity [Nm3 h1] 1.2 8
3.7. Test procedure, indirect gasication

Approximately 40 kg of bed material were charged in the

Table 3
gasier, which was then heated up to the set temperature. Biomass
Chemical composition of the bed materials selected (in wt. %).
was introduced with a calibrated feeding screw operating at con-
Bed Material Sand Austrian Olivine MgO Sorbacal calcined stant rate, while argon was used as tracer gas for the determination
SiO2 100% 46.9% e <2% of the gas ow. As anticipated, the composition of syngas and ue
MgO e 42.9% 100% <3% gas was online monitored throughout the experiments with gas
Fe2O3 e 9% e e
analyzers and micro-GC; SPA samples were taken under stable
CaO e 0.3% e >95%
conditions.

Table 4
4. Results and discussion
Operating conditions used in the experimental campaign.
4.1. Experimental campaign with silica based bed materials
Reactor Direct BFB Indirect CFB

Biomass ow rate [kg h1] 0.4e0.6
Pressure [kPa] 101.3
Bed temperature [K] 1020e1170
Steam/biomass weight ratio (S/B) 0.5e0.78
the produced gas (CO, CO2, N2, O2/Ar, CH4, C2H6, C2H4, C2H2, ben-
zene, toluene, H2S and COS). The content and composition of tars
has been measured using the SPA method [50,51].
3.6. Test procedure, direct gasication
For each experiment, about 1 kg of bed material was charged in
the gasier and the reactor was heated to a temperature of c.a. 50 K
lower than the desired gasication temperature before starting the
feeding. Biomass was introduced with a feeding screw operating at
constant rate; for each biomass type, the screw was preliminarily
calibrated to measure the correct biomass ow rate.
Once steady state was achieved, tar (SPA) and moisture samples
were taken. During experiments, a known ow rate of argon was
introduced into the gasier together with the gasication agent to
calculate the ow rate of the produced gas, whereas specic
3.2e4.8 A rst experimental campaign (Table 6) was aimed at investi-
101.3
gating the chemical composition of the gas produced by the two
970e1170
0.2e0.68 selected gasiers when operated at various conditions and
exploring two different bed materials based on silica (sand and
olivine).
Lignocel 9 could be processed without particular problems with
both gasiers and under all the conditions explored: in particular, a
temperature up to 1170 K was investigated while varying the steam
to biomass weight ratio between 0.2 and 0.8. Data of gas compo-
sition obtained from this biomass are shown in Fig. 2.
With the direct BFB (tests 1 to 4), carbon monoxide and carbon
dioxide values were similar or higher than hydrogen while
methane was quite stable and varied from 8 to 10 vol%. It is easy to
see that increasing the temperature and/or the steam-to-biomass
ratio, the produced gas is richer in hydrogen and poorer in car-
bon monoxide (thus proving a larger extent of the WGS reaction),
while carbon dioxide and methane quantities remain quite stable.
On the one hand, this conrms what was anticipated: it is not
necessary to increase the amount of steam employed beyond a
certain point as the efciency of the methane conversion is reduced
considerably by increasing the S/B ratio. On the other hand, the
stability of CO2, which should instead increase because of the WGS
 A. Chiodini et al. / Biomass and Bioenergy 106 (2017) 104e114 109

Table 5
Analytical methods applied for the characterization of biomass and bed materials.

Property Method Special equipment

Moisture content NEN-EN-ISO 18134-3 e

Ash content NEN-EN-ISO 18122 e
Volatile matter NEN-EN-ISO 18123 e
Caloric value NEN-ISO 1928, NEN-EN 14918 PARR 6300 calorimeter
CHN content NEN-EN-ISO 16948 Thermo Scientic Flash 2000 element analyzer
Minor- end major elements NEN 6966, NEN 6963 Thermo Scientic ICP-OES ICAP 6300 duo

Table 6
Experimental campaign with silica-based bed materials.

Biomass Lignocel 9 Triticale

Reactor Direct BFB Indirect CFB Direct BFB Indirect CFB

Bed material Sand Olivine Sand Olivine

Test 1 2 3 4 5 6 7 8 9 10 11 12
Biomass ow rate [kg h1] 0.41 0.55 0.41 0.41 4 3.7 3.7 5 0.6 4.8 3.2 3.2
Steam ow rate [kg h1] 0.24 0.3 0.24 0.32 2 2.2 2.2 1 0.36 2 2.2 2.2
Gas velocity Ug [m s1] 0.10 0.12 0.10 0.13 3.30 3.63 3.63 1.65 0.15 3.30 3.63 3.63
S/B (w/w) 0.59 0.55 0.59 0.78 0.5 0.6 0.6 0.2 0.6 0.42 0.68 0.68
Ug/Umf 2.94 3.68 2.94 3.93 51.2 56.4 56.4 25.6 4.42 51.2 56.4 56.4
Temperature [K] 1070 1120 1170 1170 1010 1120 1170 1170 1050 970 990 1010

reaction, is probably linked to the presence of secondary reactions
to which it takes part as a reagent, thus contributing, with its
sequestration, to enhancing further the yield in hydrogen.
Similar results were obtained with the indirect CFB (tests 5 to 8),
where an increase of the temperature led to a general gain in H2
content; however, a reduction in the steam to biomass ratio may
penalize the H2/CO ratio even at high temperature.
On the contrary, due to its high concentration of alkaline metals,
Triticale conrmed to be a difcult feedstock to gasify, since it has a
great tendency to agglomeration and hence de-uidization of the
bed at the applied gasication temperature. Data of producer gas
composition are shown in Fig. 3.
With the direct BFB gasier, only one test was conducted at
1050 K (test 9) though after few minutes the bed de-uidized and
the test was stopped. With the indirect CFB gasier (tests 10 to 12),
the maximum temperature analyzed without agglomeration was
ca. 1010 K. The resulting gas compositions did not change signi-
cantly and remained in line with data observed with Lignocel 9.
Fig. 4 summarizes the H2/CO ratios achieved in all the tests
performed by employing a bed material based on silica (sand and
olivine). Using these congurations, the maximum hydrogen/car-
bon monoxide molar ratio (1.5) was obtained with the direct BFB
reactor at high temperature (1170 K) and high S/B ratio (0.78) (test
4).
Up to this point, the use of an indirect CFB operated with a
standard conguration (with gasication taking place in the riser)
has always resulted in a maximum H2/CO ratio lower than unity,
under all the conditions investigated. In particular, the best result
accomplished with the indirect gasier, i.e. a hydrogen/carbon
monoxide ratio of 0.9 (test 7), was obtained at high temperature

Fig. 2. Composition (% vol., dry basis) of the syngas obtained from Lignocel 9 feedstock by using silica-based bed materials.
110 A. Chiodini et al. / Biomass and Bioenergy 106 (2017) 104e114
(1170 K) and high steam-to-biomass ratio; however, this outcome is
lower than the maximum value detected for the direct gasier
under similar conditions. This different result is probably due to the
very short contact time within the riser (a few tenth of seconds),
which does not allow reaching a thermodynamic equilibrium, with
a higher hydrogen content.
As a major consequence, the indirect gasier is less sensitive to
the operating conditions under which gasication is conducted: on
one hand, pushing the process on high temperature values does not
get the same gain seen in the BFB; conversely, the H2/CO ratios
observed with MILENA are generally more constant, resulting in
better quality of the produced syngas also under weak gasica-
tion conditions. This is evident by comparing the results obtained in
tests 9 and 10, despite the temperature and S/B values used with
the indirect gasier were signicantly lower.
In any case, for our purposes, even best conditions like those of
test 4 and 7 are in general quite useless in real applications, because
they are not economically viable and/or not applicable for biomass
with high alkaline metals content like those found in energy crops,
since ashes melt below the reaction temperature, thus generating a
eutectic with the bed material and a consequent de-uidization.
Even pushing the conversion of residual methane (about 10%)
through the use of a dedicated reformer would have not led to any
appreciable gain in hydrogen yield.
Therefore, specic strategies are required to improve the H2/CO
ratio, like the addition of a catalyst within the bed material, the use
of an active bed material or suitable changes in the gasier
conguration (i.e. an inverse conguration).
4.2. New experimental campaign with additive and active bed
materials
Table 7 reports the conguration investigated with Sorbacal
used as additive in olivine bed and magnesium oxide as active bed
material. As anticipated, one of the objectives of the work was to
conduct a gasication with high yields of hydrogen even at not very
severe operating conditions, both in terms of temperature and S/B.
Accordingly, this new test series was focused on operating condi-
tions weaker than those explored in the previous tests; obtained
Fig. 3. Composition (% vol., dry basis) of the syngas obtained from Triticale feedstock by using silica-based bed materials.
data are shown in Fig. 5.
In these new tests with the direct BFB gasier, hydrogen and
carbon dioxide were the main components of the produced gas,
contributing for about 30% vol. or more (in previous tests, the
amount of H2 was generally lower, in some cases being only 15% of
the total volume of the gas); CO was less than 20% vol., whereas
methane remained stable at 9% vol. These results were obtained by
using either Lignocel 9 or Triticale as feedstock.
By using an internal CFB gasier (test 15), the produced syngas
resulted to be enriched in hydrogen and carbon dioxide, yet carbon
monoxide remained the main component, as it was observed also
from tests with olivine.
The ratio between H2 and CO, for the different tests under dis-
cussion, is shown in Fig. 6. With the indirect CFB reactor, and
working under similar conditions, the simple addition of a 10% wt.
of Sorbacal to the olivine led to an increase of the H2/CO ratio from
<0.4 to 0.7 (comparison should be made between test 15 in Fig. 6
and test 5 in Fig. 4), but the result remained still far from the
desired values. Looking at the results obtained with the direct BFB,
signicant improvements were found with respect to the use of the
inert bed, the H2/CO ratio being more than doubled (test 13 vs. test
1) while working at a lower temperature (1020 K instead of 1070 K).
Actually, by working at the same temperature (test 14), it was
possible to obtain a H2/CO ratio more than ve times higher, which
resulted to be greater than the value obtained by executing the
gasier under temperature and S/B conditions much more
burdensome (test 4).
Additional tests (nn. 16 and 17), realized by using an active bed
of magnesium oxide (MgO was not just an additive), provided the
best outcomes: hydrogen was always higher than 30% vol., whereas
carbon monoxide was less than 20% vol. even at low temperature.
This resulted in a H2/CO ratio of 2 (i.e., a value higher than test 14)
but with a temperature 50 K lower (test 16), and inert gases (carbon
dioxide and methane) were less than 50% in total. These conditions
are suitable for a wide variety of feedstock as energy crop. In
addition, by slightly increasing the temperature, this conguration
allowed reaching a H2/CO ratio even higher than 2, while still
working at temperatures below 1100 K.
Conversely, the experimentation with the MILENA gasier was
 A. Chiodini et al. / Biomass and Bioenergy 106 (2017) 104e114 111

Fig. 4. H2/CO ratio (w/w) of the syngas obtained by using silica-based bed materials.

Table 7
New experimental campaign with either an additive (Sorbacal) or an active bed material (MgO).

Biomass Lignocel 9 Triticale

Reactor Direct BFB Indirect CFB Direct BFB

Bed material Olivine 90% Sorbacal 10% Olivine 90% Sorbacal 10% MgO

Test 13 14 15 16 17
Biomass ow rate [kg h1] 0.4 0.4 4 0.6 0.6
Steam ow rate [kg h1] 0.24 0.24 2 0.36 0.36
Gas velocity Ug [m s1] 0.10 0.10 3.30 0.15 0.15
S/B (w/w) 0.6 0.6 0.5 0.6 0.6
Ug/Umf 1.89 1.89 56.3 6.04 6.04
Temperature [K] 1020 1070 1030 1020 1050

Fig. 5. Composition (% vol., dry basis) of the syngas obtained by using either an additive (Sorbacal) or an active bed material (MgO).
112 A. Chiodini et al. / Biomass and Bioenergy 106 (2017) 104e114
Fig. 6. H2/CO ratio (w/w) of the syngas obtained by using either an additive (Sorba-
cal) or an active bed material (MgO).
suspended without further testing. In fact, although it would have
been of interest to evaluate the performance of this indirect gasier
with an active bed of MgO, it was readily clear that, because of the
structure of the gasier itself, the benets arising from the use of a
catalytic bed would have been lower due to the reduced contact
time.
4.3. Considerations about applicability to real BtL processes
The above-discussed results have shown that it is possible to
carry out a biomass gasication and to obtain H2/CO ratios of more
than 2 by working under mild conditions, provided proper ad-
justments of the operating conditions are made, together with the
use of an active bed. This result is inherently interesting, as it has at
least two immediate effects: on the one hand, it is possible to use
biomasses that require weak gasication conditions, due to the
composition of their ashes; on the other hand, the WGS section can
be avoided, resulting in a simplication of the process and eco-
nomic advantages. However, it is worth observing that this latter
plant modication does not involve great savings, as the WGS
section generally has a marginal weight in the BtL process (1e5%
depending on the plant complexity) [12].
Currently, the fact that MILENA [16] does not require an air
separation unit (ASU) represents a great economic advantage
(around 10e15% of the overall process [52]) that also allows simpler
installations. A proper setup should make it possible to increase
further the benets by also eliminating the WGS section, making
the gas treatment section related with the gasication process even
less expensive; overall, the BtL process would be simpler and more
attractive. Unfortunately, the use of the MILENA gasier operating
in its standard conguration (i.e., with gasication occurring in the
internal CFB) did not allow achieving the expected results even by
using a high temperature and/or a high steam to biomass ratio. In
all the tests performed with this equipment, the H2/CO ratio
remained below the unity; even by employing an additive like
Sorbacal (10%), the performances increased only slightly.
An inversed MILENA conguration [48], with the gasication
taking place in the external BFB, could represent an interesting
approach that allows the possibility of changing the residence time
in the gasication zone, thus making it possible to adjust the H2/CO
in a way similar to that of a direct BFB gasier.
5. Conclusions
In the present work, an experimental study on biomass gasi-
cation has been set up with the aim of investigating the possibility
to obtain a syngas with a higher H2/CO ratio. The latter would then
be suitable for a subsequent FT synthesis, thus removing the need
for a dedicated Water-gas shift section in BtL processes and
consequently reducing costs while making the biofuels production
more attractive.
The biomass gasication tests conrmed the potentiality of
obtaining a H2/CO molar ratio of 2 directly in the gasier, yet this
result was effectively achieved with only one of the tested equip-
ment. In particular, the structure of the direct BFB gasier, which
ensures sufcient residence times, makes it very dependent on the
operative conditions (mainly temperature and steam) and allows
tuning up the process. The best result obtained with an inert bed
material (Lignocel 9 mixed with sand) was an H2/CO ratio of 1.5 at
1170 K. However, this temperature condition is not feasible when
the feedstock ashes have a low melting point, like those deriving
from energy crops; moreover, the syngas composition obtained is
in any case not suitable for a direct FT synthesis.
The choice of catalytically active bed materials allows obtaining
a dual result: an increase of the H2/CO ratio and a reduction of the
gasication temperature. By simply adding a 10% wt. of calcium
hydrate (Sorbacal) to olivine, the H2/CO ratio rises up to 1.9 at
1070 K.
Instead, by using a bed material completely constituted of active
material, like magnesium oxide, it has been possible to reach the
same H2/CO ratio at a temperature even lower (1020 K), thus
allowing the use of energy crops as feedstock; moreover, H2/CO
ratios exceeding 2 were obtainable at slightly higher temperatures.
Under these conditions, the produced syngas could be directly used
in FT synthesis without requiring a Water-gas shift section within
the BtL process, thus resulting in a saving that in some cases
amounts to up to 10% of the production costs [53]. In addition, the
excess methane may be recycled in the gasier or used for energy
production.
However, the removal of the dedicated WGS section results in
limited gain in the case of a direct gasier, while it would be
certainly more interesting in the case of an indirect gasier. In fact,
in this latter case, the mentioned simplication would add to the
removal of the ASU, which also represents an important cost e up
to 15% in a BtL plant with direct gasier [51] e and is not required in
this type of gasiers.
Unfortunately, the MILENA standard conguration tested did
not allow achieving the expected results: even using a high tem-
perature (1170 K) and a high steam-to-biomass ratio, the best result
was a H2/CO ratio of only 0.9. In all the tests carried out with this
equipment, the H2/CO ratio remained below the unity: this is due to
the intrinsic structure of MILENA, and to the short residence times
within the gasication zone in particular, which make this gasier
less sensitive to variations in operating conditions and/or catalytic
activity of the bed.
An inversed MILENA conguration [48], with the gasication
taking place in the external BFB, could be an interesting solution for
the production of syngas with a H2/CO ratio of 2. Since a similar
conguration would offer the possibility of changing the residence
time in the gasication zone, this would make it possible to adjust
the H2/CO in a way similar to that of a direct BFB gasier, thus
allowing the obtainment of values near two also with this gasier.
The possibility to avoid not only the ASU section, but also the
WGS in a BtL process operated with this approach is even more
attractive. However, since MILENA is a fairly recent equipment,
 A. Chiodini et al. / Biomass and Bioenergy 106 (2017) 104e114
further investigation regarding the real performance of such a
conguration is needed (for example, the presence of tar can be a
problem, especially within the cold sections of the plant, that has to
be addressed by using a reformer or a proper abatement system
[54]). Moreover, as soon as similar syngas compositions are ob-
tained, a complete technical and economical comparison of BtL
processes performed with this and other gasiers needs to be
conducted (see e.g. Ref. [53]), since other important aspects have to
be taken into account in order to actualize the process. Finally, an
LCA-based investigation [55] would also be appropriate: given that
it includes aspects of environmental sustainability, it might allow
highlighting issues often unexpected in a given process (see
Ref. [56]), thus representing an increasingly important tool for the
optimization of processes and design.
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