Fuel 312 (2022) 122910

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Fuel
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Full Length Article

Conditioning the volatile stream from biomass fast pyrolysis for the
attenuation of steam reforming catalyst deactivation
Enara Fernandez a, Laura Santamaria a, Maite Artetxe a, Maider Amutio a, Aitor Arregi a,
Gartzen Lopez a, b, *, Javier Bilbao a, Martin Olazar a
a
Department of Chemical Engineering, University of the Basque Country UPV/EHU, P.O. Box 644, E48080 Bilbao, Spain
b
IKERBASQUE, Basque Foundation for Science, Bilbao, Spain

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

Keywords: The fast deactivation of the reforming catalyst greatly conditions H2 production from biomass. In order to
Biomass alleviate this problem, use of conditioning catalysts in a previous conditioning step has been proposed to modify
Pyrolysis the pyrolysis volatile stream reaching the reforming catalyst. The experimental runs have been conducted in a
Reforming
two-step reactor system, which includes a conical spouted bed reactor for the continuous pinewood sawdust
Spouted bed
Low cost catalysts
pyrolysis and an in-line fixed bed reactor made up of two sections: the conditioning and the reforming steps.
Biomass fast pyrolysis was conducted at 500 ◦ C and the reforming step at 600 ◦ C. Different conditioning beds
(inert sand, γ-Al2O3, spent fluid catalytic cracking (FCC) catalyst and olivine) were used for the conditioning of
biomass pyrolysis volatiles and the influence their composition has on the performance and deactivation of a
commercial Ni/Al2O3 reforming catalyst has been analyzed.
Considerable differences were noticed between the conditioning catalysts, with the reforming catalyst stability
decreasing as follows depending on the type of material used: γ-Al2O3 > olivine > inert sand ≈ no guard bed >
spent FCC catalyst.
The high acidity of γ-Al2O3 (with a high density of weak acid centers) is suitable for the selective cracking of
phenolic compounds (mainly guaiacol and catechol), which are the main precursors of the coke deposited on the
Ni active sites. Although H2 production is initially lower, the reforming catalyst stability is enhanced. These
results are of uttermost significance in order to step further in the scaling up of the in-line pyrolysis-reforming
strategy for the direct production of H2 from biomass.

1. Introduction promising technology under development, in which renewable sources

can be used for the sustainable production of H2 [11,12]. Amongst the
Biomass is a promising renewable source for the production of fuels, different routes for biomass valorization, thermochemical processes
chemicals and H2 [1–4] due to its availability and CO2 neutral contri­ have merited especial consideration in the literature [8,13,14], partic­
bution. Besides, H2 is a clean fuel whose potential as an energy carrier ularly biomass steam gasification [15–19], fast pyrolysis [20,21], and
makes it a promising choice for its transformation into any form of en­ the steam reforming of the bio-oil obtained in the pyrolysis process
ergy for diverse end-use applications. [22–25]. More recently, the alternative route of biomass pyrolysis and
In recent decades, the progress of technological strategies for H2 in-line catalytic steam reforming has attracted remarkable attention for
production from biomass has gained increasing attention in the litera­ the production of H2 from biomass [26–31]. Most pyrolysis-reforming
ture [5–9]. Two types of routes are used for biomass conversion into H2, studies conducted in the literature have been performed in discontin­
as are thermochemical and biological processes [10]. Thus, biomass may uous mode using batch reactors. However, a great effort has been made
be converted into H2 through the following routes: i) water bio­ in the recent years in order to implement a continuous feeding system,
photolysis using micro-algae and cyanobacteria, ii) photofermentation, and therefore to step further in the scaling-up of this process.
iii) dark-fermentation, and iv) hybrid reactor system [5]. The biological The choice of a suitable catalyst for these processes is of uttermost
H2 production (biohydrogen) from microorganism metabolism is a significance for the viability of their industrial implementation.

* Corresponding author.
E-mail address: gartzen.lopez@ehu.eus (G. Lopez).

https://doi.org/10.1016/j.fuel.2021.122910
Received 20 July 2021; Received in revised form 18 November 2021; Accepted 8 December 2021
Available online 21 December 2021
0016-2361/© 2021 The Author(s). Published by Elsevier Ltd. This is an open access article under the CC BY-NC-ND license
(http://creativecommons.org/licenses/by-nc-nd/4.0/).
E. Fernandez et al. Fuel 312 (2022) 122910

Accordingly, primary catalysts, such as dolomite, olivine, γ-Al2O3 or 2. Experimental

spent fluid catalytic cracking (FCC) catalyst, have been widely investi­
gated in biomass gasification [32–35]. Thus, several authors have re­ 2.1. Feedstock
ported the activity of dolomite and olivine for reforming and cracking
reactions [36,37], whereas γ-Al2O3 is effective in tar decomposition and The biomass used in this process was pinewood waste (pinus insig­
promoting H2 production [38]. The utilization of a spent FCC catalyst is nis), which was crushed and sieved to a particle size in the range from 1
of special relevance, since it increases the lifetime of a refinery waste to 2 mm. The ultimate and proximate analyses were determined in
material [39,40]. previous studies in a LECO CHNS-932 elemental analyzer and in a TGA
Besides, commercial Ni-based catalysts have been extensively used in Q5000IR thermogravimetric analyzer, respectively [26,49]. An iso­
steam reforming processes, since these types of catalysts involve several peribolic bomb calorimetry (Parr 1356) was used to determine the
advantages, such as their lower cost compared to noble based catalysts, higher heating value. Table 1 summarizes the main biomass features.
as well as their high activity for breaking C − C and O − H bonds. Fig. S1 in the Supplementary Information shows the TG profile of the
However, their fast deactivation, mainly by coke deposition on the pinewood sawdust.
active sites, is a great challenge to face up. Accordingly, different stra­
tegies have been proposed with the aim of improving the activity and 2.2. Conditioning and characterization of guard and reforming catalysts
stability of the reforming catalyst, as are the use of different reactor
configurations, the selection of suitable operating conditions or the Four different low-cost materials have been used in this study as
optimization of the catalyst design based on supports and promoters guard catalysts for the conditioning of the pyrolysis volatile stream, as
[8,41–43]. are: i) inert silica sand (Minerals Sibelco), ii) olivine (Minerals Sibelco),
The strategy proposed in this study to attenuate the fast catalyst with basic character and active for reforming biomass-derived oxygen­
deactivation lies in the modification of the feed into the reforming step, ates, iii) spent FCC catalyst, supplied by Petronor Refinery in Muskiz,
which may be conducted in the pyrolysis reactor itself or downstream by Spain, and iv) γ-Al2O3 (Alfa Aesar). The spent FCC catalyst and the
upgrading the bio-oil produced in the biomass pyrolysis. Thus, it is well γ-Al2O3 are of acid character and active for cracking reactions [39].
established that certain bio-oil compounds reaching the reforming Prior to use, the spent FCC catalyst was regenerated by calcination
catalyst bed significantly influence the mechanisms of catalyst deacti­ with air at 575 ◦ C for 1 h in order to burn the coke deposited during its
vation, particularly coke formation, and therefore the performance of utilization in the refinery. The FCC catalyst particles were agglomerated
the catalyst in the reforming step [44]. Although huge effort has been by wet extrusion to obtain a particle size suitable for use in the fixed bed.
made to assess the catalyst performance and its deactivation causes in Bentonite (50 wt%) was used as binder to confer mechanical and ther­
the steam reforming process, the highly complex bio-oil composition mal resistance upon this catalyst. Subsequently, the extruded sample
and the problems associated with its handling boosted use of bio-oil was dried overnight and calcined with air at 575 ◦ C for 2 h. Then, the
model compounds, such as ethanol, phenol, acetic acid, toluene, or FCC catalyst was ground and sieved to a particle size in the 0.8–1.6 mm
their mixture [45–47]. Therefore, knowledge of the reforming catalyst range. Similarly, olivine and γ-Al2O3 were also ground and sieved to
performance and the main species responsible for catalyst deactivation attain the desired particle size (0.8–1.6 mm). The fraction of inert silica
by coke deposition under real process conditions is still limited. sand was also within this range.
Based on this background, this study pursues a dual objective. On the These conditioning catalysts were characterized by N2 adsorp­
one hand, to enhance catalyst activity and stability in the reforming step tion–desorption, X-ray Fluorescence (XRF) spectrometry and NH3-TPD.
in a tandem pyrolysis-reforming reactor by conditioning the biomass The characterization procedure has been described in the Supplemen­
pyrolysis volatile stream using highly available and inexpensive cata­ tary Information.
lysts. On the other hand, to provide a further understanding of the The commercial catalyst used in the reforming reactor (ReforMax®
reactivity of the main bio-oil oxygenate compounds and their role in the 330 or G90-LDP), denoted as G90, was supplied by Süd Chemie. The
deactivation of the reforming catalyst. The results obtained in this study selection of this catalyst is based mainly on its availability and reliability
will contribute to progressing towards the understanding of the main (without reproducibility problems in its preparation), since a significant
coke precursors in the reforming step and promoting the proposal of new amount of catalyst is needed in all the experimental runs. Moreover,
strategies for improving catalyst stability, which are the main challenges commercial G90 and other similar commercial Ni/Al2O3 catalysts have
to be faced in the industrial implementation of the pyrolysis-reforming been extensively used in the literature about the steam reforming of tar
process. compounds [50,51], biomass and sewage sludge pyrolysis volatiles
Accordingly, the production of H2 from biomass (pinewood sawdust) [52–56] and pyrolysis oils produced from waste plastics [57].
has been carried out in a conical spouted bed reactor (CSBR) for the fast This commercial catalyst for CH4 reforming was provided as perfo­
pyrolysis, and an in-line fixed bed reactor for the reforming of the vol­ rated rings (19 × 16 mm), which were ground and sieved to a particle
atiles produced [48]. For the conditioning of this stream, different low size in the 0.4–0.8 mm range. This particle size range showed a suitable
cost materials (inert sand, γ-Al2O3, a spent FCC (fluid catalytic cracking)
catalyst and olivine) have been located prior to the reforming catalyst.
Table 1
Continuous biomass pyrolysis has been conducted in a conical spouted
Pinewood sawdust characterization.
bed reactor (CSBR) and the volatiles formed have been transferred into a
Ultimate analysis (wt%)a
fixed bed reactor for their conditioning and reforming. Thus, the fixed
Carbon 49.33
bed reactor includes two reaction sections, the first one with the guard Hydrogen 6.06
catalyst (conditioning step) and the second one with the steam reform­ Nitrogen 0.04
ing one. In a previous study, this reactor configuration revealed a high Oxygenb 44.57
efficiency for the conversion of the volatiles derived from biomass py­ Proximate analysis (wt%)c
Volatile matter 73.4
rolysis into a hydrogen rich syngas, with catalyst deactivation being
Fixed carbon 16.7
lower than when a fluidized bed reactor is used in the reforming step Ash 0.5
[48]. Moisture 9.4
HHV (MJ kg¡1) 19.8
a
on a dry ash free basis
b
by difference
c
on an air-dried basis

2
E. Fernandez et al. Fuel 312 (2022) 122910

performance in previous studies operating in fixed bed regime [48]. The means of a lateral outlet pipe located above the bed surface (Fig. 1). The
chemical composition of G90 catalyst is based on NiO, whose nominal gas stream is heated to the desired temperature prior to entering the
content is 14 wt%, apart from CaAl2O4 and Al2O3. The textural prop­ reactor by means of a preheater. Both the reactor and the gas preheater
erties of the fresh catalyst determined by N2 adsorption–desorption have are located inside a radiant oven of 1250 W.
been shown in previous studies [58,59]. Accordingly, the catalyst is a The temperature in the fixed bed reactor, which is located inside an
mesoporous material, with mean pore diameter of 12.2 nm. The results oven (550 W), is controlled by a thermocouple located in the catalyst
of BET surface area (19.0 m2 g− 1) are rather low. bed. The pilot plant is provided with a cyclone, which retains the char
The Ni based catalyst reduction temperature was ascertained by and sand particles entrained from the pyrolysis bed. With the aim of
temperature programmed reduction (TPR), and the results are provided avoiding steam and heavy compounds condensation, both reactors (the
elsewhere [60,61]. Accordingly, the TPR profile revealed two main CSBR and the fixed bed reactor), all interconnection pipes and the
peaks with the prevailing one located at 550 ◦ C, which was ascribed to cyclone are placed inside a forced convection oven, wherein the box
the reduction of NiO which is interacting with Al2O3 support. The peak temperature is maintained at 300 ◦ C. Avoiding the condensation of
observed at higher temperature (700 ◦ C) was associated with NiAl2O4 heavy compounds before and after the fixed bed reactor is essential to
spinel phase. Moreover, prior to the pyrolysis-reforming experiments, carry out the analysis of the products.
in-situ catalyst reduction was carried out by feeding a stream of 10 vol% The solid feeding device consists of a vessel equipped with a vertical
H2 with N2 at 710 ◦ C for 4 h. shaft connected to a piston placed below the material bed. At the same
time as the piston raises, the biomass feeder is vibrated, which ensures
continuous discharge of the biomass into the reactor.
2.3. Experimental equipment The water required in the conical spouted bed and in the reforming
step was fed by a high precision pump (Gilson 307). It was vaporized by
The biomass pyrolysis-reforming has been carried out in a bench means of an electric heater prior to entering the pyrolysis reactor.
scale laboratory plant, whose scheme is shown in Fig. 1. The pyrolysis Moreover, the plant is provided with three mass flow-meters for N2,
step was conducted in a conical spouted bed reactor (CSBR), whereas a (used as fluidizing agent in the process of heating the reaction system),
fixed bed reactor was selected to perform the catalytic reforming of the air and H2 (used for the reforming catalyst reduction prior to the
volatiles from the pyrolysis step. In the latter reactor, different condi­ reforming step).
tioning beds (sand, γ-Al2O3, FCC and olivine) were placed prior to the The product condensation system is provided with a condenser and a
reforming catalyst bed (see Fig. 1). coalescence filter, which ensure the collection of the non-reacted steam
Previous studies conducted by the research group have proven the and bio-oil compounds prior to analysis.
good performance of the CSBR for the pyrolysis of different materials,
such as biomass [49,62,63], waste plastics [64,65] or tires [66–68].
Moreover, the design of the CSBR is based on previous hydrodynamic 2.4. Experimental conditions and product analysis
studies [69], and its dimensions are as follows: conical section height,
73 mm; cylindrical section diameter, 60.3 mm; conical section angle, The pyrolysis step was carried out at 500 ◦ C, as the condensable
30◦ ; bed bottom diameter, 12.5 mm; and gas inlet diameter, 7.6 mm. volatile fraction (liquid fraction) obtained in the biomass pyrolysis is
Continuous removal of the char particles in this reactor is carried out by maximized at this temperature [49]. Based on previous hydrodynamic

Fig. 1. Scheme of the pyrolysis-reforming laboratory scale plant.

3
E. Fernandez et al. Fuel 312 (2022) 122910

studies, the CSBR contained 50 g of silica sand with a particle size in the the non-condensable gases were analyzed in a GC Varian 4900. Besides,
0.3–0.35 mm range. Besides, a water flow rate of 3 mL min− 1 was chosen the identification of the bio-oil compounds was conducted by conden­
for all the runs, which corresponds to a steam flow rate of 3.73 NL sation of the liquid sample and further analysis by means of a GC–MS
min− 1. These conditions ensure a vigorous movement in the CSBR. spectrometer (Shimadzu 2010-QP2010S) provided with a BPX-5 col­
The reforming temperature was fixed at 600 ◦ C, which was estab­ umn. In the pyrolysis-reforming runs, the overall and elemental mass
lished as the optimum one in previous biomass pyrolysis-reforming runs balances (C, H and O) were closed based on the information about the
[26]. Thus, higher temperatures (700 ◦ C) showed a limited effect on the volatile stream that reached the reforming catalyst (which has been
reforming results [58] and may favour sintering of the metallic Ni active determined as mentioned above) and the information obtained in the GC
sites. [70]. and microGC analyses of the stream at the outlet of the reforming step.
In the fixed bed reactor, the bed was divided into two sections: i) the The mass balances closure was above 95 % in all cases, and runs were
conditioning step with the guard bed, (silica sand, γ-Al2O3, spent FCC repeated at least 3 times in order to ensure reproducibility. The chro­
catalyst or olivine), which is located in the upper section of the reactor, matographic analyses were conducted in-line by means of a GC Agilent
and ii) the reforming catalyst bed, which is composed of a mixture of 6890 provided with a HP-Pona column and a flame ionization detector
inert sand (1–2 mm) and a commercial Ni/Al2O3 (G90) catalyst (0.4–0.8 (FID). In order to avoid the condensation of non-converted oxygenate
mm). A steel mesh was used to divide both fractions with the aim of compounds, the sample from the reforming reactor outlet stream has
easing their separation for further characterization when each experi­ been injected into the GC by means of a line thermostated at 280 ◦ C. The
mental run was finished. permanent gases, i.e., H2, CO2, CO, CH4 and C2-C4 hydrocarbons, were
The conditioning catalysts used in this study are significantly analyzed in a GC Varian 4900 once the outlet stream of the reforming
different concerning density, i.e., sand: 2600 kg m− 3; olivine: 3300 kg reactor was condensed and filtered.
m− 3; FCC: 1246 kg m− 3, and γ-Al2O3: 1666 kg m− 3. The bed mass of
these materials was chosen in order to have the same bed volume in all 2.5. Characterization of the deactivated conditioning and reforming
the experiments (30 mL), which was that corresponding to a GHSVvola­ catalysts
− 1
tiles of 3100 h , and the particle size of all guard catalysts was in the
0.8–1.6 mm range. The corresponding masses were 44.2 g of silica sand, The textural properties of all conditioning beds were analyzed after
46.2 g of olivine, 17.3 g of spent FCC catalyst and 19.9 g of γ-Al2O3. each experimental run by N2 adsorption–desorption technique in a
Moreover, the same bed volume of the mixture of commercial Ni/Al2O3 Micromeritics ASAP 2010 following the procedure described in the
catalyst (G90) and inert sand was used (30 mL), which corresponds to Supplementary Information.
9.4 g and 29.0 g of reforming catalyst and inert sand, respectively. The coke formed on the spent catalysts, both guard and reforming
In order to compare the influence of the conditioning step on the ones, was analyzed at the end of each continuous run. The coke content
reforming one, the same operating conditions were established. was measured by Temperature Programmed Oxidation (TPO) in a
Accordingly, all the runs were conducted in continuous regime by Thermobalance (TGA Q5000 TA Instruments) coupled to a mass spec­
feeding 0.75 g min− 1 of biomass, with the S/B ratio being 4 and the trometer (Thermostar Balzers Instrument). Given that the Ni active phase
space time 15 gcat min gvolatiles− 1. These conditions allow attaining is oxidized at the same time as the coke combustion occurs, the CO2
conversion values close to thermodynamic equilibrium without formation is monitored throughout the TPO runs, according to the
involving high energy requirements to vaporize the water supplied. following procedure: i) Signal stabilization with a N2 stream at 100 ◦ C,
Thus, given that the steam flow rate required for attaining a suitable and, ii) oxidation with air (heating rate of 5 ◦ C min− 1 to 800 ◦ C main­
spouting regime in the CSBR has been set at 3.73 NL min− 1 (3 mL min− 1 taining this temperature for 30 min to ensure complete coke combus­
of water), the corresponding biomass flow rate was 0.75 g min− 1. tion. Similarly, the amount of coke deposited on each guard catalyst
Prior to the pyrolysis-reforming runs, all the elements of the plant after the pyrolysis-reforming runs was determined following the same
were heated using N2 as fluidizing agent. Then, the fluidizing gas was procedure. The deactivated G90 catalysts were analyzed by Scanning
switched to water and once temperature had been stabilized, biomass Electron Microscopy (SEM) in a JEOL JSM-6400 apparatus.
feed started.
The analysis of the volatile stream was carried out at three different 2.6. Reaction indices
locations: i) after the pyrolysis step, ii) once the stream had passed the
guard bed (conditioning step) and, finally, iii) at the outlet of the steam In order to evaluate the influence the different guard catalysts have
reforming reactor. Furthermore, experimental runs using different on the subsequent reforming step, volatile conversion and individual
reactor configurations have been conducted under the same conditions. product yields have been taken as the key reaction indices. It should be
Thus, in the pyrolysis runs, the volatile stream is directly connected to noted that the definition of these reaction indices is based on the volatile
the condensation system without passing through the fixed bed. In the products that reach the commercial Ni/Al2O3 catalyst (G90) bed (gases
conditioning runs, both reactors (pyrolyser and conditioning fixed bed) and bio-oil derived compounds), i.e., once the volatile stream from the
were used, with the fixed bed containing the conditioning catalyst, i.e., pyrolysis step had passed the guard bed. Thus, the carbon contained in
the reforming catalyst G90 was not introduced in the reactor. Finally, the char produced in the pyrolysis step was not considered, given that
the configuration for the pyrolysis-reforming runs was made up of a this product was removed from the CSBR (through the lateral pipe) prior
CSBR and a fixed bed reactor containing both the guard and the to the conditioning step.
reforming catalysts. This latter configuration corresponds to the scheme Accordingly, the volatile conversion in the reforming step is deter­
shown in Fig. 1. mined as the ratio between the C moles in the product stream leaving the
The mass balance in the pyrolysis runs (biomass pyrolysis and reforming step (Cgas) and the C moles in the volatile stream reaching the
biomass pyrolysis + guard catalyst) was closed by weighting the char reforming catalyst (Cvolatiles):
particles, i.e., the amount of char remained in the reactor plus those
Cgas
collected through the lateral pipe and retained in the cyclone and filter, X= ​ ⋅ 100 (1)
Cvolatiles
and combining this information with that obtained by on-line chro­
matographic analysis. In these pyrolysis runs, cyclohexane was used as Similarly, the yield of each individual product, i, has been calculated
an internal standard to validate the mass balance closure. Thus, the based on the pyrolysis volatile stream.
pyrolysis product stream leaving the fixed bed reactor was analyzed in-
Fi
line in a GC Agilent 6890 provided with a HP-Pona column and a flame Yi = ​ ⋅ 100 (2)
Fvolatiles
ionization detector (FID) by means of a line thermostated at 280 ◦ C, and

4
E. Fernandez et al. Fuel 312 (2022) 122910

where Fi and Fvolatiles are the molar flow rates of each compound i and The chemical composition of each conditioning catalyst was deter­
the volatile stream at the inlet of the reforming reactor, respectively. mined by XRF analysis, and the results are set out in Table 2. As
The hydrogen yield is defined based on the maximum allowable by observed, inert sand is mainly composed of SiO2; olivine is a mineral
stoichiometry: containing MgO, SiO2 and Fe2O3; the γ-Al2O3 used in this study contains
a small amount of SiO2, apart from Al2O3; and the FCC catalyst
Y H2 =
FH2
​ ⋅ 100 (3) agglomerated with bentonite (50 wt%) is a mixture containing Al2O3,
F0H2 SiO2, Fe2O3 and P2O5, among other metal oxides. Futhermore, incor­
poration of bentonite greatly influences the composition of the spent
where FH2 is the H2 molar flow rate and F0H2 the maximum allowable by FCC catalyst (used in a previous gasification study [39]), as it leads to a
the following stoichiometry: significant increase in the amount of SiO2. Moreover, it has been widely
Cn Hm Ok + (2n − k)H2 O → nCO2 + (2n + m/2 − k)H2 (4) reported that the chemical composition of the olivine plays a positive
role in tar decomposition and reforming reactions [73,74] due to the
Finally, H2 production is defined by mass unit of the biomass in the presence of Fe0 on its surface [75].
feed: Table 2 also shows the total acidity of the conditioning catalysts
m H2 determined by NH3-TPD analysis. The results obtained revealed that
P H2 = ⋅100 (5) only the spent FCC and the γ-Al2O3 catalyst contain acid sites, with a
m0biomass
total acidity of 47 and 106 µmolNH3 gcat− 1, respectively, whereas in the
where mH2 and m0biomass are the mass flow rates of the H2 produced and case of olivine, a negligible acidity is observed (6 µmolNH3 gcat− 1). The
biomass fed into the process, respectively. acidity of these materials enhances cracking reactions involving bio-oil
oxygenated compounds, leading to a higher amount of aromatics and
3. Results paraffins.

3.1. Conditioning catalyst characterization

3.2. Biomass pyrolysis and catalytic conditioning
The textural properties (BET surface area, pore volume and pore
Biomass pyrolysis was conducted at 500 ◦ C using steam as fluidizing
diameter) of the conditioning catalysts are shown in Table 2. As
agent. Moreover, the catalytic conditioning of fast pyrolysis volatiles
observed, FCC and γ-Al2O3 are mesoporous materials, with an average
was carried out at 600 ◦ C in the fixed bed reactor (see Fig. 1). A previous
pore size of around 17.0 nm, whereas inert sand and olivine are non-
study detailed the biomass pyrolysis products obtained using these low-
porous materials with negligible BET surface area and pore volume.
cost conditioning catalysts, and the main mechanisms of bio-oil trans­
Apart from the characteristic features of the conditioning catalysts, their
formation [76].
physical properties may significantly influence the pyrolysis volatile
The pyrolysis products obtained were grouped into three different
composition to be fed into the reforming catalyst bed. Thus, meso­
fractions: i) a gaseous fraction made up of CO2, CO, H2 and small
porosity would enhance the diffusion of bulky reactants, i.e., phenolic
amounts of C1–C4 hydrocarbons, ii) a condensable volatile fraction
compounds, such as guaiacol and their derivatives [71]. In the case of
(liquid fraction or bio-oil) composed of water and a complex mixture of
the spent FCC catalyst, which is based on the HY zeolite, the use of
oxygenated compounds, and iii) a solid residue or char, which is the
bentonite as binder provides meso and macropores to the catalyst, which
non-volatilized biomass fraction. Table 3 shows the product yields ob­
minimize external blockage of the channels [72]. However, the micro­
tained once the pyrolysis stream obtained at 500 ◦ C in the CSBR had
porous structure of this zeolite is also evident, with a microporous sur­
passed the conditioning beds in the fixed bed reactor at 600 ◦ C.
face area of 57 m2 g− 1.
As observed in Table 3, a high bio-oil yield was obtained in the
biomass pyrolysis at 500 ◦ C (75.36 wt%), which evidences the good
Table 2 performance of the CSBR for biomass pyrolysis due to the characteristic
Properties of the conditioning catalysts. features of this reactor, as are high heating rates, short vapour residence
Sand γ-Al2O3 FCC Olivine times and rapid char removal from the hot reaction environment
Physical properties
[49,77,78]. Conditioning catalysts led to a significant reduction in the
SBET (m2 g− 1) 0.6 100.6 81.3 2.4 bio-oil yield at the expense of gaseous product formation. In the case of
Smicropore (m2 g− 1) 1.1 11.5 56.7 0.7 inert sand, this drop is a consequence of thermal cracking reactions,
Vpore (cm3 g− 1) – 0.42 0.09 0.003 whereas the decrease with the other catalytic materials is due to
dpore (nm) BJH 16.9 16.8
– –
simultaneous thermal and catalytic cracking reactions. These results
Chemical properties
NiO (wt%) – – 0.05 – evidence that the features of the conditioning catalysts, i.e., physical
MgO (wt%) – – 1.09 48.79
SiO2 (wt%) 98.0 0.02 53.93 43.18 Table 3
Fe2O3 (wt%) 2.10a 7.68
Effect of conditioning catalysts on the product yields (wt%).
– –
CaO (wt%) – – 0.24 0.12
Al2O3 (wt%) – 99.98 31.90 0.04 Pyrolysis Inert sand γ-Al2O3 FCC Olivine
Na2O (wt%) – – 0.38 0.06 500 ◦ C
TiO2 (wt%) – – 0.85 0.02
Gas 7.30 ± 0.29 14.37 ± 32.45 ± 26.11 ± 18.89 ±
MnO (wt%) – – 0.01 0.11
0.62 1.27 0.96 0.66
P2O5 (wt%) – – 0.22 –
V2O5 (wt%) – – 0.20 – CO 2.25 6.51 16.71 11.96 7.10
K2O (wt%) – – 0.24 – CO2 4.68 6.37 10.72 11.25 9.67
La2O3 (wt%) – – 1.25b – CH4 0.19 0.99 2.01 1.34 0.86
SO3 (wt%) – – 0.13 – C2-C4 0.12 0.37 2.66 1.41 0.87
Cl (wt%) – – 0.15b – H2 0.06 0.12 0.34 0.14 0.40
Acidity
Total acidity – 106.32 46.73 6.17 Bio- 75.36 ± 2.83 68.29 ± 50.21 ± 56.55 ± 63.77 ±
(µmolNH3 gcat− 1) oil 2.39 1.61 2.32 2.49

a Char 17.34 ± 0.81 17.34 ± 17.34 ± 17.34 ± 17.34 ±

Expressed as total Fe2O3.
b 0.81 0.81 0.81 0.81
Determined by semi-quantitative software.

5
E. Fernandez et al. Fuel 312 (2022) 122910

properties, chemical composition and catalyst acidity (see Table 2), In comparison with the bio-oil obtained in the pyrolysis at 500 ◦ C,
greatly influence the composition of the volatile stream to be fed into the the use of inert sand led to a significant drop in the amount of light al­
reforming catalyst bed. Thus, although all conditioning catalysts tested cohols, saccharides, and mainly in that of the phenolic fraction
are active for cracking (with an increase in the non-condensable gas (particularly the catechol fraction), as a result of thermal cracking re­
yield in detriment of the condensable fraction (bio-oil)), the basic nature actions. Moreover, the concentration of polycyclic aromatic alcohols
of olivine, as well as its limited porous structure (which hinders the increased from 0.27 to 2.47 wt%, respectively. The acidity of the spent
diffusion of bulky oxygenated compounds into the bed material), led to a FCC and γ-Al2O3 conditioning catalysts (Table 2) promoted deoxygen­
lower extension of cracking reactions. Besides, the mesoporous structure ation reactions, as well as cracking, oligomerization, alkylation, isom­
of FCC and Al2O3 guard catalyst, and especially the higher acidity of FCC erization, cyclization and aromatization, leading to a considerable
and γ-Al2O3 catalysts, Table 2, led to higher gas yields (26.11 and 32.45 increase in the hydrocarbon fraction (to 6.12 and 8.49 wt%, respec­
wt%, respectively) due to the promotion of bio-oil cracking. tively). Significant differences were observed in the distribution of the
The char produced is continuously extracted from the pyrolysis components in the phenolic fraction, with catechols being the major
reactor by a lateral outlet (see Fig. 1), and its yield was not therefore components with the FCC conditioning bed, whereas the phenolic
affected by conditioning catalysts. Accordingly, it remained constant in fraction obtained with the Al2O3 catalyst only contained alkyl-phenols.
all the experimental runs (17.34 wt%). The higher selectivity of the Al2O3 catalyst for the production of alkyl-
In the biomass pyrolysis at 500 ◦ C, CO and CO2, and small amounts of phenols revealed the effective dealkoxylation of guaiacols and cath­
H2 and C1–C4 hydrocarbons account mainly for the gaseous product ecols [81].
stream. Besides, when inert sand, spent FCC and γ-Al2O3 were used, CO In the case of the olivine conditioning bed, a decrease in the acid and
was the main compound in the non-condensable gaseous stream, which furan fractions was observed, with the ketone fraction remaining almost
is evidence that decarbonylation reactions prevailed rather than constant. Thus, the basic nature of this material promoted the ketoni­
decarboxylation ones. The higher extent of cracking reactions when zation of acids over basic catalysts, as well as the aldol condensation of
spent FCC and γ-Al2O3 catalysts were used was also evidenced in the small ketone and aldehyde molecules to larger chain ketones by car­
higher yield of CH4 and C2-C4 hydrocarbons in the volatile stream. bon–carbon coupling reactions [79,82]. A reduction in the guaiacol
However, in the case of olivine, the yield of CO2 was higher than that of fraction, and therefore in the overall phenolic fraction was also evi­
CO and the other gaseous compounds due to the basic nature of this denced, whereas the yield of hydrocarbons (mainly naphthalene com­
mineral, which enhanced ketonization and aldol condensation reactions pounds) increased because of secondary cracking reactions.
leading to the formation of CO2 and water [79]. Besides, the highest H2
yield was observed in the experimental runs conducted with the olivine
3.3. Effect of the conditioning beds on the activity and stability of the
guard bed. Thus, the chemical composition of olivine, which contains
reforming catalyst
Fe0 on its surface, promotes reforming and WGS reactions [73,75].
The detailed bio-oil composition obtained in each experimental run
The effect of using conditioning catalysts prior to the reforming step
is shown in Table 4. The inert nature of steam as fluidizing agent in the
has been analyzed, i.e., the influence the composition of the volatile
biomass pyrolysis at 500 ◦ C has been demonstrated in previous studies
stream fed into the reforming bed has on the catalyst activity and sta­
[26,80], and has been confirmed in this one by comparing the results
bility. Accordingly, the evolution of the volatile conversion (Fig. 2) and
obtained when steam was used as fluidizing agent (see Tables 3 and 4)
product yields (Fig. 3) was monitored with time on stream based on the
with those reported for N2 [49]. Besides, this inert nature of steam is a
following main reactions:
great advantage for process viability, as the cost of the gases is reduced
Oxygenate steam reforming:
and the problems related to inert gas separation prior to the catalytic
reforming step are avoided. However, the use of conditioning beds CnHmOk+(n-k)H2O → nCO + (n + m/2-k)H2 (6)
significantly modified the composition of the bio-oil products. As
aforementioned, all conditioning catalysts were located in a fixed bed Water Gas Shift (WGS):
reactor at 600 ◦ C (above that of pyrolysis), which may also have certain CO + H2O ↔ CO2 + H2 (7)
influence on the bio-oil composition.
Oxygenate cracking (secondary reaction):

Table 4
Effect of conditioning catalysts on the bio-oil composition (wt.%).
Pyrolysis 500 ◦ C Inert γ-Al2O3 FCC Olivine
sand

Acids 4.00 4.06 0.00 0.00 2.26

Aldehydes 3.29 5.41 1.10 0.52 3.78
Ketones 9.64 9.23 4.23 4.76 9.65
Alcohols 2.43 0.69 0.00 0.00 0.49
Polycyclic Aromatic 0.27 2.47 6.52 8.45 6.66
Alcohols
Phenols 21.98 17.45 15.94 17.92 13.14
Alkyl-phenols 2.16 2.33 15.94 5.24 2.73
Catechols 10.99 5.60 0.00 11.56 6.62
Guaiacols 8.84 9.52 0.00 1.12 3.76
Furans 3.10 3.32 0.62 3.05 1.41
Saccharides 6.03 4.11 0.00 0.00 4.22
Hydrocarbons 0.00 0.06 8.49 6.12 1.06
Non-aromatics 0.00 0.06 0.69 0.00 0.03
Light aromatics (BTX) 0.00 0.00 0.69 0.31 0.03
PAHs 0.00 0.00 7.12 5.80 0.99
Others 0.09 0.00 0.00 0.15 3.15
Unidentified 16.74 15.68 13.03 13.37 15.60
Water 32.44 37.52 50.08 45.67 38.59
Fig. 2. Effect of the conditioning bed addition on the evolution of oxygenate
conversion with time on stream in the reforming of biomass pyrolysis products.

6
E. Fernandez et al. Fuel 312 (2022) 122910
CnHmOk → oxygenates + hydrocarbons + CH4 + CO + CO2 + C (8)
inlet of the reforming catalyst bed, which is explained by the high ac­
Methane (and hydrocarbons) steam reforming:
tivity of the commercial Ni/Al2O3 (G90) catalyst.
CH4 + H2O ↔ CO + 3H2 (9) It is to note that the volatile stream reaching the reforming catalyst in
any experimental run is made up of a complex mixture of oxygenate
Fig. 2 shows that the volatiles derived from biomass pyrolysis are compounds. Most of the research studies dealing with the mechanisms
completely reformed independently of the stream composition at the involving reforming reactions and/or catalyst deactivation have been

Fig. 3. Effect of the conditioning bed addition on the evolution of the individual product yields with time on stream in the reforming step. a) Without conditioning
bed; b) Inert sand; c) γ-Al2O3; d) FCC and, e) Olivine.

7
E. Fernandez et al. Fuel 312 (2022) 122910

conducted with model compounds and synthetic mixtures simulating %). Besides, the high concentration of polycyclic aromatic alcohols
bio-oil and tar. However, different compounds reactivity has been re­ (mainly composed of indenol and naphthalenol derived compounds)
ported depending on whether they are reformed alone or in a mixture of may also contribute to the fast catalyst deactivation in the reforming
different oxygenated compounds [83]. Therefore, detailed and laborious step. These results are consistent with those obtained in other literature
studies are required to analyse, on the one hand, the reactivity of the studies. Thus, Artetxe et al. [47] investigated the steam reforming of
compounds in the biomass pyrolysis volatile stream modified by the use different tar model compounds (phenol, toluene, methyl naphthalene,
of conditioning catalysts (due to the high amount of species contained indene, anisole and furfural), and reported that the lowest conversion
and their interactions) and, on the other hand, their further contribution was attained when phenol was used as model compound. Trane-Restrup
to catalyst deactivation. and Jensen [89] studied the steam reforming of cyclic model compounds
As observed in Fig. 2, the experiments conducted without any con­ in the bio-oil (2-methylfuran, furfural, and guaiacol) over Ni-based
ditioning catalyst showed a stable catalyst performance for the first 50 catalysts, revealing that the phenolic compound guaiacol was the most
min on stream (conversion values up to 99.8 %), and it then decreased to difficult to convert to synthesis gas. Likewise, Wang et al. [90] reported
56.6 % after 86 min on stream, which is evidence of the deactivation of the lower reactivity of phenol over a Ni based catalyst compared to other
the catalyst. The runs conducted with inert sand as guard bed showed oxygenated compounds, such as furfural, hydroxyacetone or acetic acid.
similar results of conversion, which decreased to 58.2 % for 87 min on The high concentration of hydrocarbons (6.12 wt%) in the bio-oil as
stream. Despite the differences obtained in the volatile composition a result of the acidity of the FCC catalyst also influenced the reforming
when no conditioning catalyst and inert sand were used (see Table 4), reaction. This hydrocarbon fraction is mainly composed of polycyclic
similar catalytic performance in the reforming step was observed. It aromatic hydrocarbons (PAHs), namely, indene (0.12 wt%), naphtha­
seems that, in the pyrolysis-reforming experiment without any condi­ lene (2.40 wt%), fluorene (0.74 wt%), anthracene (0.65 wt%) and
tioning material, the volatile stream leaving the pyrolysis reactor un­ phenanthrene (1.89 wt%). Thus, several authors have reported the
dergoes thermal cracking reactions in parallel with catalytic ones on the lower reactivity of large cyclic hydrocarbons with higher molecular
reforming catalyst, with the thermal cracking leading to a volatile weights than oxygenate compounds in the steam reforming reactions
composition similar as the one obtained with inert sand. [47,84]. Regarding hydrocarbon reactivity in steam reforming re­
Regarding the experiments conducted using olivine guard bed, actions, several studies in the literature report lower reactivity of
almost full conversion was attained for the first 30 min on stream, and it naphthalene than other bio-oil model compounds like toluene, benzene,
then gradually decreased to 51.6 % for 98 min on stream. However, pyrene or anthracene [41,91,92]. In fact, these aromatic hydrocarbons
despite the fact that the reforming catalyst begins to lose activity earlier are well known because they undergo condensation reactions to form
when there is an olivine guard bed than without any conditioning coke, which accelerates catalyst deactivation [93,94].
catalyst or inert sand, its deactivation rate is significantly lower, which The best catalytic performance was observed when γ-Al2O3 was used
leads to greater stability over time. This fact is explained by the different as conditioning catalyst, with a stable volatile conversion for the first 30
nature of the volatile stream to be reformed. The presence of more re­ min on stream and then decreasing to 39 % subsequent to 112 min on
fractory compounds in the volatile stream when olivine was used as stream. Similarly to other conditioning catalysts, the initial loss of
conditioning catalyst, namely the hydrocarbon fraction (1.06 wt%), led catalyst activity occurred earlier than in the runs conducted without
to a faster initial loss of activity. Although the hydrocarbon fraction’s conditioning bed or with silica sand, which is a consequence of the total
reactivity is low for reforming reactions, its low concentration did not acidity of the γ-Al2O3, as it promotes secondary cracking reactions
involve a fast catalyst deactivation with time on stream. Other authors leading to a higher concentration of olefins and aromatic hydrocarbon
have also reported a higher reactivity of oxygenated compounds derived compounds. However, although there is a high concentration of this
from biomass pyrolysis in comparison with the hydrocarbon compounds hydrocarbon fraction (the highest one is obtained when Al2O3 is used as
due to the presence of C═O bonds that enhance the formation of carbon conditioning bed), these compounds do not involve a sharp decrease in
oxides in the reforming step [84,85]. The lower amount of phenolic volatile conversion. The reduction in the concentration of phenols in the
compounds when olivine was used, especially the guaiacol fraction, volatile stream to be reformed, particularly that of guiacol and catechol
resulted in a greater stability over time. The lower aldehyde fraction fractions, significantly attenuated the Ni/Al2O3 (G90) catalyst deacti­
than with inert sand may also contribute to attenuating catalyst deac­ vation. Total removal of acids and saccharides and a significant reduc­
tivation. Thus, several authors have reported that the main coke pre­ tion in the aldehyde fraction may also contribute to attenuating the fast
cursors, and therefore the main responsible for catalyst deactivation are deactivation of the reforming catalyst. Several authors have reported
aldehydes, phenols, and saccharides [83,86]. Gayubo et al. [86] state that the main coke precursors, and therefore the main responsible for
phenolic compounds (as well as aldehydes) are the main contributors to catalyst deactivation, are aldehydes, phenols, and saccharides [83,86].
catalyst deactivation by coke formation. Valle et al. [87] analyzed the The great differences in the performance of the reforming catalysts
influence the presence of phenolic compounds has on catalyst stability in when the spent FCC catalyst and γ-Al2O3 conditioning catalysts were
the reforming of raw bio-oil. Accordingly, they approached the removal used are mainly due to the differences observed in the composition of
of these phenolic compounds from the raw bio-oil by accelerated aging phenolic compounds. Thus, whereas alkyl-phenols (15.96 wt%) are only
and liquid–liquid extraction methods. They observed that catalyst obtained with the γ-Al2O3, catechols are the major fraction with the FCC
deactivation was lower than when raw bio-oil was used in the steam conditioning bed (11.56 wt%). A comparison of the reforming perfor­
reforming, since phenols removal from the bio-oil significantly reduced mance when olivine and Al2O3 conditioning beds are used reveals that
coke content. Ochoa et al. [88] associated the composition of oxygenate both total concentration of the phenolic fraction and component dis­
compounds in the reaction medium with the composition of the coke tribution in this faction influence the performance of the reforming
formed using Fourier transform infrared (FTIR) spectroscopy. They catalyst. Accordingly, the presence of guaicols, and especially catechols
concluded that methoxyphenols (guaicols) and levoglucosan (saccha­ led to a fast catalyst deactivation in the reforming step.
rides) have greater influence on coke formation than acids, ketones and Despite the stability of G90 catalyst is greatly improved when an
aldehydes. Al2O3 conditioning catalyst is used, the rapid deactivation of the
The performance of the commercial Ni/Al2O3 (G90) catalyst when reforming catalyst will entail working under reaction-regeneration cy­
the spent FCC guard catalyst was used showed full conversion for the cles when the operation is performed at large scale.
first 30 min on stream, and then sharply decreased attaining a conver­ Fig. 3 shows the evolution of the yields of gaseous product and non-
sion value of 38.2 % after 76 min on stream. This fast catalyst deacti­ converted bio-oil compounds with time on stream for the experiments
vation is mainly associated with the high concentration of the phenolic conducted without conditioning (Fig. 3a), and with conditioning cata­
fraction, especially the high amount of catechol compounds (11.56 wt lysts (Fig. 3b-e). As observed, H2 and CO2 decreased with time on stream

8
E. Fernandez et al. Fuel 312 (2022) 122910

in all cases due to the lower extension of reforming, Eqs. (6) and (9), and have been characterized by temperature programmed oxidation (TPO).
WGS reaction, Eq. (7), as the catalyst is being deactivated. The runs The main causes of catalyst deactivation in the reforming processes are
conducted without conditioning catalyst and inert sand showed a similar metal sintering and coke deposition [99]. However, previous pyrolysis-
trend in the evolution of gaseous product yields, which is evidence of the reforming studies conducted by the research group using the commer­
similarities in the volatile stream reaching the reforming bed catalyst in cial Ni/Al2O3 (G90) catalyst evidenced that metal sintering did not
both experiments. occur [100]. Thus, the low reforming temperature used in this study
When olivine and spent FCC catalysts were used, the evolution with (600 ◦ C) is slightly higher than Ni Tamman temperature (590 ◦ C), and
time on stream followed a similar trend as conversion, with a stable H2 metal sintering is therefore avoided. Accordingly, coke deposition is the
and CO2 yield for the first 30 min. Regarding the FCC guard bed, a sharp main responsible for catalyst deactivation.
decrease in H2 and CO2 yields was observed due to the attenuation of the
reforming and WGS reaction (Eqs. (6) and (7), respectively) as the 3.4.1. Coke deposition on the conditioning catalysts
catalyst was being deactivated. In the case of the γ-Al2O3 conditioning TPO analyses have been conducted to the guard materials in order to
bed, the yields of H2 and CO2 decreased from the beginning of the re­ ascertain the influence textural properties and their characteristic fea­
action. Thus, H2 yield decreased from 95.9 to 28.1 % and CO2 from 93.9 tures have on the coke deposited. It should be noted that the coke is
% to 33.1 % for 112 min on stream. formed due to the contact of the volatile stream with these materials
In all cases, the deactivation rate of the catalyst is faster as the prior to reaching the reforming catalyst. However, due to the different
concentration of the non-converted bio-oil compounds in the reaction duration of the runs (which depends on the stability of the G90 catalyst
medium is higher. In fact, an autocatalytic deactivation behaviour has in the reforming step), and in order to compare the amount of coke
been reported in the reforming of biomass pyrolysis volatiles [58,95]. deposited on each conditioning catalyst, the average coke deposition
These results clearly show that the oxygenated compounds, particularly rate per biomass mass unit has been defined as follows:
the phenolic fraction (mainly catechols) produced in the pyrolysis of
Wcoke /t
biomass using FCC conditioning bed, cause a much faster deactivation, rcoke = (10)
Wcatalyst mbiomass
which reveals that these compounds are the main coke precursors.
The results obtained at zero time on stream for H2 production (based
with Wcatalyst and Wcoke being the catalyst and coke masses, respectively,
on the biomass mass unit in the feed) revealed a high performance of the
mbiomass the biomass mass flow rate in the feed and t the reaction time in
overall pyrolysis-reforming strategy, with values between 9.5 and 10.2
each run.
wt%. Similar H2 production values were reported in a previous study
The results of coke content and average coke deposition rate per
conducted under the same experimental conditions, but using a fluidized
biomass mass unit are set out in Table 5, and the TPO profiles are shown
bed reactor in the reforming step [26]. Xiao et al. [96] studied the
in Fig. 4.
pyrolysis-reforming of pinewood chips on a Ni/coal char catalyst,
As observed in Table 5, significant differences are observed in the
obtaining a H2 production of 10 wt% at a reforming temperature of
results for the conditioning catalysts used. Thus, the runs conducted
650 ◦ C. Ma et al. [97] reported a H2 production value of 7.6 wt% in a
with silica sand and olivine led to a negligible amount of coke deposition
three-step process (biomass pyrolysis, gas–solid simultaneous gasifica­
(0.13 and 0.38 wt%, respectively), which corresponds to average coke
tion and catalytic reforming) using a Ni/MgO commercial catalyst.
deposition rates per biomass mass unit of 0.02 and 0.05 mgcoke ggc-1
Akubo et al. [98] investigated the pyrolysis-catalytic steam reforming of
gbiomass-1. The limited porous structure of these materials (see Table 2)
six agricultural biomass waste samples obtaining a H2 production in the
hindered coke deposition. Their characteristic features, i.e., the inert
3.3–5.1 wt% range.
nature of silica sand, and the basic nature of olivine, as well as the
As concerns CO yield, a slightly decreasing trend is observed in all
capability of the latter to enhance reforming reactions, may contribute
the experimental runs, which is a consequence of a balance involving its
to attenuating coke deposition.
production by the reforming reaction (decreasing with time on stream),
As concerns γ-Al2O3 and spent FCC conditioning catalysts, the
Eq. (6), formation by cracking reactions, Eq. (8), and deactivation of the
amounts of coke deposited and the average coke deposition rates per
catalyst for the WGS reaction, (Eq. (7)). As the reaction proceeded, the
biomass mass unit were considerable higher (0.98 and 2.04 mgcoke ggc-1
yields of CH4 and light hydrocarbons increased slightly, which is evi­
gbiomass-1, for FCC and γ-Al2O3, respectively). It is well-established in the
dence of cracking reactions, although to a minor extent (CH4 yields
literature that the acid properties of these materials promote the for­
lower than 2 %) due to the operating conditions used in the reforming
mation of coke deposits due to dehydration, cracking and polymeriza­
reactor, i.e., rather low temperature and residence time.
tion reactions, which take place on the acid sites [22,71,94,101,102].
Accordingly, the higher total acidity of the γ-Al2O3 compared to the FCC
catalyst (See Table 2) led to a higher amount of coke deposited on this
3.4. Coke deposition
conditioning bed. The selective coke deposition on the former condi­
tioning catalyst surface attenuates the subsequent coke formation on the
With the aim of evaluating the influence of different conditioning
reforming catalyst, and therefore improves its stability. Thus, the coke
beds on the pyrolysis volatile composition and their relationship with
precursors are deposited on the acid sites of Al2O3 conditioning catalyst,
catalysts performance and deactivation, the cokes deposited on the
leading to a volatile stream less prone to coke formation on the G90
guard catalysts as well as on the commercial Ni/Al2O3 (G90) catalyst

Table 5
Textural properties and values of coke content (CC) and average coke deposition rate per biomass mass unit (rC) on the conditioning catalysts (gc) after pyrolysis-
reforming runs.
Guard catalyst SBET Vpore dpore Cc (gc) rc (gc)
(m2 g− 1) (cm3 g− 1) (nm) (wt%) (mgcoke ggc-1 gbiomass-1)
Fresh/spent Fresh/spent Fresh/spent

Inert sand 0.6/0.1 -/- -/- 0.13 0.02

γ-Al2O3 100.6/83.9 0.42/0.30 16.9/12.3 17.12 2.04
FCC 81.3/15.1 0.09/0.04 16.8/18.7 5.61 0.98
Olivine 2.4/1.2 0.003/0.003 -/- 0.38 0.05

9
E. Fernandez et al. Fuel 312 (2022) 122910

Fig. 4. TPO profiles of the used conditioning catalysts. Fig. 5. TPO profiles of the commercial Ni/Al2O3 catalyst deactivated using
different conditioning beds prior to the reforming process.
reforming catalyst surface. Moreover, the mesoporous structure of these
materials favors coke deposition on their surface. Similarly, Li et al. [93] Ni/Al2O3 catalysts when different conditioning beds are used prior to
analyzed the main reaction pathways occurring in the catalytic cracking the reforming. As in the previous section, this average coke deposition
of different bio-oil model compounds (acetic acid, cyclopentanone and rate has been determined by Eq. (10). As observed, a similar average
guaicol). They reported a higher coke production when guaicol was coke deposition rate was obtained in the experiments conducted without
used, and ascribed it to the coke chemical structure and hydrogen to conditioning catalyst and inert sand (0.67 and 0.66 mgcoke gcat-1 gbiomass-
1
carbon effective ratios of the feedstock. Besides, these authors describe , respectively), which is consistent with their similar evolution of
coke formation as a sequence of polymerization and polycondensation conversion and product yields with time on stream (Figs. 2 and 3,
reactions involving bulky aromatic compounds formed in the catalytic respectively).
cracking of guaicol, which lead to carbon deposits on the catalyst The poor performance of the reforming process observed in Fig. 2
surface. when the FCC catalyst was used is supported by the high average coke
The textural properties of the fresh and spent conditioning catalysts deposition rate obtained (0.70 mgcoke gcat-1 gbiomass-1). Thus, the
are also shown in Table 5. As observed, the coke deposited on the con­ composition of the volatile stream reaching the reforming catalyst is
ditioning materials also influenced their textural properties. In the case responsible for this coke formation rate, and therefore for catalyst
of inert sand and olivine, no significant differences were observed prior deactivation. Accordingly, the high concentration of phenolic com­
and subsequent to use in the pyrolysis-reforming runs due to the limited pounds (catechols) in the volatile stream when the FCC guard bed is
porous structure of these materials. However, a sharp decrease in the used increases the coke deposition rate.
SBET area was observed for the FCC catalyst (from 81.3 to 15.1 m2 g− 1) The lowest average coke deposition rate was obtained when γ-Al2O3
due the full blockage of the pores, especially the micropores of the HY was used as guard catalyst, which is consistent with the better perfor­
zeolite structure. Concerning the γ-Al2O3 catalyst, the specific surface mance observed in Fig. 2. The amount of coke deposited on the condi­
area and average pore diameter decreased from 100.6 to 83.9 m2 g− 1 tioning catalyst has an influence on the amount of coke deposited on the
and from 16.9 to 12.3 nm, respectively, which is evidence of the partial reforming catalyst. As aforementioned, the higher acidity of the γ-Al2O3
blockage of the pores in this catalyst. favored coke promoters deposition on its surface (see Table 5), and so
Fig. 4 shows the TPO profiles of all conditioning catalysts, wherein decreased the coke formation rate on the subsequent Ni/Al2O3 (G90)
significant differences are revealed concerning their coke combustion catalyst used in the reforming step. Besides, the composition of the
temperature. As regards the γ-Al2O3 catalyst, one main peak located at volatile stream to be reformed, with a high fraction of hydrocarbons and
475 ◦ C is observed, whereas the main peak in the profile of the spent FCC the phenolic one containing only alkyl-phenols, attenuates coke depo­
catalyst is located at 535 ◦ C. Thus, cokes of different nature are depos­ sition. Thus, several authors have reported that oxygenated compounds
ited, with the one deposited on the γ-Al2O3 catalyst being more hydro­ are more prone to form carbon deposits than aromatic hydrocarbons
genated (higher proportion of aliphatic compounds than aromatic ones), [47,84].
whereas that on the FCC catalyst has a more structured aromatic Regarding the experiments conducted with the olivine conditioning
composition [103,104]. catalyst, a similar average coke deposition rate as in the runs without
conditioning bed and with silica sand (0.67 mgcoke gcat-1 gbiomass-1) was
3.4.2. Coke deposition on the commercial Ni/Al2O3 (G90) catalysts observed on the reforming catalyst. Thus, although the conversion of
Table 6 shows the amounts of coke deposited (CC) and the average pyrolysis volatiles decreased faster during the initial minutes on stream
coke deposition rates per biomass mass unit fed (rC) on the deactivated due to the presence of refractory compounds in the volatile stream, a

Table 6
Values of coke content (CC) and average coke deposition rate per biomass mass unit (rC) on the deactivated reforming catalyst (Ni/Al2O3 (G90)).
Conditioning catalyst Cc (Ni/Al2O3) rc (Ni/Al2O3) Time on stream Biomass fed
(wt%) (mgcoke gcat-1 gbiomass-1) (min) (g)

– 4.33 0.67 86.3 64.7

Inert sand 4.87 0.66 98.3 73.7
γ-Al2O3 4.11 0.49 112.0 84.0
FCC 3.97 0.70 76.0 57.0
Olivine 4.93 0.67 98.4 73.8

10
E. Fernandez et al. Fuel 312 (2022) 122910

similar coke formation rate was observed on the Ni/Al2O3 reforming the initial H2 production decreases when γ-Al2O3 is used as conditioning
catalyst. catalyst, the stability of the reforming G90 catalyst is enhanced, and
It should be noted that use of a fixed bed regime in the reforming step therefore a longer duration of the reaction stage is feasible.
may lead to severe coke formation on both the conditioning and the Although the deactivation of the catalyst is notably attenuated with
reforming catalysts, and therefore to operational problems, such as bed this strategy, the deactivation by coke deposition of the conditioning
plugging [60,105]. catalyst is also observed. Consequently, the scalability of this two-step
Fig. 5 shows the TPO profiles of the deactivated commercial Ni/ pyrolysis-reforming process provided with a conditioning step will
Al2O3 catalyst when different conditioning beds were used prior to the require regeneration strategies for both the G90 reforming catalyst and
pyrolysis-reforming process. In these profiles, two main peaks can be the γ-Al2O3 conditioning catalyst.
distinguished in all the catalyst samples, with the first one located at
435 ◦ C (coke I), and the second one at 525 ◦ C (coke II). The different CRediT authorship contribution statement
combustion temperatures observed are closely related to the location
and/or composition of the coke deposited. Accordingly, the lower Enara Fernandez: Investigation, Visualization, Writing – review &
combustion temperature (<475 ◦ C) is ascribed to the coke deposited on editing. Laura Santamaria: Writing – original draft, Visualization,
Ni metallic sites (encapsulating coke with an amorphous nature). This Writing – review & editing. Maite Artetxe: Writing – original draft,
coke fraction hinders the access of reactants to the active sites due to Ni Conceptualization, Writing – review & editing, Visualization, Supervi­
particle encapsulation, and is therefore the main responsible for catalyst sion, Project administration, Funding acquisition. Maider Amutio:
deactivation. Besides, this type of coke (coke I) is more hydrogenated, Conceptualization, Writing – review & editing, Visualization, Supervi­
has a higher content of aliphatic compounds than the other one at higher sion, Project administration, Funding acquisition. Aitor Arregi: Vali­
temperature and is stemmed from the decomposition of oxygenates dation, Visualization, Writing – review & editing. Gartzen Lopez:
derived from biomass pyrolysis and the re-polymerization of phenolic Conceptualization, Validation, Writing – review & editing, Visualiza­
compounds [58]. The peak located at the higher temperature (coke II) tion, Supervision, Project administration. Javier Bilbao: Writing – re­
has been related to the coke deposited on the support aside from Ni view & editing, Visualization, Supervision, Project administration,
active sites (and therefore, having less influence on catalyst deactiva­ Funding acquisition. Martin Olazar: Writing – review & editing, Visu­
tion), and is composed of highly ordered and condensed aromatic alization, Supervision, Project administration, Funding acquisition.
compounds [94,100,106]. Moreover, the SEM images shown for the
deactivated G90 catalysts in Fig. S2 in the Supplementary Information,
Declaration of Competing Interest
in which no specific morphology of the coke formed is observed, confirm
the results obtained by TPO analysis.
The authors declare that they have no known competing financial
In the case the spent FCC catalyst is used as guard bed, the TPO
interests or personal relationships that could have appeared to influence
profile of the Ni/Al2O3 catalyst reveals a higher proportion of coke I than
the work reported in this paper.
coke II, which is evidence that it promotes the formation of encapsu­
lating coke, thereby hindering the access of reactants to the metallic
sites. Therefore, although coke content has a great influence on catalyst Acknowledgement
deactivation, coke structure and location also play an essential role on
deactivation [94,107]. A minor peak appears at 660 ◦ C in the TPO This work was carried out with the financial support of the grants
profile of the G90 catalyst used without any conditioning bed. As RTI2018-101678-B-I00, RTI2018-098283-J-I00 and PID2019-
aforementioned, G90 catalyst is doped with Ca, and previous studies 107357RB-I00 funded by MCIN/AEI/ 10.13039/501100011033 and
show that this high combustion temperature peak must be ascribed to by “ERDF A way of making Europe” and the grants IT1218-19 and KK-
the decomposition of CaCO3, which is formed by carbonation of the CaO 2020/00107 funded by the Basque Government. Moreover, this proj­
contained in the commercial G90 catalyst [48]. Furthermore, all the ect has received funding from the European Union’s Horizon 2020
conditioning catalysts used in the pyrolysis-reforming process led to a research and innovation programme under the Marie Sklodowska-Curie
small peak at 610 ◦ C, which arose from the thermal cracking of hydro­ grant agreement No 823745.
carbons or oxygenates in the reaction medium [94].
Appendix A. Supplementary data
4. Conclusions
Supplementary data to this article can be found online at https://doi.
Improvements have been carried out in an integrated reaction system org/10.1016/j.fuel.2021.122910.
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