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Fluidized bed gasification of biomass from PABR: Assessment of the effect of

different catalytic bed material on the syngas metal content, lab-scale test

E. Paris1,4, F. Gallucci1, V. Ancona2, A. Palma1, B. Vincenti1, M. Carnevale1, M.V. Migliarese Caputi3, V. Belli4
Gabriele Gagliardi3 and D. Borello*3
1 CREA Centro di ricerca per l'Ingegneria e Trasformazioni agroalimentari, Monterotondo - Rome, Italy
2 CNR-IRSA Istituto di Ricerca Sulle Acque del Consiglio Nazionale delle Ricerche, Bari, Italy
3 DIMA Dipartimento di Ingegneria Meccanica e Aerospaziale, Università La Sapienza, Roma, Italy
4 DIAEE Dipartimento Ingegneria Astronautica, Elettrica e Energetica, Università La Sapienza, Roma, Italy

*Corresponding author: domenico.borello@uniroma1.it

ABSTRACT
PABR (Plant-Assisted BioRemediation) is an excellent green strategy for the recovery of contaminated soils.
A possible route for set up a circular approach for the valorisation of PABR biomass consists in gasification,
producing valuable Syngas while sequestering hazardous materials disposed in biomass. Here, materials
commonly used in Fluidized Bed Gasifier (FBG) reactors were compared during the gasification of PABR
biomass (Arundo Donax, rich in metals). The tested materials were Olivine, K-Feldspar, Limestone, Kaolinite
and Quartz Sand. The gasification process was carried out in lab-scales on a TGA-DTA (Thermogravimetric
Analysis - Differential Thermal Analysis) interfaced with a bubbler system for sampling the heavy metals
generated in emission. To assess the occurrence of metal release from bed materials, the tests were done
both on single materials and on material + PABR biomass mixtures. The products obtained from the
simulation in TGA-DTA were also analysed at SEM-EDS to characterize the surface composition of the tested
materials. The comparison of the obtained data showed that K-Feldspar and Limestone represent the most
appropriate materials, even if the second one undergoes a weight loss of over 60% at the considered
operating temperatures. The work also represents a useful assessment of new bed materials for FBG, to be
employed in pilot and real scale applications.

INTRODUCTION
Plant-assisted bioremediation (PABR) is a green strategy to recovery contaminated areas. Plant growth allows
to promote the transformation of soil contaminants in less toxic compounds and therefore, remediate soil
from pollution [1]. The pruning of such plants is generally considered contaminated products and therefore
their disposal requires attention. Numerous studies showed that the use of plants from PABR and their
pruning is compatible with biomass energy conversion systems such as pyrogasifiers [2-5]. In previous works
we considered pruning as an energy resource, in terms of composition and emissions [4,5]. Pruning can be
in gasification processes and the syngas produced is comparable to that generated by traditional biomass.
Most of the metal contaminants remain confined in the ashes inside the fluidized bed (Bottom Ash) or in the
ashes collected by the cyclone (Flying ash). The possibility of using a waste product from a soil remediation
process represents an important energy resource for a technical-scientific community that is increasingly
attentive to the circularity and sustainability issues. Among the various available solutions, Fluidized Bed
Gasifier (FBG) shows various advantages if it is compared with fixed bed gasifiers: better temperature
distribution, quicker ignition, excellent heat transfer. A FBG reactor contains an inert granular solid in the
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bed, acting as heat carrier and mixer. The semi-suspended state of the bed particles is achieved by the
passage of the fluids operating as gasification agents, the carrier gas enters from the bottom of the bed to
create the state of fluidization [6]. The biomass is injected from the top and mixes rapidly in the chamber,
being dried and then reacting with gasifier agents. The FBG reactor allows excellent gas-solid mixing, and the
large thermal inertia of the bed makes this type of gasifier unable to use a wide range of biomass [7]. On the
other hand, FBGs require a grinding of biomass and it is necessary that the bed temperature is kept below
900°C to avoid ash fusion and consequent agglomeration [8]. In FBGs the characteristic transfer of heat and
matter occurs thanks to the bubbles and their high surface permeability. [9]. The type of process and the
physical interaction between the bed and the biomass suggests that the chemical inertia of the bed material
needs to be carefully evaluated. In fact, a proper bed material gives the reactor benefits in terms of fuel
mixing, heat and mass transfer and high heat capacity allowing the reactor to maintain isothermal behaviour
and excellent temperature control capabilities. Furthermore, through a careful choice of catalytically active
materials, the bed can also be used to optimize the gasification process. In this way it is possible to increase
the quality of the gas produced by facilitating the conversion of biomass, guaranteeing limited contents of
tar, sulphur, and alkali in the gas. In previously studies [5, 10], high values of some metals, such as Fe and
Mg, were observed in syngas. Olivine (a mineral rich in these metals) was used as a material for the bed. The
main properties that distinguish the minerals used for FBG beds are resistance to mechanical degradation
and low economic value. However, it is also essential to conduct a research to evaluate its resistance to
thermal and chemical degradation, above all because, although they do not act directly on the production of
syngas, they can alter its quality. In [4,5], olivine was used as bed material and it has been seen that is not
completely inert, as at the end of the gasification process olivine showed a decrease in concentration for
some metals such as Fe, Mg, Al. This indicates that the olivine itself was a source of metals present in the
syngas. To clarify such issue, here various materials commonly used [6, 11-16] as materials for FBG beds have
been tested, such as Olivine, K-Feldspar, Kaolinite, Quartz Sand and Limestone. These materials were
subjected to heat treatments in TGA-DTA to simulate the gasification process without biomass. In fact, as
already demonstrated [10], the use of a TGA-DTA system interfaced with a thermostatic bubbling system,
represents an excellent lab scale approximation for the evaluation of the emissions generated by an FBG
gasification system. Eventually we carried out the tests also in the presence of PABR biomass, due to the
interest in combining an investigation about a chemical-physical criticality of the bed materials with an
important agroforestry residue of enormous interest for environmental sustainability and circular economy.
The analysis were carried out in lab by using the well-established TGA-DTA analysis complemented by SEM
measurements. The TGA-DTA allows to study the behaviour of materials in function of the temperature
increase. Specifically, as the T increases, in a controlled atmosphere with dry air (combustion) or N2
(pyrolysis) as carrier gas, the weight and heat exchange variations of the sample are recorded. Several studies
use the TGA-DTA as a predictive model to evaluate the behaviour of materials or fuels in the gasifier. The
innovative technique of sampling the emissions generated by the TGA-DTA during the analysis proposed in a
previous work [10] is applied here. Furthermore, SEM interfaced with the EDS detector is used to highlight
the interactions between electron beam and sample. Depending on the nature, energy and wavelength
interactions allow to obtain information useful for the analysis of the sample, making a surface mapping of
the constituent elements.

MATERIALS AND METHODS

The laboratory tests were conducted at the LASER-B (Laboratory for Experimental Renewable Energies -
Biomass) of CREA-IT (Council for agricultural research and analysis of agricultural economy – dept.
engineering and agri-food transformations). A TGA-DTA thermogravimetric scale (TGA / DSC 1 STARe System
- Mettler Toledo) was interfaced with a chiller (SC6 Dado Lab) containing 3 bubblers with a solution for
sampling the emitted metals (3.25% v / v of HNO3 and 1.5% v / v of H2O2) kept at 5±1 °C (Fig.1). This system
was set-up by using UNI EN 14385 for the sampling of heavy metals generated by stationary source emissions.
Sample collection was conducted with three bubblers containing 100ml of solution, where the first two were
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actual sampling, while the last one was considered as backup bubbler. Only the samples where the
percentage of compounds occurring in the backup bubbler did not exceed 10% of the sum of the other two
were considered relevant. This instrumental apparatus allows to simulate the conditions of a gasifier and to
collect the emissions generated through the bubbling. In a previous work [10] the excellent approximation
was demonstrated by comparing the emissions produced by the biomass in TGA-DTA and the quality of the
syngas produced by FBG. The results are shown in Fig. 2.

Figure 1:The instrumental apparatus for sampling metals layout (left) and real (right)

Figure 2: Comparison of the trends of metals in syngas obtained with the predictive instrumental apparatus and with the FBG. [10]

Five materials commonly used in FBG beds were considered and tested: Olivine, K-Feldspar, Kaolinite, Quartz
Sand and Limestone. Small quantities (about 10 mg) of the materials were sampled into the instrumental
apparatus TGA / DTA-Bubblers with a temperature ramp of 90 ° C / min from room temperature to 850 ° C
and a flow of carrier gas (N2) of 30ml / min. The final temperature was maintained for 30 min. Subsequently,
the same tests were carried out with the tested materials + arundo donax PABR biomass. These operating
conditions are representative of the pyrolysis process, i.e.: the release of volatile matters from the biomass
due to thermochemical reaction. The bubblers containing the emissions produced were analysed in ICP-MS
(Agilent 7700). Bed materials and biomass were mineralized with a microwave oven (Start D, Milestone) and
characterized in terms of metal concentration in ICP-MS. A SEM-EDS (Zeiss EVO MA 10 + EDS Bruker Quantax
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200) analysis also allowed to observe the morphology and characterize the composition of the materials
surface, before and after the gasification process. In this study Arundo Donax, coming from a contaminated
(PCB,Heavy Metals) area close to Brescia (Italy), was choose as PABR biomass. The biomass was provided by
ENI Rewind, responsible of the site decontamination.

The study discusses the comparison between the materials before and after the TGA-DTA treatment and the
differences between the material with and without biomass. The sample after the simulation in TGA-DTA
was positioned on a stab and analysed by SEM-EDS. The scanning was carried out at a distance of about 10
mm, using an acceleration voltage of 20 keV. This type of analysis provides an image of the analysed material,
and a mapping of the surface. The different colours represent the response of the elements. We report a
table with the elements found, only considering the normalized percentage mass.

RESULTS
The analysis focused on the examination of the bed materials and their heavy metals emissions generated at
the operating conditions, by considering such materials alone as well as interacting with PABR biomass. In all
tests a 3:1 bed material/biomass weight ratio was maintained. The SEM-EDS measurements were
subsequently carried out and the potential in using these materials was explored. In TGA, the ash
agglomeration process is accentuated as it operates in fixed bed conditions (without fluidization). The
agglomeration of fine carbonaceous powders is an action occurring superficially, so it is possible to evaluate
its by means of SEM spectroscopy. For this reason, it can be concluded that the mineral particles, after
biomass gasification, with a high percentage of surface carbon are more affected by the effects of
agglomeration. Therefore, they can be harmful and reduce plant efficiency affecting fluidization
effectiveness.

Biomass

The results of the chemical-physical characterization of the Arundo Donax PABR are shown in the Table 1. It
is observed that the PABR biomass obviously does not have large variations compared to the data present in
the literature (eg. [17,18]) referring to traditional biomass.
Table 1: Chemical-physical characterization of the Arundo Donax PABR

Moisture (%) Ash (%) C (%) H (%) N (%) HHV (MJ/kg) LHV (MJ/kg)
Arundo Donax 11,61 4,83 45,65 7,81 0,52 18,49 16,88

The mineralization and subsequent analysis in ICP-MS allowed to determine the concentrations of metals in
the biomass. The results are shown in Table 2:
Table 2: Heavy metals concentration in Arundo Donax PABR

Metal mg/kg Metal mg/kg

Al 3,950 Zn 4,987
Cr 0,168 Ag 0,001
Mn 3,303 Cd 0,009
Fe 20,802 Ba 0,942
Co 0,013 Tl <LoQ
Ni 0,180 Pb 0,053
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Cu 0,625 Bi 0,003

Several TGA-DTA tests were performed with different initial weights and the response in weight loss was
always between 95 ÷ 99%. The graph representing the evolution of biomass in TGA-DTA is shown in Figure 3.
Observing the trend of the weight variation curve, it is easy to notice several phenomena: at about 100 ° C
the water evaporates, between 270 ° C and 600 ° C there is a rapid weight reduction due to pyrolysis and, in
the successive phase, the release of volatiles compounds. The remaining solids consist in ashes and char. As
for the heat flow curve, the peak occurs roughly when the solid fraction is almost completely turned into ash,
or when it can no longer release heat to the system, for a value of 410 mW. The curve becomes stable only
when the energy ramp is finished, where the system acquires about 84 J.

Figure 3: Thermogravimetric and differential analysis of the arundo donax PABR

For completeness, it has also been conducted a SEM-EDS analysis, which results are shown in Figure 5.

Comparison of metals generated in emission.

To evaluate the most suitable bed material for obtaining a syngas with the minimum contamination from the
bed, a comparative analysis by using different materials was carried out. Preliminarily, we analysed the heavy
metals emissions under severe thermal stress. The heavy metals emitted expressed in mg per kg of matrix
(ppm) are shown in Figure 5. By analysing the summations of the concentrations measured by the ICP-MS,
materials subjected to high thermal stresses emit different amounts of heavy metals. We can argue that the
more the material has impurities, the heavier metals it emits during the TGA-DTA process. This circumstance
will be further examined in following sections. In fact, the quartz sand having no ferrous impurities, emits
fewer heavy metals than all the other minerals here studied. Calcite showed comparable properties, except
for a very high Fe content. The material that has emitted highest quantities of polluting heavy metals is
olivine, which under high thermal stress, has released large quantities of Fe and Pb. Kaolinite also
demonstrated to be potentially harmful, in fact, in addition to the high quantities of Fe also emitted Cr, Ni
and Pb.

In Figure 6 it is reported the comparison of the emissions of the mineral / biomass systems. TGA-DTA tests,
combining biomass with bed material, surprisingly led to different results. The concentration of HMs emitted,
assuming that the biomass samples have the same quantity of HMs, can be obtained by multiplying the
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weight of the biomass for the concentration of metals measured in ICP-MS. But it is evident that the very
high Fe concentrations are markedly decreased in the tests with biomass. This probably depends on the fact
that placing the biomass above the bed in static condition affected the release of carbonate residues,
reducing the overall metals emissions. Kaolinite showed to be the most appropriate material as it has the
lowest emissions. Limestone and K-Feldspar have an almost similar behaviour leading to the reduction of the
global overall emissions.

Figure 4: SEM-EDS ash analysis of Arundo Donax PABR after TGA-DTA process

An objective comparison between the main parameters here considered should be useful for choosing the
optimal material to be employed as a bed in an FBG. The selection criteria here considered are: a)
concentrations of heavy metals emitted during the gasification process from the simple material; b) metals
emitted from the material + PABR biomass mixture; c) percentage of carbon deposited on the mineral granule
after the TGA-DTA treatment with biomass, recorded by the SEM-EDS examination. This last parameter was
set to have the lower weight, but nevertheless it represents a non-negligible factor since the mineral
particles, post-treatment in TGA-DTA, with a high percentage of surface carbon are more affected by the
effects of agglomeration. The occurrence of bed agglomeration in such systems implies unscheduled
shutdown of the reactor and costly maintenance operations when operating on a large scale. Furthermore,
the volatile carbonaceous fine powders, if they bind to heavy metals, could favour their transport from the
reactor to the outgoing gas, causing syngas contamination. By placing the evaluation criteria in a 3D graph,
each in its own axis, as shown in Figure 7, it is possible to select the most appropriate materials. The graph is
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constructed in such a way that the points in space assume the coordinates with values expressed in
percentages. The emissions have a greater weight than the surface carbon content. The sphere segment is
constructed to incorporate the materials with the best results.

Figure 5: Comparison of heavy metals emitted from materials commonly used in FBG beds when simulating gasification operating
conditions

Figure 6: Heavy metals emitted from PABR materials + biomass during the simulation of the gasification process in TGA-DTA
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Figure 7: Material choice chart, created with GeoGebra. The axes are: emission of minerals in the bubblers [% of the total], the
percentage of surface carbon and the comparison of the emissions of minerals + biomass [% of the total]

Based on these results, the characterization of the two bed materials considered most suitable (Limestone
and K-Feldspar) is here reported. The mineralization of these materials and the subsequent analysis in ICP-
MS made it possible to determine their percentage composition in terms of heavy metals present. The results
are shown in Figure 8.

Figure 8: Limestone (left) and K-Feldspar (right) heavy metals composition. In grey the sum of other metals

Limestone

Limestone is mainly composed of Ca (included in other elements), although some heavy metals such as Mn,
Fe, Ba and Pb are also present. Such metals can affect the quality of the final syngas as they could be released
during gasification. Results of TGA-DTA analysis are shown in Figures 9-10. Pure Limestone (Fig.9 top) shows
two evident mass reduction (that also repeats when joining the mineral to the biomass). The first one is
encountered at about 350 ° C and it occurs due to the loss of CO from the crystalline structure. The second
mass reduction occurs at about 700 ° C and it is caused by the formation of CaO in the crucible for the release
of CO2 [19]. This process ends about three minutes after reaching 850°C. The weight loss is 63% compared to
the initial weight of Limestone. Such a weight loss must be considered while setting up an FBG with a
Limestone bed. As for the heat flux graphs, both have a similar trend. In the case of Limestone a peak is
reached at about 600 ° C, with a power peak of about 200 mW, while in the case of Limestone + PABR biomass
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the peak occurs at about 500 ° C, generating a value of 400 mW of power. The negative peak that is recorded
as soon as the temperature of 850 ° C is reached, is due to the release of CO2 and consists of an endothermic
reaction that generates a negative value compared to the constant energy supplied by the machinery.

Figure 9: The gravimetric variation (above) and the energetic variation (below) of the Limestone material

Figure 10: The gravimetric variation (above) and the energetic variation (below) of the Limestone + biomass

The TGA-DTA treatment drastically lowered the weight of the analysed sample and the endothermic peaks
recorded in the energy variation graphs highlighted the strong loss of CO2 suffered by the post-treatment
sample. This is demonstrated by the SEM-EDS (Fig. 11) analysis showing a strong C reduction. The bed
material shows a regular structure also after the interaction with biomass in the gasification process. When
only Limestone is tested, there is a reduction of Ca after process, while such circumstance does not happen
in the Limestone + biomass tests.
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Figure 11: SEM images of Limestone and biomass post-treatment in TGA-DTA, with normalized molar mass ratio [%].

K-Feldspar

K-Feldspar is composed by Calcium, Potassium, Aluminum and Iron. In Fig. 8 only the heavy metals are
specified. The other elements fraction is composed by 2/3 of Ca and the remaining part is K. Overall, the K-
Feldspar during mineralisation released very small quantities of heavy metals, so it can be deduced that the
material under examination it is not compromised by any structural impurities that can contaminate the
produced syngas. The trend of weight and heat emitted / absorbed by the material when it is subjected to
gasification temperatures is shown in Figure 12 while iFigure 13 shows the trends in the case of the material
+ PABR biomass mixture. Fig.12 shows the monotonous decreasing in the first minutes that can be
attributable to a constant loss of structural water and to the loss of volatile impurities, resulting in a total
weight loss of about 4%. Fig. 13 confirms that the K-Feldspar has excellent qualities of resistance to
degradation as it does not undergo significant weight losses, as previously noted. As for the energy variation,
it is possible to notice a peak at the maximum power values, due to the dehydroxylation of the kaolin that
leads to the production of metakaolin [20]. In Fig.12 a power of 200 mW is reached with a value of about 50
J of energy produced, while in Fig.13 for K-Feldspar + PABR biomass mixture curve, it is noted that the peak
due to biomass gasification is greater than 400 mW, and then it reaches a stable trend once the energy ramp
is interrupted.

SEM-EDS analysis is shown in Fig.14. It is observed that the K-Feldspar + PABR biomass residues are composed
of irregular granular material. The characterization of the surface shows high quantities of Carbon, certainly
due to the residue of the biomass that has deposited on the surface of the mineral.

Conclusions

The research activity here presented examined the behaviour of the bed materials most used in fluidized bed
gasifiers. The analysis was carried out by simulating the gasification process in TGA-DTA comparing both the
materials individually and their interaction with a PABR biomass (Arundo Donax) rich in metals. The lab-scale
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study highlighted a problem (that was underestimated in the literature) related to contaminants release from
the bed materials, which affects syngas composition. Quartz sand, followed by K-Feldspar and Limestone,
proved to be the material that less affect the gasification process. Quartz sand releases the lower quantity of
heavy metals during the process, also due to its chemical composition essentially free of contaminants.
However, these advantages are not as evident when performing the Biomass + bed material tests.

Figure 12: The gravimetric variation (above) and the energetic variation (below) of the K-Feldspar material

Figure 13: The gravimetric variation and the energetic variation of the K-Feldspar + biomass

In fact, the chemical inertia of the quartz sand probably tends to avoid the agglomeration of the ashes and
supports their volatility. It is therefore probable that in gasifiers that use quartz sand, the balance between
the formation of bottom and fly ash is very shifted towards the latter. On the other hand, the other matrices
(also because they have higher degrees of impurity) are chemically less inert and therefore interact in a small
part (although not negligible) with the biomass and the ashes that are generated. From a comparison
between all the parameters considered, it emerges that Limestone and K-Feldspar represent the best
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optimization for the materials that can be used in FBG beds. The weight loss of about 60% that Limestone
has during the process is a critical issue that must be considered. Some uncertainties related to a possible
blockage effect of biomass on heavy metal emissions in kaolinite remain. Even if the study has to be
replicated on a pilot gasifier, it already represents an useful assessment of the parameters that must be
evaluated when using a traditional or innovative bed material in a FBG process.

Figure 14: SEM images of K-Feldspar and biomass post-treatment in TGA-DTA, with normalized molar mass ratio [%].

ACKNOWLEDGMENTS
The authors thank ENI REWIND for having provided the contaminated biomass used in the presented
analysis.

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